WO2014090609A1 - Utilisation de dithionite de sodium dans un processus de cuisson de cellulose - Google Patents

Utilisation de dithionite de sodium dans un processus de cuisson de cellulose Download PDF

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Publication number
WO2014090609A1
WO2014090609A1 PCT/EP2013/075193 EP2013075193W WO2014090609A1 WO 2014090609 A1 WO2014090609 A1 WO 2014090609A1 EP 2013075193 W EP2013075193 W EP 2013075193W WO 2014090609 A1 WO2014090609 A1 WO 2014090609A1
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WO
WIPO (PCT)
Prior art keywords
digestion
cooking
acid
salt
range
Prior art date
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PCT/EP2013/075193
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German (de)
English (en)
Inventor
Stefan Erren
Dieter SCHÖNHABER
Martin Schachtl
Steffen Fischer
Christian Baeurich
Original Assignee
Basf Se
Technische Universität Dresden
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020157018595A priority Critical patent/KR20150093825A/ko
Priority to CN201380064788.6A priority patent/CN104838065A/zh
Priority to AU2013357649A priority patent/AU2013357649B2/en
Priority to RU2015127891A priority patent/RU2649301C2/ru
Priority to PL13805310T priority patent/PL2931968T3/pl
Priority to BR112015013578-1A priority patent/BR112015013578B1/pt
Priority to MX2015007586A priority patent/MX2015007586A/es
Priority to CA2892725A priority patent/CA2892725A1/fr
Application filed by Basf Se, Technische Universität Dresden filed Critical Basf Se
Priority to ES13805310T priority patent/ES2708216T3/es
Priority to JP2015546933A priority patent/JP6290244B2/ja
Priority to EP13805310.3A priority patent/EP2931968B1/fr
Publication of WO2014090609A1 publication Critical patent/WO2014090609A1/fr
Priority to PH12015501255A priority patent/PH12015501255A1/en
Priority to ZA2015/04934A priority patent/ZA201504934B/en

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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
    • D21C3/00—Pulping cellulose-containing materials
    • 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
    • D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
    • D21C11/08—Deodorisation ; Elimination of malodorous compounds, e.g. sulfur compounds such as hydrogen sulfide or mercaptans, from gas streams
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • 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
    • D21C3/22—Other features of pulping 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
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
    • D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites

Definitions

  • the present invention relates to a process for the production of cellulose from lignocellulosic material by means of sulphite digestion or sulphate pulping, as defined in the claims.
  • cellulose (herein and also referred to in the art as "pulp") from lignocellulosic material, such as wood, are known and described, for example, in U Ilmanns Enzyklopadie der ischen Chemie, 4th Edition, Volume 17, “Paper, Fiber Raw Materials ", Pp. 531-576, Verlag Chemie Weinheim, New York (1979).
  • the cellulose is obtained by chemical digestion processes from the lignocellulosic material, such as wood.
  • chemical digestion methods are, for example, the sulfite pulping used for this purpose or the likewise known sulfate exclusion. Sulphite digestion and sulphate digestion are described, for example, in the above-cited Ullmann literature.
  • lignocellulosic material in both of the above processes is treated as follows to recover cellulose.
  • lignocellulosic material usually wood
  • acidic or neutral medium in the presence of sulphites (salts of sulphurous acid H2SO3)
  • sulphites salts of sulphurous acid H2SO3
  • cooking acid so-called cooking acid
  • magnesium in the form of magnesium oxide (MgO) is used as base which is then converted to dihydrogen sulfite.
  • acidic bisulfite digestion can also cause calcium (Ca), sodium (Na) or Ammonium (NH4) + can be used as a base for the cooking solution, which are then used analogously to magnesium as corresponding oxides or hydroxides.
  • these metals can usually be used analogously, apart from calcium, also in bisulfite digestion.
  • the acid magnesium bisulfite process is the most widely used today.
  • lignocellulosic material usually coniferous wood such as spruce wood, also fir wood and the wood of Hemlocktanne in question.
  • coniferous wood such as spruce wood, also fir wood and the wood of Hemlocktanne in question.
  • deciduous species such as beech, poplar and birch are also suitable.
  • Spruce wood is preferred in the sulphite process.
  • the above-mentioned different types of processes of the sulfite process usually operate at pressures in the range of 0.1 to 10 bar and generally in certain pH ranges.
  • the acid Bisulfitauf gleich a) usually at a pH in the range of 2 to 3
  • the Bisulfitauf gleich b) usually at a pH in the range of 3 to 5
  • the neutral sulphite pulping c) usually at a pH in the range of 6 to 9
  • the alkalisulfite digestion d) usually at a pH of around 1 1.
  • the digestion temperatures differ in the sulfite process.
  • the temperature range of acid Bisulfitauf gleiches a) is usually at 120 ° C to 150 ° C
  • the bisulfite pulping b) usually at 150 ° C to 160 ° C
  • the sodium sulfite pulping c) or even the Alkalisulfitauf gleiches d ) usually at 160 ° C to 180 ° C.
  • the boiling acid of the sulphite process usually contains so-called free sulfur dioxide (SO2), which is present as SO2 and sulphurous acid (hereinafter also "H2SO3") and bound SO2, which is bound to a cation (base) Free SO2 and bound SO2 are in the Generally indicated as total SO 2.
  • the cooking acid of the sulphite process is generally composed as follows: of these, the H2SO3 and the SO2 are assigned to the free SO2 and the M2SO3 to the bound SO2.
  • M is the respective so-called base, example magnesium.
  • the proportion of the base and the SO2 in the cooking acid is given in percent by weight.
  • a cooking acid with a total S02 content of 80 g per liter contains 8% total SO2.
  • the base portion is represented as their respective oxide form such as MgO, CaO, Na 2 O.
  • the preparation of a cooking acid is usually carried out by absorption of SO 2 to water and base carrier.
  • the following equation is intended to serve as an example of the principle of Kochklareher ein the BisulfitaufInstitutes with magnesium as the base (magnesium bisulfite).
  • cellulose is usually made from lignocellulose-containing material, for example, the wood of trees or even of annual plants, for example reeds, grain (straw), sugar cane (bagasse) , Corn won.
  • woodchips of the lignocellulose-containing material for example wood or comminuted plant stems
  • pressure vessels for several hours, for example 3 to 6 hours, at elevated pressure, for example in the range from 7 to 10 bar, usually in a mixture of sodium hydroxide solution (aqueous NaOH ), Sodium sulfide
  • Na 2 S sodium sulfate
  • Na 2 CO 3 optionally sodium carbonate
  • black liquor soluble alkali lignin
  • Cellulose can be separated from lignin with the abovementioned sulphite and sulphate processes, although it is still desirable to increase the pulp yield, in particular while at the same time keeping the lignin content of the pulp low.
  • the kappa number is a measure of the lignin content of the pulp.
  • pulp components
  • pulp mainly hemicelluloses
  • a disadvantage of pulping by the sulphate process is the formation of malodorous substances such as mercaptans, in particular methylmercaptan.
  • the addition of sodium dithionite (hereinafter also "Na 2 S 2 O 4”) in the pulp production process is basically known from the following literature.
  • G. G. Jayme and Woerner describe an alkaline sulfite pulping of spruce wood at 170 ° C, 24 hours, in 100 cm 3 of the digestion solution 3 g NaOH, 1, 56 g of sodium dithionite (Na2S20 4) and 4.69 g of Na2S03 were included.
  • G. Jayme, G. Wörner, paper, Volume 6, Issue 1 1, p 220-222 (1952) In it, relatively large amounts of sodium dithionite, based on the wood to be treated, are described indirectly by means of the quantity of chemicals and the "lye ratio" (p. 221, left-hand column “Zahlentafel" and the subsequent paragraph).
  • the object of the present invention was to obtain a high pulp yield with a simultaneous low lignin content of the pulp in the digestion of lignocellulose-containing material, wherein the formation of malodorous emissions in particular in the sulphate process should be reduced.
  • Lignocellulosic material herein is any material, preferably from nature, containing lignin and cellulose.
  • Preferred lignocellulose-containing material are woods, including shredded woods, such as wood sections from sawmills. Suitable woods are softwoods, preferably spruce or pine or hardwoods such as beech.
  • lignocellulose-containing material is understood here to include grasses and annual plants, for example straw, reed, esparto grass, bamboo and bagasse, these usually not being digested by the sulphite process but preferably by alkaline digestion or the neutral sulphite process.
  • Sulphite pulping and sulphate pulping for the recovery of cellulose are known and are described in the beginning and in more detail in Ullmanns Enzyklopadie der ischen Chemie, 4th Edition, Volume 17, “Paper, Fiber Raw Materials", Verlag Chemie Weinheim, New York (1979) pp. 535-549 in chapter 1.4].
  • Salts of dithionic acid herein are all metal salts or substituted (NFV) or unsubstituted (NhV) ammonium salts of this acid.
  • Highly suitable salts of the dithionic acid are the alkali metal salts, alkaline earth metal salts, salts of the metals of group 12 of the Periodic Table of the Elements, and ammonium (NH 4 + ) salts.
  • Preferred salts of the dithionic acid are sodium dithionite (Na 2 S 2 O 4), potassium dithionite (K 2 S 2 O 4), calcium dithionite (CaS 2 O 4 ), zinc dithionite (ZnS 2 O 4 ), ammonium dithionite ((NhU) C).
  • Salts of dithionic acid including those preferred above, of course also include those individuals containing water of crystallization and / or additives, the latter for example for stabilization.
  • a well-suited dithionic acid salt is the sodium dithionite product, which is marketed by BASF SE as Blankit® or Blankit®S.
  • the digestion temperature in sulfite digestion is usually in the range of 100 ° C to 160 ° C.
  • a suitable sulphite digestion for the process according to the invention is the bisulphite process with Mg (HSC "3) 2 as a component of the cooking acid, which is described in more detail below.
  • Mg HSC "3) 2
  • lignocellulose-containing material coniferous woods, preferably spruce wood, are preferably used as woodchips
  • the amount used is calculated as dry matter (otro), in order to be able to determine, for example, the yield of pulp
  • MgCO-3 "MgCO-3" in the water and then introducing SO 2.
  • the introduction of SO 2 is usually carried out until a clear solution has formed which has a pH value for example, of about 3.8. Usually, approximately the entire dissolved substance is present as Mg (HSO) 2.
  • the pH would continue to decrease as the proportion of sulphurous acid increases.
  • the cooking of the so-called lignocellulosic material with the cooking acid takes place in the usual digesters, discontinuous or continuous. The total cooking time is in the range of 400 to 600 minutes.
  • a temperature profile is used for cooking in the bisulfite process referred to herein, preferably the bisulfite process with Mg (HSOs) 2 as a component of the cooking acid.
  • a well-suited temperature profile is as follows. 1 . Phase: Heating from a temperature in the range of 15 ° C to 30 ° C to a temperature in the range of 100 to 1 10 ° C, within 60 to 120 minutes.
  • 2nd phase Stability for 60 to 90 minutes at a temperature in the range of
  • 3rd phase heating up from a temperature in the range of 100 to 1 10 ° C, up to a temperature in the range of 150 to 160 ° C, within 45 to 90 minutes.
  • 5th phase Cooling to a temperature in the range of 100 to 90 ° C.
  • the salt of dithionous acid preferably sodium dithionite (Na2S20 4) Calciumdithionit (CaS20 4), zinc dithionite (ZnS20 4), particularly preferably sodium dithionite, in the mixture of lignocellulosic material, preferably of wood chips from spruce wood, and the cooking acid, as described above in an amount in the range from 0.1 to 4.0% by weight, preferably from 1.0 to 2.0% by weight, based in each case on the oven-dried lignocellulose-containing material, preferably the oven-dried wood chips from spruce wood.
  • the dosage of the salt of the dithionic acid at any time during the cooking process or before it happen.
  • the following dosage variants are preferred:
  • lignocellulosic material are woods, such as deciduous or preferably coniferous wood, particularly preferably spruce wood, preferably used as wood chips.
  • the mixture known for the sulphate process from sodium hydroxide solution (aqueous NaOH), sodium sulphate (Na 2 S) and sodium sulphate (hereinafter also “Na 2 SO 4") and optionally sodium carbonate (hereinafter also “Na 2 CO 3”), which contains the salt the dithionic acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, in an amount in the range of 0.1 to 4 wt .-% based on the amount of oven-dry lignocellulose-containing material was added.
  • sodium hydroxide solution aqueous NaOH
  • Na 2 S sodium sulphate
  • Na 2 SO 4 sodium sulphate
  • Na 2 CO 3 optionally sodium carbonate
  • the cooking liquor for sulphate pulping usually contains NaOH and sodium sulphide (Na2S) as effective cooking chemicals.
  • NaOH sodium sulphide
  • the necessary concentration of these substances in the cooking liquor is usually dependent on the so-called "liquor ratio.”
  • this liquor ratio is understood as meaning mass fractions of cooking liquor in relation to mass fractions of lignocellulose-containing material, preferably wood (oven-dry (otro)) usually depending on the filling density of wood in the digester, generally in the range from 4: 1 to 4.5: 1, for example 4.2: 1.
  • the concentration of active alkali in the cooking liquor is in the range from 45 to 60 g / l.
  • the content of sodium sulfide (Na2S) in the total effective alkali is the sulfidity (expressed in%). This is usually in the range of 30 to 38%, for example 30%.
  • the cooking liquor for the sulphate process according to the invention contains a salt of the dithionic acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, in an amount in the range from 0.1 to 4% by weight, based on the amount of oven-dried lignocellulose-containing Material.
  • a salt of the dithionic acid preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, in an amount in the range from 0.1 to 4% by weight, based on the amount of oven-dried lignocellulose-containing Material.
  • the pH of the cooking liquor for the sulphate process according to the invention is usually about 14 at the beginning of the cooking process.
  • the cooking of the lignocellulosic material with the cooking liquor for the sulfate process according to the invention takes place in the usual digesters discontinuous or continuous.
  • the total cooking time for the sulfate process of the invention is usually in the range of 200 to 400 minutes, preferably 240 to 300 minutes.
  • the boiling temperature for the sulfate process of the invention is in the range of 160 to 185 ° C, for example at 170 ° C.
  • the salt of the dithionic acid preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, more preferably sodium dithionite, is used in the sulphate process of the invention for mixing the lignocellulosic material and the cooking liquor in an amount ranging from 0.1 to 4.0 wt. %, preferably 1.0 to 2.0% by weight, based in each case on the oven-dried lignocellulose-containing material.
  • the dosage of the salt of the dithionic acid can be done at any time during the cooking process of the sulphate process according to the invention.
  • the salt of the dithionic acid is preferably added in the impregnation phase, the final phase of the digestion or in the main phase of the digestion of the sulphate process according to the invention, particularly preferably in the final phase of the digestion or in the main phase of the digestion of the sulphate process according to the invention.
  • the process according to the invention for the production of cellulose from lignocellulose-containing material by means of sulfite pulping or sulfate pulping produces pulp in good yield with good delignification of the lignocellulose-containing material. The whiteness of the unbleached pulp is improved.
  • the addition of a salt of the dithionic acid in the sulfate process of the invention reduces the concentration of malodorous substances, preferably mercaptans in the exhaust gas of the sulfate cooking process. Examples
  • Spruce wood chips pre-sorted and pre-dried in the room air for 2 to 3 days before cooking water content in the range of 23.4 to 33.2 wt .-%, on average about 30 wt .-%
  • 3200 g (oven-dry (otro) calculated) spruce chips with an original water content as described in A) and 16 liters of the cooking acid from B) were filled in the discontinuous cooker with a capacity of 25 liters, according to a quantitative ratio of cooking acid: otro wood of 5: 1.
  • the cooker had an acid circulation and electric jacket heating as well as a temperature controller, manometer, temperature sensor and pH electrode, as well as connected EDP system.
  • 3rd phase 60 min heating-up time from 105 ° C to final cooking temperature 155 ° C
  • the total digestion time was 510 min (8 h 30 min).
  • the pressure in the digester was 8 to 9 bar at the end of the final cooking time.
  • Sodium dithionite (Blankit®S from BASF SE) was dissolved in water by metering pump within 10 min in the digester added to the mixture and that 32 g of pure Na2S20 4 (1 wt .-% Na2S20 4 based on otro counted wood used) or 64 g pure Na2S20 4 (2 wt .-% Na2S20 4 based on used otro counted wood).
  • Sodium dithionite addition times were, per experiment, as follows:
  • experiment W 16 the chips were impregnated immediately before digestion with such an amount of aqueous solution of sodium dithionite (Blankit®S BASF SE), corresponding to 1 wt .-% pure Na 2 S 20 4 based on otro computed timber used.
  • the pulp was removed, mixed with water and defibered with a stirrer. The shredded pulp was filled into a sieve, washed with water and dehydrated in a centrifuge.
  • Acceptance of raw material means amount of pulp received (without coarse or splinter content) in relation to the wood used; It was determined by weighing and dry content measurement.
  • the kappa number indicates the hardness of the pulp and was determined in accordance with ISO 302. Put simply, when determining the kappa number in an aqueous pulp suspension in an acidic medium under defined conditions, the potassium permanganate consumption (KMnCM consumption) is measured. The higher the lignin content in the pulp, the higher the consumption of potassium permanganate and thus the kappa number. The higher the kappa number, the higher the residual lignin content of the pulp, the harder is the pulp in general.
  • Whiteness means remission at 457 nm and was determined on the Datacolor Elrepho® instrument according to ISO 2470.
  • the viscosity determination was carried out according to ISO 5351/1 (International Standard ISO 5351/1, Cellulose in dilute Solutions - Determination of liming viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) Solution, First edition 1981 -12 -01).
  • ISO 5351/1 International Standard ISO 5351/1, Cellulose in dilute Solutions - Determination of liming viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) Solution, First edition 1981 -12 -01.
  • a solution of cellulose in copper ethylenediamine solution is prepared.
  • the concentration of the solvent is fixed.
  • the concentration of cellulose in the solution should be determined according to the sample used in the determination.
  • the throughput time of both the solvent and the cellulose solution is measured by a capillary viscometer at 25 ° C.
  • the calculation of the intrinsic viscosity is based on the results of the determination and the known concentration of the cellulose solution according to the Martin equation.
  • the measurement was carried out according to the alternative A of the determination method (International Standard ISO 5351/1, Cellulose in dilute Solutions - Determination of liming viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) Solution, First edition 1981 -12 -01). It is carried out at low cellulose concentration and used for the measurement of the transit times of solvent and cellulose solution, the same capillary.
  • Lignocellulose-containing material A) Lignocellulose-containing material:
  • the cooking liquor was prepared by adding commercial laboratory chemicals in water from caustic soda (NaOH) and sodium sulfide (Na2S). The amount of chemicals used was calculated so that an alkali ratio of 23% was used at a sulphidity of 20%.
  • Table 4 shows the yield of the accepts and the kappa number. Table 4: Cooking No. Auxiliary agent addition [1] Acceptance of raw material% Kappa number
  • Acceptance yield and kappa number are as defined under (I) above.
  • exhaust gases gases from the digester
  • exhaust samples were taken at different times with a tracer pump
  • concentration of methylmercaptan in these samples was measured with methylmercaptan-specific gas detector tubes.
  • the methylmercaptan concentration is highest.
  • the use of Na2S20 4 leads to a decrease of the methyl mercatane in the exhaust gas.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne un procédé de fabrication de cellulose à partir de matière contenant de la lignocellulose par désagrégation de sulfite ou désagrégation de sulfate en présence d'un sel de l'acide dithionique, caractérisé en ce que le sel de l'acide dithionique est utilisé dans une quantité de l'ordre de 0,1 à 4,0 % en poids par rapport à la quantité de matière contenant de la lignocellulose séchée au four.
PCT/EP2013/075193 2012-12-12 2013-12-02 Utilisation de dithionite de sodium dans un processus de cuisson de cellulose WO2014090609A1 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
MX2015007586A MX2015007586A (es) 2012-12-12 2013-12-02 Uso de ditionito de sodio en un proceso de elaboracion de pulpa de celulosa.
AU2013357649A AU2013357649B2 (en) 2012-12-12 2013-12-02 Use of sodium dithionite in a cellulose pulping process
RU2015127891A RU2649301C2 (ru) 2012-12-12 2013-12-02 Применение дитионита натрия в процессе варки целлюлозы
PL13805310T PL2931968T3 (pl) 2012-12-12 2013-12-02 Zastosowanie ditioninu sodu w sposobie warzenia masy celulozowej
BR112015013578-1A BR112015013578B1 (pt) 2012-12-12 2013-12-02 método para produção de celulose a partir de material contendo lignocelulose
KR1020157018595A KR20150093825A (ko) 2012-12-12 2013-12-02 셀룰로스 펄프화 공정에서 나트륨 다이티오나이트의 용도
CA2892725A CA2892725A1 (fr) 2012-12-12 2013-12-02 Utilisation de dithionite de sodium dans un processus de cuisson de cellulose
CN201380064788.6A CN104838065A (zh) 2012-12-12 2013-12-02 连二亚硫酸钠在纤维素制浆方法中的用途
ES13805310T ES2708216T3 (es) 2012-12-12 2013-12-02 Uso de ditionito de sodio en el proceso de despulpado de celulosa
JP2015546933A JP6290244B2 (ja) 2012-12-12 2013-12-02 セルロース蒸解プロセスにおける亜ジチオン酸ナトリウムの使用
EP13805310.3A EP2931968B1 (fr) 2012-12-12 2013-12-02 Utilisation de dithionite de sodium dans un processus de cuisson de cellulose
PH12015501255A PH12015501255A1 (en) 2012-12-12 2015-06-03 Use of sodium dithionite in a cellulose pulping process
ZA2015/04934A ZA201504934B (en) 2012-12-12 2015-07-09 Use of sodium dithionite in a cellulose pulping process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12196636 2012-12-12
EP12196636.0 2012-12-12

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WO2014090609A1 true WO2014090609A1 (fr) 2014-06-19

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EP (1) EP2931968B1 (fr)
JP (1) JP6290244B2 (fr)
KR (1) KR20150093825A (fr)
CN (1) CN104838065A (fr)
AR (1) AR093929A1 (fr)
AU (1) AU2013357649B2 (fr)
BR (1) BR112015013578B1 (fr)
CA (1) CA2892725A1 (fr)
CL (1) CL2015001406A1 (fr)
ES (1) ES2708216T3 (fr)
MX (1) MX2015007586A (fr)
PH (1) PH12015501255A1 (fr)
PL (1) PL2931968T3 (fr)
PT (1) PT2931968T (fr)
RU (1) RU2649301C2 (fr)
TW (1) TWI607041B (fr)
WO (1) WO2014090609A1 (fr)
ZA (1) ZA201504934B (fr)

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PL2931968T3 (pl) 2019-04-30
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KR20150093825A (ko) 2015-08-18
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AU2013357649B2 (en) 2017-06-08
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ES2708216T3 (es) 2019-04-09
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