EP0940498B1 - Method for treatment of pulp - Google Patents

Method for treatment of pulp Download PDF

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Publication number
EP0940498B1
EP0940498B1 EP99103920A EP99103920A EP0940498B1 EP 0940498 B1 EP0940498 B1 EP 0940498B1 EP 99103920 A EP99103920 A EP 99103920A EP 99103920 A EP99103920 A EP 99103920A EP 0940498 B1 EP0940498 B1 EP 0940498B1
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EP
European Patent Office
Prior art keywords
chlorine dioxide
pulp
treatment
stage
treatment step
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP99103920A
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German (de)
English (en)
French (fr)
Other versions
EP0940498A1 (en
Inventor
Tapani Vuorinen
Sari Juutilainen
Aki Vilpponen
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Andritz Oy
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Andritz Oy
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching 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
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites

Definitions

  • the present invention relates to a method for treatment of pulp in an alkaline pulping process of chemical pulp during which process pulp is treated in a chlorine dioxide stage including an acid treatment at a temperature of over 80°C.
  • Pulp mills have recently attempted to abandon the use of elementary chlorine, and partly also chlorine dioxide, the reasons for this being both aspects of environmental protection and market factors. Disadvantages caused by elementary chlorine include both noticeable malodorous gaseous emissions and liquid effluents from chemical pulp mills into water svstems. Liquid chlorine dioxide does not cause odour disadvantages on such a large scale, it affects primarily water systems. When comparing these chlorine chemicals with each other by means of the AOX number designating the loading they incur on water systems, it can be noted that elementary chlorine is many times more detrimental than chlorine dioxide. The AOX number of chlorine is of the order of 4 - 7 and that of chlorine dioxide is 1 - 1.5, or even below one.
  • Chlorine dioxide bleaching is a well-known and widely used bleaching method.
  • Conventional chlorine dioxide bleach treatment is usually performed at a temperature of 50 - 80°C and a with a chlorine dioxide dosage of about 10 - 30 kg per ton of pulp.
  • Sequences used are for example D 0 ED 1 ED 2 and OD 0 ED 1 ED 2 and various modifications of these.
  • the treatment time in a D 0 stage is usually shorter than in other D stages, being for example 30-90 minutes.
  • the pH of the pulp decreases to the range of 1 - 3 towards the end of the D 0 stage. In the D 1 and D 2 stages the treatment time is 2 - 3 hours and the pH a little higher than in the D 0 stage.
  • the chlorine dioxide stage is usually performed at a temperature of about 70°C while the treatment time in the D 0 stage is 0.5 - 2 hours and in the D 1 and D 2 stages 2-3 hours. Higher temperatures have been avoided as the low final pH in the range of 1 - 3 in the D stage combined with a high temperature and long treatment time deteriorates the strength properties of the fibers.
  • Finnish patent application no. 944808 and WO publication no. 96/12063 disclose an acid treatment method for pulp by means of which the consumption of chlorine dioxide can be reduced.
  • This treatment removes from the pulp hexenuronic acids which can react with chlorine dioxide and thus increase chemical consumption.
  • the acids may be removed by adjusting the pH of the pulp to the range of 2 - 5, preferably to 2.5 - 4, and the temperature to over 80°C, preferably to 90 - 110°C, and by retaining the pulp in these conditions typically for 30 - 300 minutes.
  • the kappa number of the pulp reduces typically by 2 - 9 units.
  • WO 97/15713 relates to treatment of pulp in connection with bleaching.
  • the pulp is first cooked and, if necessary, oxygen delignified in order to reduce the Kappa number below 14, and after that the pulp is treated in an acid stage at a pH of 2-5 and at a temperature range of 75-130°C in order to reduce the Kappa number by 2-9 units.
  • the retention time, t min is 30 to 300 minutes and the treatment temperature, T°C is T min ⁇ T ⁇ T max .
  • the method of D1 may be applied advantageously in connection with bleaching sequences, including inter alia : digestion-O-AD-D or digestion-AD-D, wherein "O” represents “oxygen delignification", "A” acid treatment, "D” Chlorine dioxide treatment and "-” stands for an intermediate washing step.
  • a high-efficiency wood pulp bleaching process is provided to produce wood pulps with higher brightness at equal chlorine dioxide usage or of equal brightness at significantly reduced chlorine dioxide usage.
  • the process comprises reacting the chlorine dioxide with wood pulp at a pH of about 5-40 minutes and then acidifying the mixture to a pH of about 1.9-4.2. The mixture is then allowed to react for about 2 or more hours to complete the two-step high/low pH bleaching process.
  • the object of the present invention is to provide an altemative method of combining a hot acid stage with a bleaching sequence utilizing chlorine dioxide.
  • a further object of the invention is to provide a method which may be applied in an economical way particularly in the bleaching plants of existing pulp mills.
  • the object of the invention is to fit chlorine dioxide bleaching of pulp into a bleaching plant in an overall economical and environmentally acceptable way.
  • the method of the invention is characterized by the features of claim 1, in cluding that the chlorine dioxide stage comprises successively at least a first chlorine dioxide step and an acid treatment step and that the pH of the first chlorine dioxide step is adjusted so that the final pH of the step is over 4.
  • the conditions during the first chlorine dioxide treatment are such that the hexenuronic acid groups in the pulp do not react with chlorine dioxide.
  • the D stage comprises successively a D step and an A step.
  • the chlorine dioxide step of the DA stage is performed so as to have a final pH of over 4, preferably over 5.
  • the highest pH value is normally 7.
  • the final pH of the first or the second chlorine dioxide bleaching stage is less than 4, typically 1 - 3.5.
  • hexenuronic acids do not react with chlorine dioxide at the pH range of over 4 and thus no chemical is consumed by reactions with chlorine dioxide.
  • Chlorine dioxide is reduced to chlorite but it does not decompose further.
  • the chlorine dioxide dose in this step is preferably 0.1 - 1.5 % active C1 (1 - 15 kg active Cl/admt), preferably over 0.5 - 1.0 % active Cl (5 - 10 kg active Cl/admt).
  • the conditions are typically as follows:
  • the temperature in the D step of the DA stage is over 70°C, preferably 80 - 100°C, which is higher than the temperature of a conventional D stage.
  • the temperature in the D and the A steps is essentially the same and there is no remarkable need to cool or to heat the pulp between the steps which is advantageous for the energy economy.
  • the invention is not limited to the high temperature but the D step may be performed also at the conventional D step temperature of below 70°C.
  • the treatment time in the D step of the invention is short, less than 10 minutes, preferably 30 seconds to 3 minutes.
  • the chlorine dioxide treatment time is over 30 minutes, even 120 minutes depending on the temperature and therefore the treatment requires a reactor of its own.
  • the DA stage according to the invention may be practiced by performing the acid treatment in the reactor tower but because of the short retention time the D step preceding the A step may be arranged to take place for example in the feed line of the A tower.
  • the pulp flowing in the line is heated to the desired temperature, for example 90°C, and chemicals, such as chlorine dioxide, and alkali or acid if necessary to adjust the pH, are mixed into it.
  • the pulp flows under these conditions for the required period, e.g. one minute, and subsequently, acid is added to the pulp and it is supplied into the acid tower.
  • the acid demand in the A step reduces as the reactions of the chlorine dioxide with the lignin produce hydrochloric acid and organic acids as byproduct.
  • the chlorine dioxide stage as described above comprises in addition to the D and A steps described above also a second D step, i.e. the stage in question comprises a first chlorine dioxide step, a hot acid treatment step and a second chlorine dioxide step (DAD, could be marked also D/A/D).
  • the second step is performed in acidic conditions, in other words the pH may be less that 2 but preferably it is 2 - 4.
  • the pH may be less that 2 but preferably it is 2 - 4.
  • Adjustment of the temperature is not necessary, either, but the entire chlorine dioxide stage may be effected essentially at the same temperature as the A step and no essential adjustments of the temperature are needed between the steps.
  • the step in question comprises a first chlorine dioxide step, a hot acid treatment step and a second chlorine dioxide step (DAD, could be marked also D/A/D).
  • the second step is performed in acidic conditions, in other words the pH may be less that 2 but preferably it is 2 - 4.
  • Adjustment of the temperature is not necessary, either, but the entire chlorine
  • the treatment time in the second D step is preferably also short, less than 10 minutes, preferably 1 - 5 minutes and it may be performed for example in the discharge line of the A step prior to the washer following the DAD stage.
  • Chlorine dioxide is added to the pulp flowing in the discharge line and the temperature and the pH are adjusted if necessary.
  • the required chlorine dioxide dose is typically 0.5 - 2.0 % active Cl (5 - 20 kg active Cl/admt).
  • the acid treatment removes hexenuronic acids from the pulp and therefore the amount of chlorine dioxide chemical required is smaller than with pulp from which hexenuronic acids have not been removed.
  • the chlorine dioxide treatment may be considered to have been divided into two relatively short partial treatments. Both steps may be practised at a high temperature; therefore the temperature and the treatment time must be chosen so as to cause as little viscosity losses in the pulp as possible. Two partial treatments contribute to a more homogenous brightness of the pulp.
  • the DA stage may be practiced also by arranging for the pulp a chelating treatment with EDTA, DTPA or a corresponding compound after the A step in order to remove harmful metals; in this case the stage is DAQ.
  • Providing a chelating treatment in connection with the DA stage is advantageous particularly if the bleaching sequence comprises later a bleaching stage with a chemical such as peroxide which would be disturbed by heavy metals.
  • the Q step may be performed at essentially the same temperature as the preceding D and A steps.
  • the pH may be in the range of 3 - 6.
  • the total amount of chlorine dioxide needed in the DA stage is not greater than the amount needed in an AD stage although the first D step is performed before the acid treatment.
  • the final pH of over 4 in the first D step prevents reactions between the ClO 2 and the hexenuronic acids.
  • a DA stage has produced pulp of at least as good quality as an AD stage.
  • a disadvantage of the AD step may be the release of malodorous gases in the acid step if the pulp still after washing contains adequate amounts of sulfur compounds from the digestion.
  • malodorous gases are oxidized by the bleaching chemical during the DA stage.
  • the method of the invention is applicable for pulps manufactured by the sulfate process and other alkaline methods which pulps contain hexenuronic acid compounds.
  • the pulp to be treated has preferably been oxygen delignified.
  • the DA stage according to the invention may be at the beginning of the bleaching sequence for example after the oxygen delignification or later in the sequence for example after a peroxide stage. Therefore the invention is advantageously applied for example in connection with the following bleaching sequences or partial bleaching sequences:
  • Pulp is treated in a DAD stage.
  • Pulp is transferred from a preceding treatment stage 10 by means of a high consistency pump 12 to an acid tower 18.
  • the consistency of the pulp is 6 - 25 %, preferably 8 - 18 %.
  • the preceding stage may be a wash following digestion or more often an oxygen delignification following digestion or a wash following oxygen delignification.
  • Alkali or acid is added to the pulp in order to adjust the initial pH for the chlorine dioxide treatment or the first D step so that the final pH is over 4, preferably over 5, in order to prevent reactions between chlorine dioxide and hexenuronic acids.
  • the alkali and the chlorine dioxide may be added directly to the pump 12, it may be injected into duct 15 between the pump 12 and the tower, or to a particular mixer 14 provided for this purpose.
  • the typical chlorine dioxide amount added is 0.5 -1.5 % active Cl.
  • Steam is added to the pulp in order to raise the temperature typically up to 80 - 100°C. Steam may be added prior to the pump 12 in a steam mixer (not illustrated) or mixed in the duct 15 following the pump 12. Alternatively, pulp may be heated indirectly in the duct 15.
  • the first D step is performed in the feed line 15 of the acid tower while the pulp flows in the line.
  • the treatment time in this step is typically 30 seconds to 3 minutes.
  • the D step is followed by an acid treatment in the tower 18.
  • the pH of the pulp is decreased to the level 2 - 5 required by the acid treatment by adding acid (sulfur acid, hydrochloric acid, waste acid from the production of chlorine dioxide or any suitable organic acid) to the pulp in the mixer 14.
  • acid sulfur acid, hydrochloric acid, waste acid from the production of chlorine dioxide or any suitable organic acid
  • the temperature may be adjusted if necessary but according to the invention the steps of the DAD stage are preferably effected at the same temperature, for example 95°C, whereby no essential temperature adjustment is required between the steps.
  • the feed and flow of pulp to the acid tower should be as even as possible by using a distributor 16 or a doctor.
  • the distributor mentioned is disclosed for example in U.S. patent no. 4,964,950, and its use for the above purpose is described in Finnish patent publication no. 94442.
  • the device 16 has adequate mixing properties and if desired, acid may be added through it and thus even avoid the use/purchase of the device 14. Pulp flows from the device 16 to the reactor tank 18 dimensioned for the treatment time required by the acid treatment, for example 120 minutes at 95°C. Using the distributing feeder described in the FI publication no. 94442 mentioned ascertains that all portions of the tower are filled evenly and that the pulp column rises up evenly in the tower so that harmful channelling can not occur. Correspondingly, the top of the tower has been provided with a discharger 20 or a discharge doctor to guide pulp to the discharge line 24 of the tower.
  • the second D step is performed in the discharge line 24 in order to bleach the pulp.
  • Chlorine dioxide may be added to the pulp via the acid tower discharger 20 of a pump 22 in the discharge line.
  • a separate mixer (not illustrated) may be arranged in the line 24 for addition of chemical which is about 0.5 - 2.0 % active Cl.
  • the addition of chemicals to the pulp is fitted so that a proper treatment time for carrying out the D step in the discharge line 24 before a washer 26 is reached.
  • the retention time is less than 10 minutes, preferably 1 - 5 minutes.
  • the treatment temperature of this D step is preferably the same as the one in the previous D and A steps; thus no essential adjustment of the temperature after the A step is needed here either.
  • pulp may be heated or cooled in a heat exchanger or by direct feeding of steam. A higher temperature than conventionally is, however, required in order to obtain adequate bleaching during the short treatment time mentioned.
  • the pH of the second D step is tower than that of the first D step.
  • the pH is about 2 - 4; thus adjustment of the pH is usually not needed after the A step.
  • the chemical adjusting the pH may be added in the same stage as the chlorine dioxide.
  • Pulp has been bleached in a DAD stage the way described above and subsequently the pulp is treated in the washer 26 and is transported to further treatment.
  • the subsequent stage is an E stage.
  • Oxygen-bleached pulp was tested in a laboratory, the kappa number of which was 11.9, viscosity 1061 ml/g and the ISO brightness 49.2 %.
  • the pulp was treated with the following sequences:

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
EP99103920A 1998-03-06 1999-03-05 Method for treatment of pulp Expired - Lifetime EP0940498B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI980519A FI119383B (fi) 1998-03-06 1998-03-06 Menetelmä massan käsittelemiseksi
FI980519 1998-03-06

Publications (2)

Publication Number Publication Date
EP0940498A1 EP0940498A1 (en) 1999-09-08
EP0940498B1 true EP0940498B1 (en) 2006-05-17

Family

ID=8551173

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Application Number Title Priority Date Filing Date
EP99103920A Expired - Lifetime EP0940498B1 (en) 1998-03-06 1999-03-05 Method for treatment of pulp

Country Status (7)

Country Link
US (1) US20020056533A1 (fi)
EP (1) EP0940498B1 (fi)
CA (1) CA2264423C (fi)
DE (1) DE69931295D1 (fi)
ES (1) ES2263236T3 (fi)
FI (1) FI119383B (fi)
PT (1) PT940498E (fi)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE524896C2 (sv) * 2003-03-07 2004-10-19 Kvaerner Pulping Tech Blekning av cellulosamassa med klordioxid i två faser med uppvärmning mellan faserna
US20060201642A1 (en) * 2005-03-08 2006-09-14 Andritz Inc. Methods of treating chemical cellulose pulp
US8920603B2 (en) 2006-10-11 2014-12-30 Akzo Nobel N.V. Bleaching of pulp
CA2665969C (en) * 2006-10-11 2016-04-12 Magnus Bjoerklund Bleaching of pulp

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5268075A (en) * 1989-10-19 1993-12-07 North Carolina State University High efficiency two-step, high-low pH chlorine dioxide pulp bleaching process
FI102301B1 (fi) * 1994-10-13 1998-11-13 Ahlstrom Machinery Oy Menetelmä selluloosamassojen käsittelemiseksi
US6776876B1 (en) * 1994-10-13 2004-08-17 Andritz Oy Method of treating cellulosic pulp to remove hexenuronic acid
FI105701B (fi) * 1995-10-20 2000-09-29 Ahlstrom Machinery Oy Menetelmä ja laitteisto massan käsittelemiseksi

Also Published As

Publication number Publication date
DE69931295D1 (de) 2006-06-22
CA2264423A1 (en) 1999-09-06
EP0940498A1 (en) 1999-09-08
PT940498E (pt) 2006-09-29
FI980519A (fi) 1999-09-07
US20020056533A1 (en) 2002-05-16
CA2264423C (en) 2003-01-28
FI119383B (fi) 2008-10-31
FI980519A0 (fi) 1998-03-06
ES2263236T3 (es) 2006-12-01

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