EP0578305B1 - Verfahren zur Delignifizierung von chemischen Zellstoffen - Google Patents

Verfahren zur Delignifizierung von chemischen Zellstoffen Download PDF

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Publication number
EP0578305B1
EP0578305B1 EP93201887A EP93201887A EP0578305B1 EP 0578305 B1 EP0578305 B1 EP 0578305B1 EP 93201887 A EP93201887 A EP 93201887A EP 93201887 A EP93201887 A EP 93201887A EP 0578305 B1 EP0578305 B1 EP 0578305B1
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EP
European Patent Office
Prior art keywords
acid
peroxyacid
process according
treatment
delignification
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Revoked
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EP93201887A
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English (en)
French (fr)
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EP0578305A1 (de
Inventor
Johan Devenyns
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Solvay Chimie SA
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Solvay Interox SA
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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
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/166—Bleaching ; Apparatus therefor with per compounds with peracids
    • 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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents

Definitions

  • the invention relates to a method of delignification of a chemical paper pulp.
  • This first step delignifying is traditionally carried out by treating the dough unbleached by chlorine in an acid medium or by a chlorine association - chlorine dioxide, in mixture or in sequence, so as to cause a reaction with the residual lignin in the pulp and give rise to chlorolignins which can be extracted of the paste by solubilization of these chlorolignins in the medium alkaline in a subsequent processing step.
  • the invention aims to remedy the drawbacks of the methods known by providing a process which achieves delignification effective unbleached chemical pulp which allows obtaining pasta with high intrinsic qualities in a wide temperature range.
  • the invention relates to a method for improving the selectivity of the delignification of a dough chemical paper using an organic peroxyacid that treating the unbleached dough from the cooking operation by an aqueous solution of this organic peroxyacid in the presence of a stabilizer of said peroxyacid comprising at least one compound selected from the class of phosphonic acids and their salts, the pH of the aqueous peroxyacid solution in contact with the dough being acidic and preferably from 3.5 to 6.5.
  • chemical paper pulp the pulp which has already undergone a delignifying treatment in the presence of chemical reagents such as sodium sulfide in alkaline medium (kraft or sulfate cooking), sulfur dioxide or a metallic salt of sulfurous acid in an acid medium (cooking with sulfite or bisulfite).
  • chemical reagents such as sodium sulfide in alkaline medium (kraft or sulfate cooking), sulfur dioxide or a metallic salt of sulfurous acid in an acid medium (cooking with sulfite or bisulfite).
  • pulps called in the literature "semi-chemical pulps” such as those where the cooking was carried out using a salt of sulfurous acid in neutral medium (cooking with neutral sulfite, also called NSSC cooking), as well as the pastes obtained by processes using solvents, such as the ORGANOSOLV, ALCELL (R) , ORGANOCELL (R) and ASAM pastes described in Ullmann's Encyclopedia of Industrial Chemistry , 5th Edition, Vol A18, 1991, pages 568 and 569.
  • solvents such as the ORGANOSOLV, ALCELL (R) , ORGANOCELL (R) and ASAM pastes described in Ullmann's Encyclopedia of Industrial Chemistry , 5th Edition, Vol A18, 1991, pages 568 and 569.
  • the invention is particularly intended for pasta which has undergone kraft cooking.
  • All types of wood used for production of chemical pulps suitable for processing of the process of the invention and, in particular those used for kraft pulp, i.e. softwood such as, for example, various species of pines and firs and deciduous woods such as, for example, beech, oak, eucalyptus and charm.
  • the peroxyacid organic is usually selected from acid performique and aliphatic carboxylic peroxyacids comprising a single percarboxylic group and a chain saturated linear or branched alkyl of less than 11 atoms carbon. Chain aliphatic carboxylic peroxyacids linear saturated alkyl with less than 6 carbon atoms are preferred. Examples of such peroxyacids are acid peracetic, perpropanoic acid, n-perbutanoic acid and n-perpentanoic acid. Peracetic acid is particularly preferred because of its efficiency and relative simplicity of its preparation methods.
  • the peroxyacid organic is selected from diperoxycarboxylic acids comprising a linear or branched alkyl chain of less than 16 carbon atoms and two percarboxylic groups substituted on carbon atoms located in position alpha-omega relative to each other.
  • diperoxycarboxylic acids comprising a linear or branched alkyl chain of less than 16 carbon atoms and two percarboxylic groups substituted on carbon atoms located in position alpha-omega relative to each other.
  • Examples of such peroxyacids are 1,6-diperoxyhexanedioic acid, acid 1,8-diperoxyoctanedioic acid and 1,10-diperoxydecanedioic acid, and 1,12-diperoxydodecanedioic acid.
  • the organic peroxyacid is selected from peroxyacids aromatics comprising at least one percarboxylic group by benzene nucleus.
  • peroxyacids aromatics which have only one percarboxylic group by benzene nucleus.
  • An example of such an acid is acid peroxybenzoic.
  • Another variant of the process according to the invention consists in choose an organic peroxyacid substituted by one or more halogen atoms or any other functional substituent organic.
  • any other organic functional substituent intends to designate a functional group such as the group carbonyl (ketone, aldehyde or carboxylic acid), the group alcohol, nitrogen-containing groups such as nitrile, nitro, amine and amide groups, the groups containing sulfur such as the sulfo and mercapto groups.
  • the peroxyacid used can be an aqueous solution commercial comprising at least 10% by weight of peroxyacid, equilibrium with at least 12% by weight of organic acid corresponding and at least 1.5% by weight of hydrogen peroxide most often in the presence of a small amount of catalyst in the form of at least 0.3% by weight of a strong acid, usually an inorganic acid.
  • An example of composition commercial organic peroxyacid which is well suited is a concentrated aqueous solution of peracetic acid comprising about 34% by weight of peracetic acid, about 44% by weight acetic acid, about 5% by weight of hydrogen peroxide and about 1% by weight of sulfuric acid.
  • the peroxyacid can indifferently be used at the state of an aqueous solution of peroxyacid or in the form an ammonium, alkali metal, or alkaline earth metal salt of this peroxyacid.
  • the peroxyacid treatment according to the invention can take place over a wide range of temperatures.
  • the process according to the invention is particularly well suitable for the use of high temperatures, i.e. at least minus 50 ° C and preferably at least 75 ° C.
  • the treatment is carried out with peroxyacid organic at atmospheric pressure.
  • the duration of this treatment depends on the temperature and the type of wood used prepare the dough, as well as the efficiency of the baking which has preceded. Duration between approximately 120 minutes and about 360 minutes is fine.
  • the pH of the treatment stage with peroxyacid is in the acid pH range. In practice, we prefer to fix the pH at a value of at least 3.5. It will also be most often not to exceed a pH value of 6.5.
  • the treatment according to the invention can be done in any type of suitable equipment for the treatment of paper pulp using acid reagents.
  • the retention tank for the unbleached dough present in all bleaching and playing facilities the role of buffer tank between the wood cooking unit and the dough bleaching unit is particularly suitable for carrying out the method according to the invention.
  • the dough can thus be treated there during its storage without requiring the investment of an expensive specific device.
  • the consistency of the dough in the processing step with the organic peroxyacid will generally be chosen to be at least 5% of dry matter and preferably at least 10% matter dry. Most often, the consistency will not exceed 40% of dry matter and preferably not 30%.
  • the amount of peroxyacid organic used is chosen according to the rate of residual lignin in the dough as well as the average duration of the treatment. Generally, amounts of at least 0.1% and, of preferably at least 1% by weight of peroxyacid relative to dry dough is fine. Most often, we will use a quantity of peroxyacid not exceeding 10% by weight per compared to dry dough and preferably not more than 5% of this weight.
  • the stabilizer used belongs to the class of phosphonic acids and their salts.
  • it will be selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDPA), ethylenediaminetetra acid (methylenephosphonic) (EDTMPA), diethylenetriaminepenta acid (methylenephosphonic) (DTMPA), triethylenetetraminehexa acid (methylenephosphonic) (TTHMPA), acid pentaethylenehexamineocta (methylenephosphonic) (PHOMPA), cyclohexanediaminetetra (methylenephosphonic acid) (CDTMPA) and nitrilotri (methylenephosphonic) acid (NTMPA).
  • HEDPA 1-hydroxyethylidene-1,1-diphosphonic acid
  • EDTMPA ethylenediaminetetra acid
  • DTMPA diethylenetriaminepenta acid
  • TTHMPA triethylenetetraminehexa acid
  • PHOMPA acid pentaethylenehexamineo
  • the total amounts of stabilizer to be used depend on the type of wood and the cooking process used. In as a general rule, it is recommended to implement a amount of stabilizer of at least 0.05% by weight relative to the dry matter and preferably at least 0.2% by weight. Amounts of stabilizer not exceeding 3% by weight per dry matter and preferably not more than 2% by weight are generally sufficient.
  • Treatment with organic peroxyacid according to the invention can also be performed in the presence of several stabilizers comprising at least one phosphonic acid or one of its salts and / or sodium silicate. It can also be interesting to associate with at least one phosphonic acid and / or with the silicate of sodium a water-soluble magnesium salt such as sulphate magnesium.
  • washing or pretreatment acid decontaminant is also carried out in the presence of an agent complexing metal ions.
  • mixtures of strong inorganic acids mentioned above with acids organic from the class of aminopolycarboxylic acids or aminopolyphosphonic acid or their alkali metal salts are particularly suitable.
  • acids suitable aminopolycarboxylics are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CDTA) and acid nitrilotriacetic (NTA).
  • Diethylenetriaminepentaacetic acid (DTPA) is preferred.
  • aminopolyphosphonic acids are diethylenetriaminepenta (methylenephosphonic acid) (DTMPA), ethylenediaminetetra acid (methylenephosphonic) (EDTMPA), cyclohexanediaminetetra acid (methylenephosphonic) (CDTMPA) and nitrilotri acid (methylenephosphonic). DTMPA is preferred.
  • DTMPA diethylenetriaminepenta
  • EDTMPA ethylenediaminetetra acid
  • CDTMPA cyclohexanediaminetetra acid
  • nitrilotri acid methylenephosphonic
  • DTMPA is preferred.
  • the amounts of complexing agent to be used depend on the effectiveness of the complexing agent selected and the metal content of the pulp to be treated. In practice, we put generally at least 0.01% by weight of agent complexing compared to dry dough and, more often, to minus 0.05%. Similarly, we generally do not exceed 1% in weight of complexing agent relative to the dry paste and, most often not 0.25%.
  • the operating conditions of the decontaminating pretreatment acid are not critical. They must be determined in each particular case depending on the type of pulp and the apparatus in which the treatment is carried out. Of a in general, the choice of acid and the quantity used to impose on the medium a pH below 7, for example between approximately 1 and approximately 6.5. PH especially advantageous are those between about 3.0 and about 6.0. Temperature and pressure are not critical, ambient temperature and atmospheric pressure suitable generally fine. The duration of the pretreatment can vary within large proportions depending on the type of equipment used, the choice acid, temperature and pressure, for example from About 15 minutes to several hours.
  • delignification by means of chemical reagents we mean both reagents non-oxidizing agents such as an alkaline reagent such as hydroxide or sodium, magnesium or calcium carbonate as reactants oxidizers in an acid medium such as chlorine, dioxide chlorine, ozone, an inorganic peroxyacid such as acid peroxymonosulfuric, hydrogen peroxide in an acid medium, and oxidizing reagents in an alkaline medium such as peroxide of hydrogen in an alkaline medium, sodium hypochlorite or calcium, molecular oxygen or ozone. It is also possible to combine two or more in a single treatment step of these reagents.
  • this step with hydrogen peroxide in an alkaline medium can advantageously be done using hydrogen peroxide which generally accompanies peroxyacid: after treatment with the peroxyacid, an alkali is added to the paste and then proceeds with bleaching with hydrogen peroxide, without perform intermediate washing between steps with peroxyacid and alkaline hydrogen peroxide. If necessary, we will do supplementing with additional hydrogen peroxide so as to reach the total quantity required to achieve a effective whitening.
  • the process according to the invention applies to the delignification and bleaching of all types of dough chemical. It is well suited for delignifying and blanching pasta kraft and sulfite pastes. It is particularly good suitable for processing kraft pasta.
  • a sample of baked hardwood pulp kraft (initial whiteness 33.7 ° ISO measured according to the standard ISO 2470, kappa index 12.4 measured according to the SCAN C1-59 standard and degree of polymerization 1370 expressed in number of units glucose and measured according to SCAN C15-62) has been delignified by means of a two-step sequence comprising a first step with peracetic acid (Paa) and a second step alkaline extraction with sodium hydroxide. The dough has been washed with demineralized water between the two stages.
  • Paa peracetic acid
  • the peracetic acid used was an equilibrium aqueous solution containing 240 g / l of CH 3 CO 3 H, 420 g / l of CH 3 COOH, 100 g / l of H 2 O 2 and 7 g / l of H 2 SO 4 .
  • the treated dough was made whiteness, kappa index and degree of determination polymerization.
  • stage E peracetic acid stage
  • stage E stage with Na hydroxide
  • Examples 1R and 2R were reproduced, replacing the stabilizer DTPA or EDTA with 0.5 g of the heptasodium salt of diethylenetriaminepenta (methylenephosphonic acid) (DTMPNa 7 ) per 100 g of dry paste.
  • DTMPNa 7 diethylenetriaminepenta
  • a softwood pulp having undergone kraft cooking with a whiteness of 30.5 ° ISO, a kappa index of 26.7 and a degree of polymerization of 1510 was bleached using a sequence completely free of chlorine reagents in 4 steps 0 QP Paa under the following operating conditions: 1st stage: oxygen stage (0) pressure, bar 5.5 NaOH content, g / 100 g dry paste 4.0 MgSO 4 .7H 2 O content, g / 100 g dry paste 0.5 temperature, degrees C 120 duration, min 60 consistency,% by weight of dry matter 14 2nd stage: stage with a sequestering acid DTPA content 40%, g / 100 g of dry paste 0.5 H 2 SO 4 for initial pH of 5.00 temperature, degrees C 55 duration, min 30 consistency,% by weight of dry matter 4.0 3rd stage: H 2 O 2 stage (P) H 2 O 2 content , g / 100 g of dry paste 2.0 NaOH content, g / 100 g of dry paste 1.5 temperature, degrees C
  • a sample of kraft softwood pulp (initial whiteness 30.5 ° ISO measured according to ISO 2470, kappa index 26.7 measured according to standard SCAN C1-59 and degree of polymerization 1510 expressed in number of glucose units and measured according to the standard SCAN C15-62) has been delignified using a two-part sequence stages comprising a first stage with peracetic acid (Paa) and a second stage of alkaline extraction with sodium hydroxide. The dough was washed with demineralized water between the two stages.
  • Paa peracetic acid
  • the peracetic acid used was an equilibrium aqueous solution containing 240 g / l of CH 3 CO 3 H, 420 g / l of CH 3 COOH, 100 g / l of H 2 O 2 and 7 g / l of H 2 SO 4 .
  • the treated dough was made whiteness, kappa index and degree of polymerization determinations.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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Claims (10)

  1. Verfahren zur Verbesserung der Selektivität der Delignifizierung eines chemisches Zellstoffs mittels einer organischen Peroxysäure, gemäß dem man den ungebleichten Zellstoff, der aus dem Kochvorgang hervorgeht, mit einer wäßrigen Lösung dieser organischen Peroxysäure in Gegenwart eines Stabilisators für besagte Peroxysäure behandelt, dadurch gekennzeichnet, daß der Stabilisator wenigstens eine Verbindung umfaßt, die unter der Klasse der Phosphonsäuren und deren Salzen ausgewählt ist, und daß der pH-Wert der wäßrigen Peroxysäurelösung, die mit dem Zellstoff in Kontakt steht, sauer und vorzugsweise 3,5 bis 6,5 ist.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die organische Peroxysäure Peressigsäure ist.
  3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Behandlung mit der organischen Peroxysäure bei einer Temperatur zwischen 50 und 98 °C ausgeführt wird.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Phosphonsäure Diethylentriaminpenta(methylenphosphonsäure) ist.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Stabilisator außerdem Natriumsilicat umfaßt.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Stabilisator für die Peroxysäure eine Vereinigung einer Phosphonsäure oder eines ihrer Salze mit einem wasserlöslichen Magnesiumsalz ist.
  7. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man vor der Behandlung mit der organischen Peroxysäure wenigstens einen Waschvorgang oder einen Behandlungsschritt mit einer sauren wäßrigen Lösung durchführt.
  8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man zwischen den Kochvorgang und die Behandlung mit der Peroxysäure einen oder mehrere Schritte zur Delignifizierung des Zellstoffs mittels chemischer Reagentien einschiebt.
  9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man der Behandlung mit der Peroxysäure einen Bleichschritt mit Wasserstoffperoxid in alkalischem Medium folgen läßt.
  10. Anwendung des Verfahrens gemäß einem der Ansprüche 1 bis 9 auf die Delignifizierung und auf das Bleichen von Kraft-Zellstoffen, Sulfit-Zellstoffen und Zellstoffen, die durch Kochverfahren unter Verwendung von Lösungsmitteln erhalten wurden.
EP93201887A 1992-07-06 1993-06-29 Verfahren zur Delignifizierung von chemischen Zellstoffen Revoked EP0578305B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9200627 1992-07-06
BE9200627A BE1006057A3 (fr) 1992-07-06 1992-07-06 Procede pour la delignification d'une pate a papier chimique.

Publications (2)

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EP0578305A1 EP0578305A1 (de) 1994-01-12
EP0578305B1 true EP0578305B1 (de) 1998-03-04

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EP93201887A Revoked EP0578305B1 (de) 1992-07-06 1993-06-29 Verfahren zur Delignifizierung von chemischen Zellstoffen

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US (1) US5552018A (de)
EP (1) EP0578305B1 (de)
JP (1) JPH06166976A (de)
AR (1) AR247259A1 (de)
AT (1) ATE163697T1 (de)
AU (1) AU654624B2 (de)
BE (1) BE1006057A3 (de)
BR (1) BR9302765A (de)
CA (1) CA2099513A1 (de)
DE (1) DE69317169T2 (de)
ES (1) ES2115719T3 (de)
FI (1) FI933104A (de)
NZ (1) NZ248028A (de)
SI (1) SI9300363A (de)
SK (1) SK70393A3 (de)

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EP0801170A1 (de) * 1996-04-12 1997-10-15 Chemoxal Sa Verfahren zur Delignifizierung und/oder Bleichen eines Papierzellstoffs
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WO2013096045A1 (en) 2011-12-19 2013-06-27 E. I. Du Pont De Nemours And Company Perhydrolase variants providing improved specific activity in the presence of surfactant
BR112014024207B1 (pt) 2012-03-30 2022-04-05 E.I. Du Pont De Nemours And Company Processo para a produção de um ácido peroxicarboxílico, composição e sistema de geração e fornecimento de perácido
EP2831226B1 (de) 2012-03-30 2021-11-24 DuPont US Holding, LLC Enzyme zur herstellung von persäure
BR112014024216B1 (pt) 2012-03-30 2022-04-05 E.I. Du Pont De Nemours And Company Processo para a produção de um ácido peroxicarboxílico, composição e sistema de geração e fornecimento de perácido
JP6574376B2 (ja) 2012-03-30 2019-09-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 過酸生成に有用な酵素
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ES2115719T3 (es) 1998-07-01
JPH06166976A (ja) 1994-06-14
SI9300363A (en) 1994-03-31
AR247259A1 (es) 1994-11-30
DE69317169D1 (de) 1998-04-09
FI933104A0 (fi) 1993-07-06
BR9302765A (pt) 1994-02-08
NZ248028A (en) 1995-12-21
AU654624B2 (en) 1994-11-10
FI933104A (fi) 1994-01-07
US5552018A (en) 1996-09-03
DE69317169T2 (de) 1998-10-08
AU4170693A (en) 1994-01-13
EP0578305A1 (de) 1994-01-12
BE1006057A3 (fr) 1994-05-03
ATE163697T1 (de) 1998-03-15
CA2099513A1 (fr) 1994-01-07
SK70393A3 (en) 1994-05-11

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