EP2082096B1 - Zellstoffbleiche - Google Patents
Zellstoffbleiche Download PDFInfo
- Publication number
- EP2082096B1 EP2082096B1 EP07808867A EP07808867A EP2082096B1 EP 2082096 B1 EP2082096 B1 EP 2082096B1 EP 07808867 A EP07808867 A EP 07808867A EP 07808867 A EP07808867 A EP 07808867A EP 2082096 B1 EP2082096 B1 EP 2082096B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chlorine dioxide
- pulp
- bleaching
- stage
- process according
- 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.)
- Not-in-force
Links
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
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
- D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
- D21C9/142—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 in a multistage process involving ClO2/Cl2 exclusively
Definitions
- the present invention relates to a bleaching process which decreases the brightness reversion or yellowing of an ECF bleached pulp.
- EP-A-0 940 498 discloses a bleaching process using three chlorine dioxide stages.
- the present invention relates to a process of bleaching pulp derived from an alkaline pulping process having a hexenuronic acid content prior to the final bleaching stage from 1 to 80 mmol/kg dry pulp, said process comprising three chlorine dioxide stages D0, D1, and D2, wherein the chlorine dioxide charges based on the total chlorine dioxide charge in
- the pulp to be bleached may be derived from lignocellulose-containing material which may comprise e.g. wood logs, finely-divided raw materials, and woody materials, such as wood particles and non-wood such as fibres of annual or perennial plants.
- the woody raw material can be derived from hardwood or softwood species, such as birch, beech, aspen, alder, eucalyptus, maple, acacia, mixed tropical hardwood, pine, fir, hemlock, larch, spruce, and mixtures thereof.
- Non-wood plant raw material can be provided from e.g.
- pulp derived from recycled pulp may be used, either separately or in mixtures with virgin pulps.
- the pulp can be a chemical pulp, produced using an alkaline pulping process, for example sulphate, soda processes or modifications thereof with optional additives such as anthraquinone, e.g. the soda anthraquinone (AQ) pulping process.
- the chemical pulp obtainable from lignocellulose-containing materials may be subjected to one or more oxygen treatment stages subsequent to the pulping process.
- the process can be applied to chemically digested pulps having an initial kappa number, i.e. a kappa number after digestion but before oxygen delignification, in the range from 5 to 40, for example from 8 to 30, or from 8 to 25
- the referred kappa number is measured according to the ISO 302 Standard Method.
- the content of hexenuronic acids in the bleached pulp prior to the final bleaching stage is from 5 to 80 or from 5 to 25, or from 5 to 15 mmol/kg dry pulp.
- the pH of the first chlorine dioxide bleaching stage ranges from 2 to 4, for example from 2.5 to 3.5.
- the pH of the second chlorine dioxide bleaching stage ranges from 2.5 to 4.5, for example from 3 to 4.
- the pH of the final chlorine dioxide bleaching stage ranges from 2 to 3.5, such as from 2 to 3.4 or from 2 to 3.3 or from 2.5 to 3, or any other sub-range within the range from 2.5 to 4.5.
- the temperature of the first chlorine dioxide bleaching stage ranges from 40 to 90, for example from 50 to 80 or from 55 to 70°C.
- the temperature of the second chlorine dioxide bleaching stage ranges from 70 to 90, for example from 80 90°C.
- the temperature of the final chlorine dioxide bleaching stage ranges from 80 to 100, for example from 85 to 100, or from 87 to 100 °C.
- the pulp consistency in the chlorine dioxide bleaching stages ranges from 1 to 40, for example from 3 to 30 or from 5 to 15 wt%.
- the charge of chlorine dioxide charge based on the total chlorine dioxide charge in D0 is from 45 to 55, for example from 45 to 50, or from 45 to 48 %.
- the charge of chlorine dioxide charge based on the total chlorine dioxide charge in D1 is from 35 to 50, for example from 40 to 50, or from 45 to 50 %.
- the charge of chlorine dioxide charge based on the total chlorine dioxide charge in D2 is from 5 to 15, for example from 5 to 12, or from 5 to 10%.
- the retention time of the first chlorine dioxide bleaching stage is from 20 to 60, for example from 30 to 50, or from 35 to 45 minutes.
- the retention time of the second chlorine dioxide bleaching stage is from 60 to 240, for example from 60 to 120, or from 60 to 90 minutes.
- the retention time in the final chlorine dioxide bleaching stage is from 90 to 360, for example from 110 to 240, or from 110 to 180 minutes.
- the bleaching process may comprise besides chlorine dioxide stages for example ozone, peracid, oxygen and/or peroxide-containing, as well as enzyme-containing bleaching stages either in addition to the sequence of three chlorine dioxide stages or substituting any of the initial chlorine dioxide stages.
- also washing and/or extraction stages, acidification and/or chelating agent stages may be present in the bleaching process preceeding, between and/or subsequent to any bleaching stages.
- chlorine dioxide and chelating agent stages can be carried out without any make-up chemicals added, as both stages can be performed at similar pH ranges.
- a chelating agent stage is carried out essentially in absence of chlorine dioxide, as essentially most of the chlorine dioxide is washed away by the washing stage.
- an acid readily available in the pulp mill may be employed.
- the pulp can be bleached with a peroxide-containing compound which can be an inorganic peroxide compound such as hydrogen peroxide or peroxomonosulphuric acid (caro's acid) or an inorganic peroxide compound like aliphatic peracids and aromatic peracids and salts thereof.
- a peroxide-containing compound which can be an inorganic peroxide compound such as hydrogen peroxide or peroxomonosulphuric acid (caro's acid) or an inorganic peroxide compound like aliphatic peracids and aromatic peracids and salts thereof.
- Suitable organic peroxides are peracetic acid and performic acid.
- the peroxide-containing compound is hydrogen peroxide or a mixture of hydrogen peroxide and peracetic acid commonly referred to as equilibrium peracetic acid.
- the pH of the pulp suspension is suitably 7, for example in the range from 7 to 13, from 8 to 12, or from 9.5 to 11.5.
- the temperature of the hydrogen peroxide bleaching may be from 30 to 130, for example from 50 to 100, or from 50 to 90 °C.
- the length of the hydrogen peroxide treatment may be from 3 to 960, for example from 10 to 360, or from 60 to 240 minutes.
- the amount of added hydrogen peroxide is from 1 to 60, for example from 6 to 50, or from 13 to 40 kg per tonne dry pulp.
- Other bleaching agents may be added to the hydrogen peroxide bleaching stage such as oxygen.
- the bleaching process comprises an ECF (Elemental Chlorine Free) or a substantially ECF sequence, for example according to the following sequence: D0(OP)D1nD2, where D0, D1, and D2 indicate three chlorine dioxide (D) stages, OP indicates an oxygen-containing peroxide stage, and n indicates a neutral washing stage.
- the bleached pulp is subsequently treated as an aqueous suspension prior to papermaking by dewatering and drying said suspension, wherein the pH of the suspension to be treated ranges from 6.5 to 12.
- the bleached pulp may be further treated as set out in US appl.11/847374 .
- the invention also relates to a bleached pulp obtainable by the process defined herein.
- the experiments were carried out employing an industrial oxygen-delignified eucalyptus pulp.
- the characteristics of the oxygen-delignified pulp is shown in table 1.
- the pulp could be characterized as a low bleaching chemical demand pulp with high content of hexenuronic acid (HexA).
- the pulp had an unbleached kappa number of 10.7 and required 1.5 kg/t H 2 O 2 and 27 kg/t ClO 2 in the sequence D0(OP)D1nD2 to reach the brightness target 90.5% ISO.
- Table 1 Oxygen delignified eucalyptus pulp Kappa number ISO Brightness (%) Viscosity dm 3 /kg Hexenuronic acid mmol/kg 10.7 58.9 1030 71
- the aim of the experiments was to improve a standard ECF sequence, D0(OP)D1nD2, in view of brightness reversion within the limitations of an existing mill.
- the same total dosage of chlorine dioxide was made in all experiments.
- the conditions in the D1 and D2 stages and the distribution of chlorine dioxide were varied whereas the conditions in the D0 and (OP) stages were kept constant.
- the retention time and temperature in the D0 stage were 45 minutes and 60°C.
- the (OP) stage was performed at a pressure of 0.5 MPa, a retention time of 60 minutes, a temperature of 80°C and a final pH between 11.6 and 11.9.
- the hydrogen peroxide (H 2 O 2 ) dosage was 1.5 kg/t on oven dry pulp in all experiments.
- the pulp and chemicals were mixed at 10 wt% pulp consistency and distributed uniformly in polypropylene bags, the atmosphere of which was saturated with oxygen.
- the plastic bags were sealed and placed in autoclaves which were pressurized with oxygen.
- the chlorine dioxide dosages were given as active chlorine.
- the consistency was 10 wt% in all bleaching stages. All non-pressurised stages were carried out in sealed plastic polyethylene bags.
- the pulp was washed with distilled water.
- the neutral wash stage (n) between the D1 and D2 stages the pH was adjusted to between 7 and 10 with NaOH.
- the kappa number and ISO brightness were determined according to ISO 302 and ISO 2470 respectively.
- the hexenuronic acid was determined by acidic hydrolysis of the pulp in a formate buffer followed by UV analysis of the 2-furoic acid formed in the hydrolysate.
- the accelerated heat-induced brightness reversion was evaluated as humid brightness reversion.
- the "humid brightness reversion” was evaluated by measuring the brightness loss after the sheet had been conditioned at 23°C and 50% relative humidity, sealed in a polyethylene bag, kept at 70°C for 64h and finally removed from the bag and allowed to temperate at room temperature for at least 1 h.
- the brightness reversion was reported as the difference in ISO brightness units before and after reversion treatment.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Claims (10)
- Verfahren zum Bleichen von Zellstoff, der aus einem alkalischen Kochprozess stammt und vor dem abschließenden Bleichungsschritt einen Hexenuronsäuregehalt von 1 bis 80 mmol/kg trockenen Zellstoffs aufweist, wobei das Verfahren drei Chlordioxidschritte D0, D1, und D2 umfasst, wobei die Chlordioxidbeschickung basierend auf der Gesamtchlordioxidbeschickung beia) D0 von 40 bis 60 % beträgt;b) D1 von 30 bis 55 % beträgt;c) D2 von 4 bis 20 % beträgt, und wobei der abschließende Chlordioxidschritt D2 bei einem pH-Wert von 2 bis 3,5 durchgeführt wird.
- Verfahren gemäß Anspruch 1, wobei der Hexenuronsäuregehalt von 5 bis 25 mmol/kg trockenen Zellstoffs beträgt.
- Verfahren gemäß Anspruch 1 oder 2, wobei der Hexenuronsäuregehalt von 5 bis 15 mmol/kg trockenen Zellstoffs beträgt.
- Verfahren gemäß einem der Ansprüche 1 - 3, wobei der abschließende Chlordioxidschritt bei einem pH-Wert von 2 bis 3,4 durchgeführt wird.
- Verfahren gemäß einem der Ansprüche 1 - 4, wobei die Temperatur des abschließenden Chlordioxidbleichungsschritts im Bereich von 85 bis 100°C liegt.
- Verfahren gemäß einem der Ansprüche 1 - 5, wobei der abschließende Chlordioxidschritt bei einem pH-Wert von 2 bis 3,3 durchgeführt wird.
- Verfahren gemäß einem der Ansprüche 1 - 6, wobei die Chlordioxidbeschickung bei a) D0 von 45 bis 55 % beträgt, b) D1 von 35 bis 50 % beträgt, und c) D2 von 5 bis 15 % beträgt.
- Verfahren gemäß einem der Ansprüche 1 - 7, wobei die Chlordioxidbeschickung bei a) D0 von 45 bis 50 % beträgt, b) D1 von 40 bis 50 % beträgt, und c) D2 von 5 bis 12 % beträgt.
- Verfahren gemäß einem der Ansprüche 1 - 8, wobei die Temperatur des abschließenden Chlordioxidbleichungsschritts im Bereich von 85 bis 100°C liegt.
- Gebleichter Zellstoff, erhältlich durch das in einem der Ansprüche 1 bis 9 definierte Verfahren.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07808867A EP2082096B1 (de) | 2006-10-11 | 2007-09-06 | Zellstoffbleiche |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06122119 | 2006-10-11 | ||
PCT/SE2007/050630 WO2008044988A1 (en) | 2006-10-11 | 2007-09-06 | Bleaching of pulp |
EP07808867A EP2082096B1 (de) | 2006-10-11 | 2007-09-06 | Zellstoffbleiche |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2082096A1 EP2082096A1 (de) | 2009-07-29 |
EP2082096B1 true EP2082096B1 (de) | 2013-02-20 |
Family
ID=37807769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07808867A Not-in-force EP2082096B1 (de) | 2006-10-11 | 2007-09-06 | Zellstoffbleiche |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP2082096B1 (de) |
AR (1) | AR063160A1 (de) |
BR (1) | BRPI0719893A2 (de) |
CA (1) | CA2665969C (de) |
CL (1) | CL2007002906A1 (de) |
EA (1) | EA013901B1 (de) |
ES (1) | ES2403371T3 (de) |
NO (1) | NO20091815L (de) |
PT (1) | PT2082096E (de) |
UY (1) | UY30634A1 (de) |
WO (1) | WO2008044988A1 (de) |
ZA (1) | ZA200903205B (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI20105862A0 (fi) | 2010-08-18 | 2010-08-18 | Bo Akademi University | Menetelmä hekseeniuronihappojen poistamiseksi |
US9970157B2 (en) | 2013-08-09 | 2018-05-15 | Novozymes A/S | Reducing content of hexenuronic acids in cellulosic pulp |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501374A (en) * | 1968-12-26 | 1970-03-17 | Hooker Chemical Corp | Sequential bleaching of kraft pulp with chlorine dioxide and chlorine |
US5268075A (en) * | 1989-10-19 | 1993-12-07 | North Carolina State University | High efficiency two-step, high-low pH chlorine dioxide pulp bleaching process |
US5030324A (en) * | 1990-01-29 | 1991-07-09 | Champion International Corporation | Sequential bleaching procedure using chlorine and chlorine dioxide in a first chlorination stage of a multistage bleaching process |
US6776876B1 (en) * | 1994-10-13 | 2004-08-17 | Andritz Oy | Method of treating cellulosic pulp to remove hexenuronic acid |
FI119383B (fi) * | 1998-03-06 | 2008-10-31 | Andritz Oy | Menetelmä massan käsittelemiseksi |
JP2004522008A (ja) * | 2001-06-06 | 2004-07-22 | クヴアナ・パルピング・アクチボラグ | 二酸化塩素漂白で形成された有機結合塩素の低減 |
US20060201642A1 (en) * | 2005-03-08 | 2006-09-14 | Andritz Inc. | Methods of treating chemical cellulose pulp |
-
2007
- 2007-09-06 BR BRPI0719893-0A2A patent/BRPI0719893A2/pt not_active Application Discontinuation
- 2007-09-06 ES ES07808867T patent/ES2403371T3/es active Active
- 2007-09-06 EP EP07808867A patent/EP2082096B1/de not_active Not-in-force
- 2007-09-06 WO PCT/SE2007/050630 patent/WO2008044988A1/en active Application Filing
- 2007-09-06 PT PT07808867T patent/PT2082096E/pt unknown
- 2007-09-06 CA CA2665969A patent/CA2665969C/en not_active Expired - Fee Related
- 2007-09-06 EA EA200970367A patent/EA013901B1/ru not_active IP Right Cessation
- 2007-10-08 UY UY30634A patent/UY30634A1/es not_active Application Discontinuation
- 2007-10-09 AR ARP070104434 patent/AR063160A1/es active IP Right Grant
- 2007-10-09 CL CL2007002906A patent/CL2007002906A1/es unknown
-
2009
- 2009-05-08 ZA ZA200903205A patent/ZA200903205B/xx unknown
- 2009-05-08 NO NO20091815A patent/NO20091815L/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EA013901B1 (ru) | 2010-08-30 |
PT2082096E (pt) | 2013-04-26 |
CA2665969C (en) | 2016-04-12 |
ZA200903205B (en) | 2010-03-31 |
CA2665969A1 (en) | 2008-04-17 |
NO20091815L (no) | 2009-07-10 |
EP2082096A1 (de) | 2009-07-29 |
UY30634A1 (es) | 2007-11-30 |
WO2008044988A1 (en) | 2008-04-17 |
BRPI0719893A2 (pt) | 2014-05-06 |
CL2007002906A1 (es) | 2008-05-02 |
AR063160A1 (es) | 2008-12-30 |
EA200970367A1 (ru) | 2009-08-28 |
ES2403371T3 (es) | 2013-05-17 |
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