EP0496782B1 - Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd - Google Patents

Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd Download PDF

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Publication number
EP0496782B1
EP0496782B1 EP90915570A EP90915570A EP0496782B1 EP 0496782 B1 EP0496782 B1 EP 0496782B1 EP 90915570 A EP90915570 A EP 90915570A EP 90915570 A EP90915570 A EP 90915570A EP 0496782 B1 EP0496782 B1 EP 0496782B1
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EP
European Patent Office
Prior art keywords
bleaching
chlorine dioxide
process according
bleaching process
stage
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Revoked
Application number
EP90915570A
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English (en)
French (fr)
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EP0496782A4 (en
EP0496782A1 (de
Inventor
Hou-Min Chang
Geoffrey Eugene C/O Proctor & Gamble Seger
Hasan Jameel
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North Carolina State University
University of California
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North Carolina State University
University of California
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Publication of EP0496782A4 publication Critical patent/EP0496782A4/en
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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
    • D21C9/12—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 the bleaching of pulp and more particularly to an improved process for bleaching wood pulp with chlorine dioxide in a manner whereby the wood pulp is subjected to a 2-step high pH/low pH bleaching stage which results in a substantial decrease in the usage of chlorine dioxide required to brighten wood pulp.
  • the main objectives of wood pulp bleaching are to increase the brightness of the pulp and to make it suitable for the manufacture of printing and tissue grade papers by removal or modification of some of the constituents of the unbleached pulp, including the lignin and its degradation products, resins, metal ions, non-cellulosic carbohydrate components, and various other types of flecks.
  • the bleaching of chemical wood pulp is normally carried out in multiple processing stages utilizing elemental chlorine, caustic soda, hypochlorites, oxygen, hydrogen peroxide, and chlorine dioxide. The number of stages required in a particular bleaching process is dependent upon the nature of the unbleached pulp as well as the end use to which the pulp will be put.
  • DE-A-3239811 discloses a process for bleaching cellulose-containing materials in a multi-stage sequence.
  • the cellulose-containing materials are treated with chlorine (Cl2) under careful pH control, followed by chlorine dioxide.
  • U.S.-A-3433702 discloses a process employing a chlorine dioxide stage followed by a chlorination stage, instead of a chlorination stage followed by a chlorine dioxide stage, as is conventional.
  • a sulphate or kraft pulp is today most typically bleached in a five stage sequence which is designated as (CD)(EO)DED.
  • D denotes chlorine dioxide
  • C denotes elemental chlorine
  • E denotes caustic extraction
  • O denotes oxygen gas.
  • the multi-stage process in essence comprises a chlorination step (CD), a first oxidative extraction stage (EO), a first bleaching stage (D1), a second caustic extraction stage (E2), and a second and final bleaching stage (D2).
  • each of the two chlorine dioxide bleaching stages is carried out in an one-step process at an end pH of about 3.8 for three hours at 70°C. It is commonly known that pH has an important bearing on brightness and strength properties as well as the chemical species present in the wood pulp mixture, and this particular pH has heretofore been considered optimal for each of the two chlorine dioxide bleaching stages in the (CD)(EO)DED sequence. It should also be appreciated that although the (CD) (EO)DED sequence has been specifically addressed, the one-step chlorine dioxide bleaching stage can be used in any D stage for most other three, four, five or six-stage bleaching processes known to those familiar with the art of wood pulp bleaching.
  • a shortcoming of the one-step chlorine dioxide bleaching stage presently used in the pulp and paper industry is that approximately 30% of the chlorine dioxide is lost to the formation of the unreactive species chlorite and chlorate, and this is very undesirable in view of the relatively high cost of chlorine dioxide.
  • the present invention solves this well-known deficiency in state of the art chlorine dioxide bleaching by significantly reducing the chlorine dioxide loss during the chlorine dioxide bleaching process.
  • the advantages of the reduced loss of chlorine dioxide are a very significant reduction in the cost of the wood pulp bleaching process as well as the reduction of pollution levels.
  • a bleaching process for bleaching wood pulp in the D1 or D2 bleaching stage in an aqueous suspension using chlorine dioxide and providing high brightness and a high brightness ceiling characterised by the steps of:
  • Chlorine dioxide bleaching of kraft pulps is typically carried out at an end pH of 3.8 for 3 hours at 70° centigrade. It is commonly known that pH has an important bearing on brightness and strength properties as well as the chemical species present in the mixture. As shown in Figure 1 of the drawings, the formation of chlorate increases as the pH of the solution is decreased. Below pH 5 a major loss of oxidizing power occurs since the chlorate formed is inactive as a bleaching agent. Conversely, as the pH is increased, the conversion of chlorine dioxide to the chlorite anion is increased which is also inactive toward lignin. The sum of chlorite plus chlorate is lowest at end pH 3.8 which is found to be optimal for chlorine dioxide bleaching. However, formation of chlorite is not actually lost oxidizing capability since acidifying the chlorite solution forms chlorous acid which is known to be very reactive toward lignin.
  • Chlorination stage charges were varied to achieve target (CD)E kappa numbers, and all charges are on OD brownstock pulp. Optimum high/low pH values are 6-7.5 and 3.8, respectively. Large batches of (CD)E pulp were made and then divided into individual DED runs for comparison. All comparisons were made on pulps from the same (CD)E batch, and all water used in bleaching and washing was distilled. Chlorine dioxide solutions used in testing were generated on site by acidifying sodium chlorite solution and absorbing the ClO2 gas in cold distilled water. Chlorine content in the solutions was kept between 7 and 10% (active basis).
  • Pulp viscosity measurements were made using TAPPI standard T 230 os-76. Earlier experimental work has indicated that chlorine dioxide at a pH of less than 5 reacts selectively with lignin, and at a pH greater than 7 chlorine dioxide reacts with the carbohydrate and lignin in the pulp vigorously, which in turn degrades the cellulose chain. As shown in Figure 7, pulp viscosity depends heavily on the pH of the reacting mixture. Pulp viscosity decreases slowly from pH 6 to 7, then falls rapidly at pH values higher than 7. The decrease in viscosity at the high pH for the two-step high/low pH bleaching process is not significant because of the low reaction time in the high pH step. From viscosity and brightness data obtained, a pH of 6-7.5 and a pH of 3.8 is optimal for the high pH and low pH, respectively, in the two-step high/low pH bleaching process.
  • TOCl (AOX) measurements in applicant's tests were made on both the D1 and E2 for one data set. The values were added together and are shown in Figure 8 of the drawings. Surprisingly, conventional bleaching TOCl values were parabolic versus an increasing ClO2 charge while TOCl values with the high/low pH bleaching method varied only slightly. A greater decrease in TOCl from bleaching with the two-step high/low pH bleaching process can be realized by substituting the chlorine dioxide saved in the D1 stage back into the chlorination stage (CD) of the multi-stage bleach sequence. This would result in a decrease in TOCl (AOX) in effluents from the bleach plant.
  • CD chlorination stage
  • Chlorate (ClO 3 - ) is a well known herbicide, and discharge of chlorate from paper mills has been gaining more attention from environmentalists now that possible detrimental effects on various microalgaes have been observed. Thus, improving the efficiency of chlorine dioxide bleaching by lowering chlorate production may have a favorable impact on both economic and environmental issues. Conversion of chlorine dioxide to chlorate can be lowered by the two-stage high/low pH bleaching method for most chemical charges on pulp. At very high chemical charges (or lower lignin concentrations), chlorate formation is independent of whether the new or conventional bleaching method is used, because a brightness ceiling is reached.
  • Equation 1 2ClO2 + 2OH ⁇ ----> ClO 3 - + ClO 2 - + H2O Equation 2 2HClO2 ----> H+ + HClO + ClO 3 -
  • Equation 1 is not a very prominent reaction in bleaching carried out at pH 7 since only a small concentration of hydroxyl ions are present. Under typical bleaching conditions, the pH starts around 5 and drops to less than 4 by the end of the bleaching process. At pH 5, less than 1% hydroxyl ions would be present for reaction, and at pH 4 only 0.1% exist. Supporting evidence for this observation is shown in Figure 9 of the drawings. The trend indicated shows that as the pH is increased up to 9, the formation of chlorate decreases.
  • Equation 2 The major pathway for chlorate formation is Equation 2 above.
  • chlorous acid reacts with itself to form chlorate and hypochlorous acid. This is a biomolecular reaction which is considered to be slow at low concentrations.
  • Chlorous acid as stated above, is very reactive toward lignin. Chlorous acid oxidizes lignin and is reduced to hypochlorous acid according to Equation 3: Equation 3 HClO2 + LIGNIN ---> HClO + OXIDIZED LIGNIN
  • FIG. 10 shows a plot of D1 charge of chlorine dioxide versus % chlorine dioxide converted to chlorate for conventional chlorine dioxide bleaching. As the lignin concentration is increased (low chemical charge or higher kappa number) less chlorate is formed. Likewise if a high concentration of chemical is present (low kappa number), the higher the formation of chlorate. The same trend also holds true for the two-step high/low pH bleaching process as can be seen in Figure 11. From Figures 10 and 11, it is evident that the two-step high/low pH bleaching process significantly lowers chlorate formation at most chemical charges. However, little difference is seen at high charges where the brightness ceiling is reached.
  • the two-step high/low pH bleaching process can be implemented in both a new plant or an existing pulp bleaching plant.
  • the optimum design schematic is shown in Figure 15, where ClO2 and caustic are added to the first mixer.
  • the pulp flows into a J or U tube ( Figure 15A) or upflow tower ( Figure 15B) with a retention time of approximately 5-40 minutes.
  • a second mixer is provided to mix the acid for pH adjustment of the wood pulp.
  • the pulp can then be discharged directly to a downflow tower.
  • the retention time in the downflow tower is 2 or more hours and most suitably between about 2.5-3.9 hours.
  • the simplest method for implementing the two-step high/low pH bleaching process technology would be to install a mixer on the discharge from the upflow leg of the tower to the downflow leg of the tower.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Noodles (AREA)

Claims (17)

  1. Bleichverfahren zum Bleichen von Zellstoff in der D₁- oder D₂-Bleichstufe in einer wäßrigen Suspension unter Verwendung von Chlordioxid, wobei ein hoher Weißgrad und eine hohe Weißgrad-Grenze erreicht werden,gekennzeichnet durch die folgenden Schritte:
    - die wäßrige Zellstoffsuspension wird einem ersten Bleichschritt während der D₁- oder D₂-Bleichstufe unterworfen, indem sie mit Chlordioxid und/oder Alkali während etwa 5 bis 40 Minuten gemischt wird so daß der pH am Ende des ersten Bleichschritts zwischen etwa 6,0 und 10,0 liegt.
    - der pH der Mischung wird nach dem ersten Bleichschritt verringert; und
    - die Mischung wird während der D₁- und/oder D₂-Bleichstufe einem zweiten Bleichschritt während etwa zwei oder mehr Stunden unterworfen, so daß der pH am Ende des zweiten Schritts zwischen etwa 1,9 und 4,2 liegt.
  2. Bleichverfahren nach Anspruch 1, worin im ersten Bleichschritt die Zellstoffsuspension mit Alkali und 10% bis 50% der gesamten Chlordioxid-Zugabe gemischt wird und die restliche Chlordioxid-Zugabe beim zweiten Bleichschritt zugegeben wird.
  3. Bleichverfahren nach Anspruch 1 oder 2, worin das Alkali Natriumhydroxid enthält.
  4. Bleichverfahren nach einem der vorangehenden Ansprüche, worin der End-pH-Wert des Gemisches während des ersten Bleichschritts zwischen etwa 6,0 und 7,5 liegt.
  5. Bleichverfahren nach einem der vorangehenden Ansprüche, worin die Temperatur während des ersten Bleichschritts zwischen etwa 50 und 85°C liegt.
  6. Bleichverfahren nach Anspruch 5, worin die Temperatur während des ersten Bleichschritts etwa 50°C beträgt.
  7. Bleichverfahren nach einem der vorangehenden Ansprüche, worin der End-pH-Wert der Gemisches während des zweiten Bleichschrittes etwa 3,8 ist.
  8. Bleichverfahren nach einem der vorangehenden Ansprüche, worin die Temperatur während des zweiten Bleichschritts etwa 55 bis 85°C ist.
  9. Bleichverfahren nach Anspruch 8, worin die Temperatur während des zweiten Bleichschritts etwa 70°C ist.
  10. Bleichverfahren nach einem der vorangehenden Ansprüche, worin die End-Konsistenz des Gemisches nach dem zweiten Bleichschritt zwischen etwa 3 und 12% liegt.
  11. Bleichverfahren nach Anspruch 10, worin die End-Konsistenz des Gemisches nach dem zweiten Bleichschritt etwa 10 % ist.
  12. Bleichverfahren nach einem der vorangehenden Ansprüche, worin die Dauer des zweiten Bleichschritts etwa 2,5 bis 3,9 Stunden ist.
  13. Bleichverfahren nach einem der vorangehenden Ansprüche, worin der pH-Wert mit einer Säure herabgesetzt wird.
  14. Bleichverfahren nach Anspruch 13, worin die Säure ausgewählt ist aus der Gruppe Schwefelsäure und Chlorwasserstoffsäure.
  15. Bleichverfahren nach einem der vorangehenden Ansprüche, worin das Bleichverfahren in einem Drei-Stufen-Sequenzverfahren verwendet wird.
  16. Bleichverfahren nach Anspruch 15, worin das Bleichverfahren in der ersten Chlordioxid-Bleichstufe in einem Fünf-Stufen-Sequenzverfahren verwendet wird.
  17. Bleichverfahren nach Anspruch 16, worin das Fünf-Stufen-Sequenzverfahren ein (CD), (EO), D₁E₂D₂-Verfahren ist und auf die erste Bleichstufe die üblichen Extraktions- und Bleichstufen folgen.
EP90915570A 1989-10-19 1990-10-17 Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd Revoked EP0496782B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US42434789A 1989-10-19 1989-10-19
US424347 1989-10-19
PCT/US1990/005825 WO1991005909A1 (en) 1989-10-19 1990-10-17 High efficiency chlorine dioxide pulp bleaching process

Publications (3)

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EP0496782A1 EP0496782A1 (de) 1992-08-05
EP0496782A4 EP0496782A4 (en) 1993-02-03
EP0496782B1 true EP0496782B1 (de) 1996-03-20

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EP90915570A Revoked EP0496782B1 (de) 1989-10-19 1990-10-17 Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd

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EP (1) EP0496782B1 (de)
CN (1) CN1052157A (de)
AR (1) AR243945A1 (de)
AU (1) AU6537690A (de)
CA (1) CA2069322A1 (de)
DE (1) DE69026105T2 (de)
ES (1) ES2085358T3 (de)
MX (1) MX172853B (de)
NZ (1) NZ235754A (de)
PL (1) PL164745B1 (de)
WO (1) WO1991005909A1 (de)
ZA (1) ZA908341B (de)

Families Citing this family (8)

* 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
BR9901291B1 (pt) * 1999-04-27 2011-11-01 processo para branqueamento de polpas quìmicas de baixa consistência.
SE524896C2 (sv) * 2003-03-07 2004-10-19 Kvaerner Pulping Tech Blekning av cellulosamassa med klordioxid i två faser med uppvärmning mellan faserna
EP1880053B1 (de) * 2005-05-04 2019-07-31 Novozymes North America, Inc. Chlordioxidbehandlungszusammensetzungen und verfahren
FI122626B (fi) * 2006-03-31 2012-04-30 Laennen Tutkimus Western Res Inc Oy Kemiallisen massan valkaisumenetelmä
CN103469663B (zh) * 2013-08-13 2016-05-04 广西大学 一种通过响应面法优化纸浆二氧化氯漂白方法
FR3062138B1 (fr) * 2017-01-23 2019-06-07 Centre Technique De L'industrie Des Papiers, Cartons Et Celluloses Procede de blanchiment d'une pate a papier
CN111979818A (zh) * 2020-08-07 2020-11-24 齐鲁工业大学 一种硫酸盐木浆短程序ecf漂白工艺x/z/d-eop-d或x/d/z-eop-d

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1004805A (en) * 1973-10-18 1977-02-08 Louis O. Torregrossa Non-neutral bleaching of pulp
CA1239253A (en) * 1983-05-20 1988-07-19 Louis O. Torregrossa Method of chlorine dioxide bleaching

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3433702A (en) * 1965-06-28 1969-03-18 Hooker Chemical Corp Woodpulp bleaching process
FR2432574A1 (fr) * 1978-08-01 1980-02-29 Europeen Cellulose Procede de blanchiment de pate a papier
SE8106334L (sv) * 1981-10-27 1983-04-28 Sunds Defibrator Sett att behandla cellulosahaltigt material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1004805A (en) * 1973-10-18 1977-02-08 Louis O. Torregrossa Non-neutral bleaching of pulp
CA1239253A (en) * 1983-05-20 1988-07-19 Louis O. Torregrossa Method of chlorine dioxide bleaching

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. Wong, Effect of Tetrahydroanthraquinone (THAQ) on the Neutral Sulphite Pulping of Seed Flax Fibres, Journal of Pulp and Paper Science: Vol. 13 No. 1, Jan 1987. A. Teder and Lisa Tormund, Carbohydrate degradation in chlorine dioxide bleaching, Tappi, Vol. 61, No 12, Dec 1978 *

Also Published As

Publication number Publication date
ZA908341B (en) 1991-08-28
WO1991005909A1 (en) 1991-05-02
PL287415A1 (en) 1991-09-23
CA2069322A1 (en) 1991-04-20
CN1052157A (zh) 1991-06-12
ES2085358T3 (es) 1996-06-01
MX172853B (es) 1994-01-17
AR243945A1 (es) 1993-09-30
PL164745B1 (pl) 1994-10-31
DE69026105T2 (de) 1996-09-26
NZ235754A (en) 1993-03-26
EP0496782A4 (en) 1993-02-03
AU6537690A (en) 1991-05-16
EP0496782A1 (de) 1992-08-05
DE69026105D1 (de) 1996-04-25

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