WO1994020670A1 - Production de materiaux ligneux chimiomecaniques et/ou chimiothermomecaniques - Google Patents

Production de materiaux ligneux chimiomecaniques et/ou chimiothermomecaniques Download PDF

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Publication number
WO1994020670A1
WO1994020670A1 PCT/EP1994/000627 EP9400627W WO9420670A1 WO 1994020670 A1 WO1994020670 A1 WO 1994020670A1 EP 9400627 W EP9400627 W EP 9400627W WO 9420670 A1 WO9420670 A1 WO 9420670A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
raw materials
lignocellulose
wood
solution
Prior art date
Application number
PCT/EP1994/000627
Other languages
German (de)
English (en)
Inventor
Rudolf Patt
Jens Neumann
Original Assignee
Stora Feldmühle Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stora Feldmühle Ag filed Critical Stora Feldmühle Ag
Priority to DE59400830T priority Critical patent/DE59400830D1/de
Priority to EP94910362A priority patent/EP0688373B1/fr
Priority to JP6519572A priority patent/JPH08507333A/ja
Publication of WO1994020670A1 publication Critical patent/WO1994020670A1/fr
Priority to NO953389A priority patent/NO953389D0/no
Priority to FI954231A priority patent/FI954231A0/fi

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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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/04—Pretreatment of the finely-divided materials before digesting with acid reacting compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/14—Disintegrating in mills
    • D21B1/16—Disintegrating in mills in the presence of chemical agents
    • 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

Definitions

  • the invention relates to a method according to the preamble of claim 1 for the production of chemo-mechanical and / or chemo-thermo-mechanical wood materials from raw materials containing lignocellulose, such as wood chips, wood chips, pre-fiberized wood or sawdust.
  • a major disadvantage of wood pulp is the low binding capacity of lignin fibers.
  • Lignin as a hydrophobic substance has hardly any starting points for hydrogen bonds. Sulphonation of lignin increases its hydrophilicity and thus the binding potential of lignin-containing fibers.
  • sulfonation is also the first step in dissolving the lignin, for which a minimum degree of sulfonation must be achieved.
  • a solution of sodium sulfite is used for the sulfonation can sulfonate the so-called A ⁇ and Ay groups of the lignin, of which only between 15 and 30 mol% are present in the lignin (SARydholm, Pulping Processes, Intersciences Publishers, New York, London, Sydney, 1965).
  • the lignin is sulfonated by
  • the sulfonation of the lignin requires a certain temperature level.
  • the rate of sulfonation increases with falling pH.
  • lignin condensation occurs, which not only prevent sulfonation, but also cause the lignin to turn dark. Therefore, the reaction temperatures in acid sulfite processes can be limited (maximum 140 ° C), or the pH value and the bisulfite concentration can be increased through increased use of bases.
  • PCT-WO 91/19040 teaches that wood can be sulfonated in the gas phase, the sulfonation with SO 2 taking place below 100.degree. Then the wood chips are treated with alkaline solutions and the temperature raised to a maximum of 130 ° C so that no carbohydrate breakdown takes place in the wood. Jayme et al. however, higher temperatures up to 180 ° C apply in the vapor phase digestion. However, you have to increase the amount of base considerably and work with bisulfite solutions with a pH of around 4 (G. Jayme, L. Broschinsky and W. Matzke. Paper 1_8, 7, 308-314, 1964. G. Jayme and W. Matzke. Wbl. Textilfabrik. 11/12, 311-314, 1964).
  • Object of the present invention is now ulfitten a CTMP-making process using acid S to develop, which does not require methanol and with minimal amounts of base metal.
  • the solution according to the invention surprisingly shows that, contrary to the prior art, sulfonation can take place under the selected conditions at high temperatures without lignin condensation reactions, in particular with regard to the whiteness of the lignocellulose-containing raw material to be treated, resulting in reaction products colored dark or black.
  • lignocellulose-containing raw materials in particular wood chips
  • the wood chips saturated with the impregnation solution are then very quickly heated to a reaction temperature of 130 to 180 ° C. and left at this temperature and a low pH in the gas phase for a period of 2 to 15 minutes.
  • the wood chips are removed from the reaction chamber, the excess Sulfur dioxide gas is withdrawn from the reaction material.
  • the wood chips are fed to a defibrating device known per se, where the reaction material is defibrated to a preselected degree of fineness by means of preselected specific grinding work from 1,200 to 1,900 kWh / t of fiber.
  • a major advantage of pretreatment with acidic sulfite solution is the easy recovery of S0 2 . Since only small amounts of base are required, the chemical loss is low: After the pretreatment of the wood, the S0 2 can , if it is not chemically bound to the wood or irreversibly bound to the base, in a degassing step, u. U. can also be recovered with the support of a vacuum.
  • the specific grinding energy can be reduced by 40% compared to conventional pretreatment without increasing yield losses.
  • the wood chips are impregnated until they are saturated at a temperature ⁇ 100 ° C. This has the advantage that when using solutions with a high sulfur dioxide content, the partial pressure of the SO 2 gas is still relatively low, so that no great demands are placed on the impregnation vessel with regard to pressure resistance.
  • the impregnation solution itself contains 1 - 34 g / 1 base and 20 - 145 g / 1 S0 2 , depending on the impregnation conditions.
  • gaseous S0 2 is additionally pressed into the closed impregnation or reaction vessel.
  • a further measure for obtaining the desired degree of impregnation consists in the selection of the dry content of the wood chips before the impregnation, which can be adjusted, for example, by treatment with a screw press to squeeze out water.
  • S0 2 in high concentration is fundamental in this process. It is important to use a high concentration of free S0 2 compared to the amount of base used.
  • MgO is advantageously used as the base. It is also possible to use other bases based on sodium, calcium or ammonium which are customary in sulfite technology. However, MgO has the advantage of simple handling in the process and a low price.
  • the necessary reaction time is not only a function of the amount of chemicals used, but also of the temperature. After the impregnation, the wood chips are transferred directly into the gas phase of the reactor, where the reaction takes place. The desired sulfonation rates are only achieved if the temperature in the reaction area is sufficiently high.
  • Spruce wood chips (industrial waste wood) are acidified at room temperature
  • the volume of the gas phase is 35 l.
  • the chips are removed from the reactor, suspended in hot water at 80 ° C., filled into a defibrator and defibrated under a steam atmosphere at 130 ° C. and 20% consistency.
  • the defibrator coarse material is then ground in a laboratory refiner under atmospheric pressure.
  • 1,730 kWh / t of grinding energy are required, while for spruce wood chips that have been pretreated with 5% Na 2 S0 3 / otro wood at 130 ° C, 2,660 kWh / t are required to achieve this degree of grinding.
  • the conventional CTMP reaches a breaking length of 6,060, the acid pretreatment achieves a breaking length of 6,380 m.
  • Spruce wood chips (industrial waste wood) are impregnated as described in Example 1.
  • the solution contains 68 g S0 2/1 and 10 g of MgO /. 1
  • the wood chips absorb 1.7% MgO / otro wood and 13% S0 2 / otro wood.
  • a treatment is then carried out as described in Example 1.
  • the reaction temperature is 157 ° C for 6 minutes.
  • 2,040 kWh / t are used to achieve 75 ° SR.
  • the tear length is then 6,540 m. To achieve a tearing length of 5,000 m, 1,150 kWh / t grinding energy is used.
  • the energy saving compared to conventional CTMP is 39%.
  • Spruce wood chips (industrial waste wood) are impregnated as described in Example 1.
  • the solution contains 30 g S0 2/1 and 1.7 g Mg ⁇ /. 1
  • the wood chips absorb 0.4% MgO / otro wood and 4.1% S0 2 / otro wood.
  • the further treatment is carried out as in Example 1.
  • the spec. Grinding energy to reach 50 ° SR is 1,189 kWh / t.
  • a tear length of 4,800 m is achieved. After pretreatment with 5% Na 2 S0 3 / otro wood, 1,750 kWh / t grinding energy is required to achieve this degree of grinding.
  • the tear length is then 4,720 m.
  • Spruce wood chips (industrial waste wood) are impregnated as described in Example 1.
  • the solution contains 50 g S0 2/1 and 16.7 g Mg ⁇ /. 1
  • the wood chips absorb 3.1% MgO / otro wood and 11% S0 2 / otro wood.
  • the further treatment is carried out as in Example 1.
  • 1,650 kWh / t are used for grinding to 75 ° SR.
  • 3,640 kWh / t grinding energy is required. If the same grinding energy is used, a tearing length of 7.170 is achieved after treatment with 5% Na 2 S0 3 / otro wood.
  • Spruce wood chips (industrial waste wood) are impregnated as described in Example 1.
  • the solution contains 68 g S0 2/1 and 14 g Ca ⁇ /. 1
  • a treatment is then carried out as described in Example 1.
  • the reaction temperature is 157 ° C for 6 minutes.
  • 1,380 kWh / t are used to achieve 75 ° SR.
  • the tear length is then 5,190 m.
  • 1,330 kWh / t grinding energy is used. This saves energy compared to conventional CTMP 29%.
  • Spruce wood chips (industrial waste wood) are impregnated as described in Example 1.
  • the solution contains 68 g S0 2/1 and 20 g NaOH /. 1
  • a treatment is then carried out as described in Example 1.
  • the reaction temperature is 157 ° C for 6 minutes.
  • 1,770 kWh / t are used to achieve 75 ° SR.
  • the tear length is then 5,810 m.
  • 1,350 kWh / t grinding energy is used.
  • the energy saving compared to conventional CTMP is 28%.
  • the physical properties of the fiber materials obtained are summarized in Table 1.
  • the white contents of the acidic magnesium bisulfite substances are 5 to 10% higher than when using Na 2 S0 3 , so that when these substances are used in graphic printing papers, additional bleaching can either be completely omitted or can be carried out with considerably less chemicals can.
  • the strength potential of the fiber materials produced by the process according to the invention is close to that of conventional cellulose materials, so that these are at least z. T. can be replaced. Table 1

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Processing Of Solid Wastes (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Debarking, Splitting, And Disintegration Of Timber (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Selon un procédé de production de matériaux ligneux chimiomécaniques et/ou chimiothermomécaniques à partir de matières premières lignocellulosiques, telles que des copeaux de bois, on imprègne les matières premières d'une solution contenant du SO2 puis on les soumet à une réaction de sulfonation dans une phase gazeuse ou vapeur à une valeur de pH égale ou inférieure à 2. Une fois la réaction de sulfonation achevée, les matières premières ou copeaux de bois sont défibrés dans une unité de défibrage connue en soi et broyés jusqu'à un degré de finesse présélectionné. Les matériaux ligneux ainsi obtenus se caractérisent par une solidité remarquable et par le fait qu'ils nécessitent une énergie de broyage spécifique réduite.
PCT/EP1994/000627 1993-03-11 1994-03-03 Production de materiaux ligneux chimiomecaniques et/ou chimiothermomecaniques WO1994020670A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE59400830T DE59400830D1 (de) 1993-03-11 1994-03-03 Herstellung chemo-mechanischer und/oder chemo-thermo-mechanischer holzstoffe
EP94910362A EP0688373B1 (fr) 1993-03-11 1994-03-03 Production de pates a papier chimio-mecaniques et/ou chimio-thermo mecaniques
JP6519572A JPH08507333A (ja) 1993-03-11 1994-03-03 ケミカル・メカニカル及び／又はケミカル・サーモ・メカニカルパルプの製法
NO953389A NO953389D0 (no) 1993-03-11 1995-08-29 Fremstilling av kjemimekaniske og kjemitermomekaniske masser
FI954231A FI954231A0 (fi) 1993-03-11 1995-09-08 Menetelmä kemimekaanisten ja/tai kemitermomekaanisten puumassojen valmistamiseksi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4307660.2 1993-03-11
DE4307660A DE4307660C1 (de) 1993-03-11 1993-03-11 Herstellung chemo-mechanischer und/oder chemo-thermo-mechanischer Holzstoffe

Publications (1)

Publication Number Publication Date
WO1994020670A1 true WO1994020670A1 (fr) 1994-09-15

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ID=6482482

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000627 WO1994020670A1 (fr) 1993-03-11 1994-03-03 Production de materiaux ligneux chimiomecaniques et/ou chimiothermomecaniques

Country Status (10)

Country Link
EP (1) EP0688373B1 (fr)
JP (1) JPH08507333A (fr)
AT (1) ATE144011T1 (fr)
CA (1) CA2157886A1 (fr)
DE (2) DE4307660C1 (fr)
DK (1) DK0688373T3 (fr)
ES (1) ES2095755T3 (fr)
FI (1) FI954231A0 (fr)
NO (1) NO953389D0 (fr)
WO (1) WO1994020670A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009057208A1 (de) * 2009-11-27 2011-06-01 Technische Universität Dresden Verfahren zur Herstellung von lignozellulosen Papierfaserstoffen sowie daraus gewonnene Papiere, Kartone und Pappen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH430421A (de) * 1963-05-21 1967-02-15 Defibrator Ab Verfahren zur chemisch-mechanischen Herstellung von Faserstoffen durch Erhitzung und Zerfaserung von mit Sulfitlösungen imprägniertem, lignozellulosehaltigem Material in Dampfatmosphäre unter Druck und bei erhöhter Temperatur
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
WO1991005102A1 (fr) * 1989-09-28 1991-04-18 Feldmühle Aktiengesellschaft Procede pour fabriquer des pates chimio-mecaniques et/ou chimio-thermo-mecaniques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2445523A1 (de) * 1974-09-24 1976-04-01 Waldhof Aschaffenburg Papier Verfahren zur herstellung von zellstoff
SE404044B (sv) * 1975-11-13 1978-09-18 Mo Och Domsjoe Ab Ljusabsorberande lignirik hogutbytescellulosamassa samt forfarande for framstellning av denna
US4634499A (en) * 1983-05-02 1987-01-06 The Procter & Gamble Company Sulfite process for making pulp having a tactile softness from hardwood chips
SE9002039D0 (sv) * 1990-06-07 1990-06-07 Svenska Traeforskningsinst Saett att framstaella massa

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH430421A (de) * 1963-05-21 1967-02-15 Defibrator Ab Verfahren zur chemisch-mechanischen Herstellung von Faserstoffen durch Erhitzung und Zerfaserung von mit Sulfitlösungen imprägniertem, lignozellulosehaltigem Material in Dampfatmosphäre unter Druck und bei erhöhter Temperatur
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
WO1991005102A1 (fr) * 1989-09-28 1991-04-18 Feldmühle Aktiengesellschaft Procede pour fabriquer des pates chimio-mecaniques et/ou chimio-thermo-mecaniques

Also Published As

Publication number Publication date
DK0688373T3 (da) 1997-03-24
EP0688373A1 (fr) 1995-12-27
EP0688373B1 (fr) 1996-10-09
ES2095755T3 (es) 1997-02-16
DE59400830D1 (de) 1996-11-14
CA2157886A1 (fr) 1994-09-15
FI954231A (fi) 1995-09-08
FI954231A0 (fi) 1995-09-08
NO953389L (no) 1995-08-29
DE4307660C1 (de) 1994-08-04
ATE144011T1 (de) 1996-10-15
NO953389D0 (no) 1995-08-29
JPH08507333A (ja) 1996-08-06

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