EP0351330A1 - Verfahren zur Herstellung von gebleichten chemithermomechanischen Zellstoffen - Google Patents

Verfahren zur Herstellung von gebleichten chemithermomechanischen Zellstoffen Download PDF

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Publication number
EP0351330A1
EP0351330A1 EP19890420245 EP89420245A EP0351330A1 EP 0351330 A1 EP0351330 A1 EP 0351330A1 EP 19890420245 EP19890420245 EP 19890420245 EP 89420245 A EP89420245 A EP 89420245A EP 0351330 A1 EP0351330 A1 EP 0351330A1
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EP
European Patent Office
Prior art keywords
bleaching
treatment
pulp
bleached
dough
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Granted
Application number
EP19890420245
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English (en)
French (fr)
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EP0351330B1 (de
Inventor
Michel Devic
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Arkema France SA
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Elf Atochem SA
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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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D21C3/06—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides sulfur dioxide; sulfurous acid; bisulfites sulfites
    • 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
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the invention relates to the manufacture of bleached chemothermal-mechanical pulps.
  • chemothermal mechanical pulps designated in all that follows by CTMP pastes, is meant the pastes which result from the application to a lignocellulosic material, generally wood in the form of chips, of a treatment using one or more chemical agents combined with heating and mechanical defibration operations.
  • CTMP pastes are of certain industrial interest because they achieve an interesting compromise between mechanical and chemical pulps themselves.
  • the treatment can take place before, during or after defibration.
  • treatment is meant here and in all that follows, the operation during which the lignocellulosic material is present with a sulfite, in practice sodium sulfite Na2SO3, or a bisulfite, in practice sodium bisulfite NaHSO3, or more generally a mixture of sulfur dioxide SO2 and sodium hydroxide NaOH, at a temperature equal to or higher than 100 ° C., under saturated steam pressure, said sulfite, bisulfite or mixture being indifferently designated by sulfite in all following.
  • the treatment includes, where appropriate, a conventional impregnation of the lignocellulosic material using a solution of the selected reagents.
  • the temperature at which the treatment is carried out generally does not exceed 200 ° C. and is preferably between approximately 120 ° C. and 160 ° C.
  • the treatment medium has an initial pH generally chosen preferably between 6 and 12.5.
  • the consistency, concentration by weight of paste expressed in the dry state in the medium is, in the treatment, for example between 10% and 40%, most often between 15% and 30%.
  • the duration of the treatment depends on the choice of other parameters but generally does not exceed 1 hour.
  • the amount of sulfite is for example between about 0.1% and 10%, most often between 0.5% and 3%, the percentages being given by weight relative to the weight of the lignocellulosic material considered at the dry state, as will be the case, unless otherwise specified or evident, for the percentages of material in all that follows.
  • Chemical agents can be used in the treatment at the same time as the sulphite, such as for example complexing or sequestering agents such as diethylenetriaminepentaacetic acid (DTPA) or ethylenetriaminetetraacetic acid (EDTA) used in the form of sodium salts in an amount generally between approximately 0.1% and 1%.
  • complexing or sequestering agents such as diethylenetriaminepentaacetic acid (DTPA) or ethylenetriaminetetraacetic acid (EDTA) used in the form of sodium salts in an amount generally between approximately 0.1% and 1%.
  • CTMP pasta for example to the work of James P. CASEY, PULP & PAPER CHEMISTRY & CHEMICAL TECHNOLOGY, 3rd edition, vol.I, 1980, in particular pages 241-245, 213-219-229, to the work PULP & PAPER MANUFACTURE, VOL. 2, 1987 - MECHANICAL PULPING -, in particular chapters VIII D and XI, or even to the patent of the United States of America n ° 4718980 in particular figure 1 .
  • bleached CTMP pulps here the CTMP pulps defined above, after they have been bleached using hydrogen peroxide H2O2 in an alkaline medium.
  • the dough before being bleached with hydrogen peroxide, must be as far as possible free of chemical agent (s) such as sulphite ions, which it is known that they must cause consumption of H2O2 harmful to money laundering as indicated for example by H. KRUGER, HUSUSS, TAPPI PROCEEDINGS, 1982 INTERNATIONAL SULFITE PULPING CONFERENCE, 143-148.
  • chemical agent such as sulphite ions
  • the dough is carefully washed before being bleached, and this washing is conventionally carried out, for example by virtue of a repeated or not a sequence of dilution and reconcentration of the dough.
  • Reconcentrating the whitening dough to a consistency at least equal to approximately 10%, starting from values which are very low, is an operation which the known technique requires not only to effectively eliminate the chemical agent or agents considered to be undesirable in bleaching. but also so that the hydrogen peroxide, in the very absence of these compounds, has a satisfactory effectiveness.
  • the whitening of the CTMP pulp using hydrogen peroxide in an alkaline medium is usually carried out by using an amount of hydrogen peroxide of between approximately 0.5% and 10%, in the presence of approximately 1% to 6 % of a sodium silicate solution of density 1.33, at a pH between about 9 and 11, at a temperature between about 40 ° C and 100 ° C for about 0.5 to 2 hours, with a consistency included between about 10% and 30%.
  • the bleaching bath can contain additives such as mainly one or more sequestering or complexing agents, such as for example DTPA, in an amount generally between approximately 0.1% and 1%.
  • the dough After bleaching the dough is preferably treated with an acid such as SO2 to stabilize its whiteness, before being diluted with water to a very low consistency, for example of the order of 1%, to allow its transfer, storage and use in stationery.
  • an acid such as SO2
  • aqueous effluents coming mainly from washing operations, classification, separation of the final dilution water before or during the manufacture of the paper, depending on whether or not this manufacture is integrated into the manufacture of pulp, which contain practically no more sulphite but a still high pollutant load, are necessarily recycled and serve in particular as a pulp washing agent to remove the sulphite before bleaching with hydrogen peroxide.
  • the present invention makes it possible to avoid the above drawbacks of the known industrial technique for manufacturing bleached CTMP pastes, without the white level of these pastes being felt, on the contrary.
  • a process for manufacturing bleached CTMP pulps which comprises a treatment in which the lignocellulosic material is present with the sulphite at a temperature equal to or greater than 100 ° C. under saturated steam pressure, and a bleaching using hydrogen peroxide in an alkaline medium, characterized in that solid or liquid material is not removed from the pulp from the start of said treatment until the end of said bleaching.
  • the reducing agent is most often chosen from thiourea dioxide or formamidinesulfinic acid, sodium hydrolsulfite or dithionite, or sodium borohydride.
  • the amount of reducing agent used can vary depending on the nature thereof. It is generally understood, for the first two cited between about 0.1% and 5% and between about 0.01% and 0.5% for the third that is conveniently used in the form of an aqueous solution as for example the solution containing 12% by weight of sodium borohydride and marketed under the name of BOROL® by the company VENTRON Corporation.
  • the invention finds all its interest in practice when it is aimed at obtaining CTMP pulps bleached to a high degree of white, for example 80 ° and more when it is measured in the usual way today at the length d wave of 457 nm with magnesium oxide as a reference standard using the spectrophotometer of the General Electric or Elrepho type.
  • the amount of sulfite expressed as SO2 is then preferably between approximately 0.5% and 3% and the amount of hydrogen peroxide preferably between 3% and 10%, most often between 4% and 6%.
  • Another object of the invention is a method according to the invention in which the bleached CTMP pulp is refined directly at the outlet of the bleaching. This refining is carried out at atmospheric pressure.
  • the invention is therefore also a process for manufacturing bleached CTMP doughs, according to what has already been presented of said invention, characterized in that the bleached CTMP dough is refined directly after bleaching and therefore in that it is not removed from solid or liquid matter from the dough from the start of treatment until the end of refining after bleaching.
  • the classification can thus be carried out on bleached and refined pulp. Dilute with clear industrial water and recycle the classification refusals to the bleached pulp refiner is then done without inconvenience.
  • the method of the invention in which there is no need to reheat the dough, makes it possible to dispense with a supply of calories from a source external to the system provided that the conservation of the calories of the system is sufficiently well ensured .
  • the process of the invention compared to known techniques, therefore saves mechanical as well as thermal energy.
  • the invention applies to softwoods or softwoods, such as hardwoods or hardwoods.
  • the wood shavings are conveyed from the feed hopper 101 to 102, a chamber for preheating the shavings with steam introduced by 103, from which they come out to pass with the solution of the reagents introduced by 104, into the refiner 105 then into the cyclone 106 from which water vapor is separated by 107.
  • the dough passes through the latency zone 108 before being intimately mixed with the bleaching reagents supplied by 109, to be bleached in the bleaching tower 110.
  • the bleached pulp leaving 110 is directly brought into the refiner at atmospheric pressure 111 from which it leaves to be classified in 112 after dilution by clear industrial water introduced by 113.
  • Refusals of classification sufficiently reconcentrated, are refined separately (circuit not shown) or recycled by 114 at the entrance of the refiner 111.
  • the dough is acidified ée in a known manner and sent to storage 115 and / or to the manufacture of paper by 116.
  • the means indexed with 2 in hundred correspond in structure and in function to those of FIG. 1 indexed with 1 in hundred.
  • the additional means 217 is a thickening equipment, for reconcentrating the dough between its classification in 212 and its bleaching in 210.
  • the aqueous effluent collected from 217 by 218 contributes to forming the clear industrial water which is introduced par 213 to serve as a paste washing agent.
  • - by DTPA is designated an aqueous solution at 40% by weight of sodium salt of diethylenetriaminepentaacetic acid and the amount of DTPA is that of this solution
  • - by washing is designated the operation combining dilution and pressing of the dough
  • - sodium borohydride is applied in the form of BOROL® and the quantity indicated is that of this presentation
  • - by silicate is designated an aqueous solution of sodium silicate with a density equal to 1.33
  • - the degree of white is measured at the wavelength of 457 nm with magnesium oxide as a reference standard using a spectrophotometer of ELREPHO type manufactured by KARL ZEISS.
  • Softwood shavings are refined under saturated steam pressure at 120 ° C with 2.75% Na2SO2 to yield a paste with a white degree of 57 °.
  • This paste is bleached, without removing any liquid or solid material, using H2O2: 5%, NaOH: 2%, silicate: 4%, DTPA: 0.5%, for 2 hours at 90 ° C at a consistency of 15%.
  • the bleached pulp obtained has a white degree of 77.9 °.
  • the dough is washed by dilution to a consistency of 1.25% using industrial white water taken from an industrial plant with reconcentration by pressing up to a consistency of 20% so that 95% of the sulphite is removed before adding the bleaching reagents in aqueous solution, its degree of white after bleaching is 77.4 °. It is therefore lower than that achieved by conforming to the invention.
  • a mechanical softwood pulp pulp, the degree of white of which is equal to 53.7 ° is subjected to a pressure treatment of saturated steam at 120 ° C with 2.75% Na2SO3 and 0.5% of DTPA for 30 minutes at a consistency of 20%, before being bleached directly, without elimination of solid or liquid material, as in Example 1.
  • the bleached pulp obtained has a degree of white equal to 78.7 °
  • the dough is bleached after washing with industrial white water as in Example 1, its degree of white is 78.6 ° and is still lower, at most equal to that achieved by operating according to the invention.
  • Example 2 and the comparison which it includes, is repeated with the difference that 1% of BOROL® is present with the sulfite.
  • the degree of white of the bleached pulp is equal to 82.2 ° while it is only 80.9 ° in the comparison.
  • the degree of white of the bleached pulp is only 1 ° higher than that achieved by proceeding according to the invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Seasonings (AREA)
  • Glass Compositions (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
EP89420245A 1988-07-12 1989-07-06 Verfahren zur Herstellung von gebleichten chemithermomechanischen Zellstoffen Expired - Lifetime EP0351330B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8809703 1988-07-12
FR8809703A FR2634233B1 (fr) 1988-07-12 1988-07-12 Procede de fabrication de pates chimicothermomecaniques blanchies

Publications (2)

Publication Number Publication Date
EP0351330A1 true EP0351330A1 (de) 1990-01-17
EP0351330B1 EP0351330B1 (de) 1998-09-30

Family

ID=9368520

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89420245A Expired - Lifetime EP0351330B1 (de) 1988-07-12 1989-07-06 Verfahren zur Herstellung von gebleichten chemithermomechanischen Zellstoffen

Country Status (12)

Country Link
EP (1) EP0351330B1 (de)
JP (1) JPH0268377A (de)
AT (1) ATE171741T1 (de)
AU (1) AU616541B2 (de)
CA (1) CA1335406C (de)
DE (2) DE68928822T2 (de)
ES (1) ES2012324T3 (de)
FI (1) FI96522C (de)
FR (1) FR2634233B1 (de)
NO (1) NO176726C (de)
NZ (1) NZ229902A (de)
PT (1) PT91128B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509905A1 (de) * 1991-04-17 1992-10-21 Elf Atochem S.A. Verfahren zur Herstellung von gebleichtem Hochausbeutepapierzellstoff
EP1258559A1 (de) * 2001-05-09 2002-11-20 Rohm And Haas Company Verfahren zum bleichen von mechanischen Pulpe

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2615874B1 (fr) * 1987-05-25 1992-02-21 Atochem Procede de preparation de pates chimicothermomecaniques
JP4501329B2 (ja) * 2002-03-29 2010-07-14 日本製紙株式会社 グラビア印刷用塗工紙
JP5371955B2 (ja) * 2007-04-24 2013-12-18 ビーエーエスエフ ソシエタス・ヨーロピア 漂白された木材粒子及び淡色ないし白色の木材料の製造方法
US20100224333A1 (en) * 2009-03-09 2010-09-09 Prasad Duggirala Method and chemical composition to improve efficiency of mechanical pulp
US9932709B2 (en) 2013-03-15 2018-04-03 Ecolab Usa Inc. Processes and compositions for brightness improvement in paper production
EP2924166A1 (de) 2014-03-25 2015-09-30 Basf Se Verfahren zur Herstellung von gebleichtem Holzfaserstoff

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE834808C (de) * 1950-08-31 1952-03-24 Degussa Verfahren zum Bleichen von mechanisch erzeugten, schwer bleichbaren Faserstoffen, insbesondere Holzschliff
FR1389308A (fr) * 1964-02-17 1965-02-12 Fmc Corp Pâtes cellulosiques à grand brillant
FR2389712A1 (de) * 1977-05-02 1978-12-01 Mo Och Domsjoe Ab
EP0172135A1 (de) * 1984-07-17 1986-02-19 Rudy Vit Weise, Verfahren und Vorrichtung zur Verwandlung von Holz, Holzrückständen, Pflanzenfasern und Biomassen in Pulpe
US4718980A (en) * 1985-12-30 1988-01-12 Weyerhaeuser Company Interstage treatment of mechanical pulp

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2615874B1 (fr) * 1987-05-25 1992-02-21 Atochem Procede de preparation de pates chimicothermomecaniques
SE460124B (sv) * 1988-09-14 1989-09-11 Sunds Defibrator Saett foer framstaellning av kemimekanisk massa av loevved

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE834808C (de) * 1950-08-31 1952-03-24 Degussa Verfahren zum Bleichen von mechanisch erzeugten, schwer bleichbaren Faserstoffen, insbesondere Holzschliff
FR1389308A (fr) * 1964-02-17 1965-02-12 Fmc Corp Pâtes cellulosiques à grand brillant
FR2389712A1 (de) * 1977-05-02 1978-12-01 Mo Och Domsjoe Ab
EP0172135A1 (de) * 1984-07-17 1986-02-19 Rudy Vit Weise, Verfahren und Vorrichtung zur Verwandlung von Holz, Holzrückständen, Pflanzenfasern und Biomassen in Pulpe
US4718980A (en) * 1985-12-30 1988-01-12 Weyerhaeuser Company Interstage treatment of mechanical pulp

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAPPI JOURNAL, vol. 68, no. 2, février 1985, pages 64-68, Easton, Pennsylvania, US; N. JACKSON et al.: "Chemithermomechanical pulp production and end-uses in Scandinavia" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509905A1 (de) * 1991-04-17 1992-10-21 Elf Atochem S.A. Verfahren zur Herstellung von gebleichtem Hochausbeutepapierzellstoff
FR2675518A1 (fr) * 1991-04-17 1992-10-23 Atochem Procede de preparation de pate a papier a haut rendement et blanchie, a partir de copeaux de bois.
EP1258559A1 (de) * 2001-05-09 2002-11-20 Rohm And Haas Company Verfahren zum bleichen von mechanischen Pulpe

Also Published As

Publication number Publication date
FI96522B (fi) 1996-03-29
PT91128B (pt) 1994-12-30
ES2012324T3 (es) 1998-11-16
DE68928822T2 (de) 1999-05-27
FI893372A0 (fi) 1989-07-11
CA1335406C (fr) 1995-05-02
AU3799989A (en) 1990-01-18
JPH0268377A (ja) 1990-03-07
AU616541B2 (en) 1991-10-31
FI893372A (fi) 1990-01-13
EP0351330B1 (de) 1998-09-30
DE68928822D1 (de) 1998-11-05
FI96522C (fi) 1996-07-10
NO892805D0 (no) 1989-07-06
NO176726C (no) 1995-05-16
NO176726B (no) 1995-02-06
PT91128A (pt) 1990-02-08
NO892805L (no) 1990-01-15
ES2012324A4 (es) 1990-03-16
ATE171741T1 (de) 1998-10-15
NZ229902A (en) 1991-09-25
JPH0250236B2 (de) 1990-11-01
FR2634233B1 (fr) 1995-04-14
FR2634233A1 (fr) 1990-01-19
DE351330T1 (de) 1990-06-13

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