EP0791099B1 - Cellulose extraction process - Google Patents

Cellulose extraction process Download PDF

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Publication number
EP0791099B1
EP0791099B1 EP95939246A EP95939246A EP0791099B1 EP 0791099 B1 EP0791099 B1 EP 0791099B1 EP 95939246 A EP95939246 A EP 95939246A EP 95939246 A EP95939246 A EP 95939246A EP 0791099 B1 EP0791099 B1 EP 0791099B1
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Prior art keywords
radicals
sio
univalent
pulp
units
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EP95939246A
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German (de)
French (fr)
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EP0791099A1 (en
Inventor
Willibald Burger
Outi Neubig
Kimmo Lappalainen
Hannu Wahlberg
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Wacker Chemie AG
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Wacker Chemie AG
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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
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes

Definitions

  • the invention relates to a method for the production of pulp from fibrous materials, in which organosilicon compounds be added to the chemical digestion process.
  • lignin a polymer made up of hydroxyphenylpropane units.
  • lignin a polymer made up of hydroxyphenylpropane units.
  • organic surfactants are added.
  • organic surfactants are added.
  • For example is from US-A-3,909,345 the use of ethylene oxide / propylene oxide block copolymers and from US-A-5,250,152 the use of ethoxylated alcohols and ethoxylated Dialkylphenols known in the alkaline sulfate process.
  • GB-A-951 325 describes a process for the production of Pulp, in which the pulp with a chemical Digestion solution in the presence of organopolysiloxane or Organosilane compounds are implemented.
  • the task was to develop an improved method Obtaining pulp from fiber by a chemical To provide digestion procedures.
  • a particular Residual lignin content in the pulp requires less digestion solution.
  • a measure of the residual lignin content in the pulp is Kappa number, which is the normal consumption of milliliters 0.1 (3.161 g / l) potassium permanganate solution per gram of pulp.
  • the reduction in digestion solution causes an increase the pulp yield based on the fiber used, because fewer carbohydrates, especially hemicelluloses, are released and there are fewer by-products.
  • a certain number of kappa can be used when using the organosilicon compounds can also be achieved by the cooking time is shortened.
  • the kappa number is below constant digestion conditions decreased.
  • organosilicon compounds lead to a higher one Yield and smaller amounts of undigested Fibrous materials.
  • the organosilicon compounds also improve the strength values of pulp and reduce cellulose breakdown.
  • Preferred organosilicon compounds are organic siloxanes and silanes, which are an organic polar group and have a hydrophobic siloxane or sil content and thereby surface-active properties at the phase boundaries have liquid / liquid, liquid / gaseous and liquid / solid.
  • the formula range [O (CR 2 ) a ] b can be a polyethylene glycol / polypropylene glycol block copolymer.
  • hydrocarbon radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo Pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octt
  • radicals R are methyl, Ethyl or phenyl radicals, especially methyl radicals.
  • divalent radicals R 1 are saturated straight-chain or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and also propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene radicals, or unsaturated alkylene or arylene radicals such as Hexenylene and phenylene.
  • hydrocarbon radicals on the ammonium ions in X are the hydrocarbon radicals mentioned for R.
  • Examples of the C 1 - to C 6 -acyl radicals R 3 are the acetyl, propionyl and n-butyryl radical.
  • glycoside residues Z examples include hexoses and pentoses, such as glucose, fructose, galactose, mannose, talose, allose, old rose, idose, arabinose, xylose, lyxose and ribose, with glucose being particularly preferred.
  • the glycoside residues Z preferably contain one or two monosaccharide units.
  • a is 2 or 3.
  • R b represents integer values from 3 to 100, in particular 10 to 70 wt.
  • the organopolysiloxane compound Preferably at least 95%, especially at least 99% of the units of the organopolysiloxane compound units of the general formulas (II), (VI) and (I). Still is preferred that the organopolysiloxane compound have an average Viscosity from 20 to 500,000 mPa.s, in particular from 200 to 60,000 mPa.s at 25 ° C.
  • organosilicon compound it can also be mixtures several organosilicon compounds are used.
  • Dry fibers are preferred per 100 parts by weight 0.001 to 1, especially 0.01 to 0.1 parts by weight Organosilicon compounds used.
  • the sulfate process is preferably used.
  • the process preferably contains 10 to 35, in particular 20 to 30 parts by weight of Na 2 O in the form of NaOH per 100 parts by weight of dry wood.
  • the process is preferably carried out at 0.1 to 3 MPa, in particular at 0.5 to 1.5 MPa.
  • the chemical processes can be batch or continuous be carried out in a pulp cooker.
  • the residence time of the mixture in the pulp cooker is preferably 10 min to 7 h.
  • all of them can be used as fiber materials vegetable raw materials (fiber plants) that are sufficient Have cellulose content and are sufficiently light processed.
  • Woods are preferably used, with many in countries today also on a large scale in the sawmills resulting wood waste is used as a raw material. Besides However, certain annual plants and grasses also play a role subordinate role.
  • the wood is in the form of, for example, wood chips, Chips or wood flour used.
  • a polyglycol ether-functional water-soluble silicone surfactant (Pulpsil® 950 S from Wacker-Chemie GmbH, Kunststoff) was used as the organosilicon compound.
  • the resulting organosilicon compound is represented by the formula (XV) (H 3 C) 3 SiO [(H 3 C) 2 SiO] 75 [Y (CH 3 ) SiO] 5 Si (CH 3 ) 3 , where Y is the formula (XVI) - (H 2 C) 3 O [CH 2 CH 2 O] 25 [CH 2 CH (CH 3 ) O] 25 H has marked.
  • a continuous pulp cooker with a capacity of 270 tons of dry wood substance in the form of sawdust per day was operated at 172 ° C and 0.95 MPa.
  • the residence time of the mixture in the cooker was 15 minutes.
  • 28 parts by weight of Na 2 O and 7 parts by weight of Na 2 S were present per 100 parts by weight of dry wood.
  • the pulp obtained had a kappa number of about 52.
  • the amount of Na 2 O was then reduced to 25 parts by weight per 100 parts by weight of dry wood.

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  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicon Polymers (AREA)

Abstract

In a process for extracting cellulose from fibrous materials such as wood, the fibrous materials are reacted with a chemical disintegration solution in the presence of organosilicic compounds.

Description

Die Erfindung betrifft ein Verfahren zur Gewinnung von Zellstoff aus Faserstoffen, bei dem Organosiliciumverbindungen dem chemischen Aufschlußverfahren zugesetzt werden.The invention relates to a method for the production of pulp from fibrous materials, in which organosilicon compounds be added to the chemical digestion process.

Die in Faserstoffen, wie Holz enthaltenen Cellulosefasern und Hemicellulosefasern werden durch Lignin, ein Polymer, aufgebaut aus Hydroxyphenylpropaneinheiten, zusammengehalten. Bei der Gewinnung von Zellstoff, einer mehr oder minder verunreinigten Cellulose, wird Lignin von der Cellulose getrennt. Das weitaus wichtigste Verfahren zur Gewinnung von Zellstoff aus Faserstoffen ist das als alkalischer sulfatprozeß oder Kraftprozeß bezeichnete Verfahren, bei dem Lignin durch eine wäßrige Aufschlußlösung, welche als Hauptkomponenten NaOH und Na2S enthält, aus dem Faserstoff herausgelöst wird.The cellulose fibers and hemicellulose fibers contained in fibrous materials such as wood are held together by lignin, a polymer made up of hydroxyphenylpropane units. When cellulose, a more or less contaminated cellulose, is obtained, lignin is separated from the cellulose. By far the most important process for obtaining pulp from fibrous materials is the process known as the alkaline sulfate process or kraft process, in which lignin is dissolved out of the fibrous material by an aqueous digestion solution which contains NaOH and Na 2 S as the main components.

Zur Steigerung der Zellstoffausbeute können in chemischen Aufschlußverfahren organische Tenside zugesetzt werden. Beispielsweise ist aus US-A-3,909,345 der Einsatz von Ethylenoxid/Propylenoxid-Blockcopolymeren und aus US-A-5,250,152 der Einsatz von ethoxylierten Alkoholen und ethoxylierten Dialkylphenolen im alkalischen Sulfatprozeß bekannt. To increase the pulp yield, chemical Digestion processes organic surfactants are added. For example is from US-A-3,909,345 the use of ethylene oxide / propylene oxide block copolymers and from US-A-5,250,152 the use of ethoxylated alcohols and ethoxylated Dialkylphenols known in the alkaline sulfate process.

GB-A-951 325 beschreibt ein Verfahren zur Gewinnung von Zellstoff, bei dem die Faserstoffe mit einer chemischen Aufschlußlösung in Gegenwart von Organopolysiloxan- bzw. Organosilanverbindungen umgesetzt werden.GB-A-951 325 describes a process for the production of Pulp, in which the pulp with a chemical Digestion solution in the presence of organopolysiloxane or Organosilane compounds are implemented.

Es bestand die Aufgabe, ein verbessertes Verfahren zur Gewinnung von Zellstoff aus Faserstoffen durch ein chemisches Aufschlußverfahren bereitzustellen.The task was to develop an improved method Obtaining pulp from fiber by a chemical To provide digestion procedures.

Die Erfindung betrifft ein Verfahren zur Gewinnung von Zellstoff aus Faserstoffen, bei dem die Faserstoffe mit einer chemischen Aufschlußlösung in Gegenwart von Organosiliciumverbindungen umgesetzt werden, die ausgewählt werden aus Organopolysiloxanverbindungen, welche aus Einheiten der allgemeinen Formeln (I) bis (VII) R3SiO½ R2SiO RSiO3/2 SiO4/2 R2R'SiO½ RR'SiO R'SiO3/2 aufgebaut sind, worin

R
einwertige Kohlenwasserstoffreste mit 1 bis 18 Kohlenstoffatomen,
R'
einwertige Reste der allgemeinen Formeln (VIII), (IX), (X) oder (XI)
-R1-[O(CR2 2)a]bOR3
Figure 00030001
-R1-[O(CR2 2)a]bZ -R1-[NR2(CH2)a]dNHR2 bedeuten, in denen
R1
zweiwertige C1- bis C18-Kohlenwasserstoffreste,
R2
Wasserstoffatome oder einwertige C1- bis C6-Alkylreste,
R3
Wasserstoffatome, einwertige C1- bis C6-Acylreste, C1-bis C6-Kohlenwasserstoffreste, oder OSO3X,
X
Wasserstoffatome, Alkali- oder gegebenenfalls mit C1-bis C18-Kohlenwasserstoffresten substituierte Ammoniumionen,
Z
Glycosidylreste, aufgebaut aus 1 bis 10 Monosaccharideinheiten,
a
die Werte 1, 2, 3, 4 oder 5,
b
ganzzahlige Werte von 0 bis 200,
c
die Werte 0 oder 1 und
d
die Werte 0, 1, 2, 3 oder 4 bedeuten, mit der Maßgabe, daß die Organopolysiloxanverbindungen mindestens eine Einheit der allgemeinen Formeln (V) bis (VII) aufweisen oder
Organosilanen der allgemeinen Formel (XII), R3SiR' worin
R'
einwertige Reste der vorstehenden allgemeinen Formel (VIII) bedeutet und
R
die vorstehenden Bedeutungen aufweist.
The invention relates to a process for obtaining pulp from fibrous materials, in which the fibrous materials are reacted with a chemical digestion solution in the presence of organosilicon compounds which are selected from organopolysiloxane compounds which consist of units of the general formulas (I) to (VII) R 3 SiO 1/2 R 2 SiO RSiO 3/2 SiO 4/2 R 2 R'SiO ½ RR'SiO R'SiO 3/2 are built up in what
R
monovalent hydrocarbon radicals with 1 to 18 carbon atoms,
R '
monovalent radicals of the general formulas (VIII), (IX), (X) or (XI)
-R 1 - [O (CR 2 2 ) a ] b OR 3
Figure 00030001
-R 1 - [O (CR 2 2 ) a ] b Z -R 1 - [NR 2 (CH 2 ) a ] d NHR 2 mean in which
R 1
divalent C 1 to C 18 hydrocarbon residues,
R 2
Hydrogen atoms or monovalent C 1 -C 6 -alkyl radicals,
R 3
Hydrogen atoms, monovalent C 1 -C 6 -acyl radicals, C 1 -C 6 -hydrocarbon radicals, or OSO 3 X,
X
Hydrogen atoms, alkali or ammonium ions optionally substituted with C 1 to C 18 hydrocarbon radicals,
Z.
Glycosidyl residues, built up from 1 to 10 monosaccharide units,
a
the values 1, 2, 3, 4 or 5,
b
integer values from 0 to 200,
c
the values 0 or 1 and
d
have the values 0, 1, 2, 3 or 4, with the proviso that the organopolysiloxane compounds have at least one unit of the general formulas (V) to (VII) or
Organosilanes of the general formula (XII), R 3 SiR ' wherein
R '
means monovalent radicals of the above general formula (VIII) and
R
has the above meanings.

Beim erfindungsgemäßen Verfahren wird für einen bestimmten Restligningehalt im Zellstoff weniger Aufschlußlösung benötigt. Ein Maß für den Restligningehalt im Zellstoff ist die Kappazahl, die dem Verbrauch an Millilitern 0,1 normaler (3,161 g/l) Kaliumpermanganatlösung pro Gramm Zellstoff entspricht.In the method according to the invention, a particular Residual lignin content in the pulp requires less digestion solution. A measure of the residual lignin content in the pulp is Kappa number, which is the normal consumption of milliliters 0.1 (3.161 g / l) potassium permanganate solution per gram of pulp.

Die Verringerung an Aufschlußlösung bewirkt eine Erhöhung der Zellstoffausbeute bezogen auf eingesetzten Faserstoff, da weniger Kohlehydrate, insbesondere Hemicellulosen herausgelöst werden, und somit auch weniger Nebenprodukte entstehen.The reduction in digestion solution causes an increase the pulp yield based on the fiber used, because fewer carbohydrates, especially hemicelluloses, are released and there are fewer by-products.

Eine bestimmte Kappazahl kann bei Verwendung der Organosiliciumverbindungen auch erreicht werden, indem die Kochzeit verkürzt wird.A certain number of kappa can be used when using the organosilicon compounds can also be achieved by the cooking time is shortened.

Beim erfindungsgemäßen Verfahren wird die Kappazahl unter konstanten Aufschlußbedingungen erniedrigt.In the method according to the invention, the kappa number is below constant digestion conditions decreased.

Da die Aufschlußlösung nun besser wirkt, weist der Zellstoff eine geringere Menge an gröberen, nicht aufgeschlossenen Faserrohstoffen ("rejects") auf. Since the digestion solution now works better, the pulp shows a smaller amount of coarser, undigested fiber raw materials ("rejects").

Generell führen Organosiliciumverbindungen zu einer höheren Zellstoffausbeute und geringeren Mengen an nicht aufgeschlossenen Faserstoffen.In general, organosilicon compounds lead to a higher one Yield and smaller amounts of undigested Fibrous materials.

Ferner verbessern die Organosiliciumverbindungen die Festigkeitswerte von Zellstoff und vermindern den Celluloseabbau.The organosilicon compounds also improve the strength values of pulp and reduce cellulose breakdown.

Bevorzugte Organosiliciumverbindungen sind organische Siloxane und Silane, welche eine organische polare Gruppe und einen hydrophoben Siloxan- oder Silanteil aufweisen und dadurch grenzflächenaktive Eigenschaften an den Phasengrenzen flüssig/flüssig, flüssig/gasförmig und flüssig/fest aufweisen. Preferred organosilicon compounds are organic siloxanes and silanes, which are an organic polar group and have a hydrophobic siloxane or sil content and thereby surface-active properties at the phase boundaries have liquid / liquid, liquid / gaseous and liquid / solid.

Wenn in den allgemeinen Formeln (VIII) bis (XI) b einen Wert von mindestens 2 aufweist kann a innerhalb des Formelbereichs [O(CR2)a]b eines Restes unterschiedliche Werte annehmen. Beispielsweise kann der Formelbereich [O(CR2)a]b ein Polyethylenglykol/Polypropylenglykol Blockcopolymeres sein.If in the general formulas (VIII) to (XI) b has a value of at least 2 a within the formula range [O (CR 2 ) a ] b of a radical can assume different values. For example, the formula range [O (CR 2 ) a ] b can be a polyethylene glycol / polypropylene glycol block copolymer.

Beispiele für Kohlenwasserstoffreste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, isoButyl-, tert.-Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.-Pentylrest; Hexylreste, wie der n-Hexylrest; Heptylreste, wie der n-Heptylrest; Octylreste, wie der n-Octylrest und iso-Octylreste, wie der 2,2,4-Trimethylpentylrest; Nonylreste, wie der n-Nonylrest; Decylreste, wie der n-Decylrest; Dodecylreste, wie der n-Dodecylrest; Octadecylreste, wie der n-Octadecylrest; Alkenylreste, wie der Vinyl-, Allyl- und der 5-Hexen-1-ylrest; Cycloalkylreste, wie Cyclopentyl-, Cyclohexyl-, Cycloheptylreste und Methylcyclohexylreste; Arylreste, wie der Phenyl-, Naphthyl- und Anthryl-und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste, Xylylreste und Ethylphenylreste; Aralkylreste, wie der Benzylrest, der alpha- und der β-Phenylethylrest.Examples of hydrocarbon radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo Pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Alkenyl radicals, such as the vinyl, allyl and 5-hexen-1-yl radicals; Cycloalkyl residues such as cyclopentyl, cyclohexyl, cycloheptyl residues and methylcyclohexyl residues; Aryl radicals, such as the phenyl, naphthyl and anthryl and phenanthryl radical; Alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; Aralkyl radicals, such as the benzyl radical, the alpha and the β-phenylethyl radical.

Vorzugsweise sind mindestens 90 Mol-% der Reste R Methyl-, Ethyl- oder Phenylreste, insbesondere Methylreste.Preferably at least 90 mol% of the radicals R are methyl, Ethyl or phenyl radicals, especially methyl radicals.

Beispiele für die zweiwertigen Reste R1 sind gesättigte gerad- oder verzweigtkettige oder cyclische Alkylenreste wie der Methylen- und Ethylenrest sowie Propylen-, Butylen-, Pentylen-, Hexylen-, 2-Methylpropylen-, Cyclohexylenreste, oder ungesättigte Alkylen- oder Arylenreste wie der Hexenylenrest und Phenylenreste.Examples of the divalent radicals R 1 are saturated straight-chain or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and also propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene radicals, or unsaturated alkylene or arylene radicals such as Hexenylene and phenylene.

Beispiele für die einwertigen Alkylreste R2 und R3 sind bei den vorstehenden Beispielen für R aufgeführt. Examples of the monovalent alkyl radicals R 2 and R 3 are listed in the above examples of R.

Beispiele für die Kohlenwasserstoffreste an den Ammoniumionen in X sind die für R genannten Kohlenwasserstoffreste.Examples of the hydrocarbon radicals on the ammonium ions in X are the hydrocarbon radicals mentioned for R.

Beispiele für die C1- bis C6-Acylreste R3 sind der Acetyl-, Propionyl- und n-Butyrylest.Examples of the C 1 - to C 6 -acyl radicals R 3 are the acetyl, propionyl and n-butyryl radical.

Beispiele für Monosaccharide, aus denen die Glycosidreste Z aufgebaut sein können, sind Hexosen und Pentosen, wie Glucose, Fructose, Galactose, Mannose, Talose, Allose, Altrose, Idose, Arabinose, Xylose, Lyxose und Ribose, wobei Glucose besonders bevorzugt ist. Vorzugsweise enthalten die Glycosidreste Z eine oder zwei Monosaccharideinheiten.Examples of monosaccharides from which the glycoside residues Z can be constructed are hexoses and pentoses, such as glucose, fructose, galactose, mannose, talose, allose, old rose, idose, arabinose, xylose, lyxose and ribose, with glucose being particularly preferred. The glycoside residues Z preferably contain one or two monosaccharide units.

Vorzugsweise bedeutet a die Werte 2 oder 3. Vorzugsweise bedeutet b ganzzahlige Werte von 3 bis 100, insbesondere 10 bis 70.Preferably, a is 2 or 3. Preferably, R b represents integer values from 3 to 100, in particular 10 to 70 wt.

Vorzugsweise weisen 2 bis 50 % insbesondere 5 bis 20 % der Einheiten der Organopolysiloxanverbindung die allgemeinen Formeln (V) bis (VII) auf.Preferably 2 to 50%, in particular 5 to 20%, of the Units of the organopolysiloxane compound the general Formulas (V) to (VII).

Vorzugsweise sind mindestens 95 %, insbesondere mindestens 99 % der Einheiten der Organopolysiloxanverbindung Einheiten der allgemeinen Formeln (II), (VI) und (I). Weiterhin ist bevorzugt, daß die Organopolysiloxanverbindung eine durchschnittliche Viskosität von 20 bis 500 000 mPa.s, insbesondere von 200 bis 60 000 mPa.s bei 25°C aufweist.Preferably at least 95%, especially at least 99% of the units of the organopolysiloxane compound units of the general formulas (II), (VI) and (I). Still is preferred that the organopolysiloxane compound have an average Viscosity from 20 to 500,000 mPa.s, in particular from 200 to 60,000 mPa.s at 25 ° C.

Es kann eine organosiliciumverbindung, es können auch Gemische mehrerer Organosiliciumverbindungen eingesetzt werden.It can be an organosilicon compound, it can also be mixtures several organosilicon compounds are used.

Vorzugsweise werden auf 100 Gewichtsteile trockene Faserstoffe 0,001 bis 1, insbesondere 0,01 bis 0,1 Gewichtsteile Organosiliciumverbindungen eingesetzt. Dry fibers are preferred per 100 parts by weight 0.001 to 1, especially 0.01 to 0.1 parts by weight Organosilicon compounds used.

Als chemische Aufschlußverfahren können beispielsweise angewandt werden:

  • 1) das Sulfitverfahren Beim Sulfitaufschluß werden Hackschnitzel mit Lösungen von Hydrogensulfiten gekocht. Je nachdem, ob die Hydrogensulfit-Lösungen überschüssiges Schwefeldioxid enthalten oder nicht, bezeichnet man die Verfahren als saure Bisulfit-Verfahren oder nur als Bisulfit-Verfahren. Als Überbegriff hat sich "Sulfitverfahren" eingebürgert.
  • 2) das Sulfatverfahren Beim Sulfatverfahren besteht die Aufschlußlösung, auch als Weißlauge bezeichnet, aus den Hauptkomponenten NaOH und Na2S.
    • The following chemical digestion processes can be used:
  • 1) The sulfite process In the sulfite digestion, wood chips are cooked with solutions of hydrogen sulfites. Depending on whether the hydrogen sulfite solutions contain excess sulfur dioxide or not, the processes are referred to as acidic bisulfite processes or only as bisulfite processes. "Sulphite process" has become the general term.
  • 2) The sulfate process In the sulfate process, the digestion solution, also known as white liquor, consists of the main components NaOH and Na 2 S.

    • Vorzugsweise wird nach dem Sulfatverfahren gearbeitet.The sulfate process is preferably used.

    Wenn das alkalische Sulfatverfahren angewendet wird, sind im Verfahren vorzugsweise pro 100 Gewichtsteile trockenes Holz 10 bis 35, insbesondere 20 bis 30 Gewichtsteile Na2O in Form von NaOH vorhanden. Vorzugweise sind im Verfahren pro 100 Gewichtsteile trockenes Holz 3 bis 15, insbesondere 6 bis 10 Gewichtsteile Na2S vorhanaen. Vorzugsweise wird das Verfahren bei 0,1 bis 3 MPa, insbesondere bei 0,5 bis 1,5 MPa durchgeführt.If the alkaline sulfate process is used, the process preferably contains 10 to 35, in particular 20 to 30 parts by weight of Na 2 O in the form of NaOH per 100 parts by weight of dry wood. Preferably, 3 to 15, in particular 6 to 10 parts by weight of Na 2 S are present per 100 parts by weight of dry wood in the process. The process is preferably carried out at 0.1 to 3 MPa, in particular at 0.5 to 1.5 MPa.

    Die chemischen Verfahren können absatzweise oder kontinuierlich in einem Zellstoffkocher durchgeführt werden.The chemical processes can be batch or continuous be carried out in a pulp cooker.

    Die Verweilzeit der Mischung im Zellstoffkocher beträgt vorzugsweise 10 min bis 7 h. The residence time of the mixture in the pulp cooker is preferably 10 min to 7 h.

    Als Faserstoffe können beispielsweise eingesetzt werden alle pflanzlichen Rohstoffe (Faserpflanzen), die einen hinreichenden Cellulose-Gehalt besitzen und sich genügend leicht verarbeiten lassen.For example, all of them can be used as fiber materials vegetable raw materials (fiber plants) that are sufficient Have cellulose content and are sufficiently light processed.

    Vorzugsweise werden Hölzer eingesetzt, wobei man in vielen Ländern heute auch in großem Umfang die in den Sägewerken anfallenden Holzabfälle als Rohstoff verwendet. Daneben spielen jedoch auch gewisse Einjahrespflanzen und Gräser eine untergeordnete Rolle.Woods are preferably used, with many in Countries today also on a large scale in the sawmills resulting wood waste is used as a raw material. Besides However, certain annual plants and grasses also play a role subordinate role.

    Das Holz wird in Form von beispielsweise Hackschnitzeln, Spänen oder Holzmehl eingesetzt.The wood is in the form of, for example, wood chips, Chips or wood flour used.

    In den nachfolgenden Beispielen sind, falls jeweils nicht anders angegeben,

  • a) alle Mengenangaben auf das Gewicht bezogen;
  • b) alle Drücke 0,10 MPa (abs.);
  • c) alle Temperaturen 20° C
  • d) EO Ethylenethereinheit (-CH2-CH2-O-).
    • In the following examples, unless otherwise stated,
  • a) all quantities based on weight;
  • b) all pressures 0.10 MPa (abs.);
  • c) all temperatures 20 ° C
  • d) EO ethylene ether unit (-CH 2 -CH 2 -O-).

    • BeispieleExamples Beispiel 1example 1 Zellstoffaufschluß im kontinuierlichen ZellstoffkocherPulp pulping in a continuous pulp cooker

    Als Organosiliciumverbindung wurde ein polyglykoletherfunktionelles wasserlösliches Silicontensid (Pulpsil® 950 S von Wacker-Chemie GmbH, München) eingesetzt. Pulpsil® 950 S wird durch Umsetzung der Organosiloxanverbindung der Formel (XIII) (H3C)3SiO[(H3C)2SiO]75[HCH3SiO]5Si(CH3)3 mit dem Allylpolyglykol der Formel (XIV) H2C=CH-CH2-O[CH2CH2O]25[CH2CH(CH3)O]25H in Gegenwart eines Platinkatalysators hergestellt. Die dabei entstehende Organosiliciumverbindung wird durch die Formel (XV) (H3C)3SiO[(H3C)2SiO]75[Y(CH3)SiO]5Si(CH3)3, wobei Y die Formel (XVI) -(H2C)3O[CH2CH2O]25[CH2CH(CH3)O]25H aufweist, gekennzeichnet.A polyglycol ether-functional water-soluble silicone surfactant (Pulpsil® 950 S from Wacker-Chemie GmbH, Munich) was used as the organosilicon compound. Pulpsil® 950 S is obtained by reacting the organosiloxane compound of the formula (XIII) (H 3 C) 3 SiO [(H 3 C) 2 SiO] 75 [HCH 3 SiO] 5 Si (CH 3 ) 3 with the allyl polyglycol of the formula (XIV) H 2 C = CH-CH 2 -O [CH 2 CH 2 O] 25 [CH 2 CH (CH 3 ) O] 25 H made in the presence of a platinum catalyst. The resulting organosilicon compound is represented by the formula (XV) (H 3 C) 3 SiO [(H 3 C) 2 SiO] 75 [Y (CH 3 ) SiO] 5 Si (CH 3 ) 3 , where Y is the formula (XVI) - (H 2 C) 3 O [CH 2 CH 2 O] 25 [CH 2 CH (CH 3 ) O] 25 H has marked.

    Ein kontinuierlicher Zellstoffkocher mit einer Kapazität von 270 to Trockenholzsubstanz in Form von Sägespänen pro Tag wurde bei 172°C und 0,95 MPa betrieben. Die Verweilzeit der Mischung im Kocher betrug 15 Minuten. Im Verfahren waren pro 100 Gewichtsteile Trockenholz 28 Gewichtsteile Na2O und 7 Gewichtsteile Na2S vorhanden. Der erhaltene Zellstoff wies eine Kappazahl von etwa 52 auf.A continuous pulp cooker with a capacity of 270 tons of dry wood substance in the form of sawdust per day was operated at 172 ° C and 0.95 MPa. The residence time of the mixture in the cooker was 15 minutes. In the process, 28 parts by weight of Na 2 O and 7 parts by weight of Na 2 S were present per 100 parts by weight of dry wood. The pulp obtained had a kappa number of about 52.

    Nach 36 Stunden wurden kontinuierlich zusätzlich 0,022 Gewichtsteile der vorstehenden Organosiliciumverbindung pro 100 Gewichtsteile Trockenholzsubstanz in die Aufschlußlösung unmittelbar vor dem Kocher gegeben. Die Kappazahl des Zellstoffs sank daraufhin auf etwa 48. After 36 hours, an additional 0.022 parts by weight was added continuously the above organosilicon compound per 100 parts by weight of dry wood substance in the digestion solution given immediately in front of the stove. The kappa number of the pulp then dropped to about 48.

    Anschließend wurde die Menge an Na2O auf 25 Gewichtsteile pro 100 Gewichtsteile Trockenholz gesenkt. Der erhaltene Zellstoff wies wieder eine Kappazahl von etwa 52 auf.The amount of Na 2 O was then reduced to 25 parts by weight per 100 parts by weight of dry wood. The pulp obtained again had a kappa number of about 52.

    Beispiel 2:Example 2: Zellstoffaufschlußversuche im LaborCell pulping tests in the laboratory

    Die nachfolgend beschriebenen Zellstoffaufschlußversuche in Gegenwart von Organosiliciumverbindungen im Labor demonstrieren ebenfalls deren Wirksamkeit bei der Herstellung von Zellstoff.The pulping experiments described below in Demonstrate the presence of organosilicon compounds in the laboratory also their effectiveness in the production of Cellulose.

    Aufschlußbedingungen für die Laborversuche:Disruption conditions for the laboratory tests:

    • Laborkocher:Zellstoffkocher, in welchem gleichzeitig 6 Autoklaven mit je einem Volumen von 2,5 l unter gleichen Bedingungen betrieben werden können. Laboratory cooker: cellulose cooker in which 6 autoclaves with a volume of 2.5 l each can be operated under the same conditions.
    • Holzarten:Types of wood:
      • Nadelholz: Kiefer ("Scot spine", pinus silvestris) aus Ostfinnland;Softwoods: Pine ("Scot spine", pinus silvestris) from eastern Finland;
      • Laubholz: Birke ("Betula birch") aus einer finnischen ZellstoffmühleHardwood: Birch ("Betula birch") from one Finnish pulp mill
    • Einwaage an Holzschnitzel:300 g gemäß Prüfmethode SCAN-CM 39 : 88 Holzschnitzel (bezogen auf Trockengewicht) Weighing of wood chips: 300 g according to test method SCAN-CM 39: 88 wood chips (based on dry weight)
    • effektives Alkali:(als NaOH in %, bezogen auf Trockengewicht an Holzschnitzel)20 % bei Laubholz bzw. 21 % bei Nadelholz (gemäß Prüfmethode SCAN-N 2 : 88) effective alkali: (as NaOH in%, based on dry weight of wood chips) 20% for hardwood or 21% for softwood (according to test method SCAN-N 2: 88)
    • Sulfidität: 32 %(gemäß Prüfmethode SCAN-N 2 : 88) Sulfidity: 32% (according to test method SCAN-N 2: 88)
    • Kochlauge/Holz-Verhältnis:5 : 1, einschließlich des Wassergehalts der Holzschnitzel Cooking liquor / wood ratio: 5: 1, including the water content of the wood chips
    • Zugabenenge an oberflächenaktiven Verbindungen:0,04 % bezogen auf Trockengewicht an Holzsubstanz Addition of surface-active compounds: 0.04% based on dry weight of wood substance
    • Aufheizzeit:Die Zeit, die benötigt wird, um von 80 °C auf 161 °C bei Laubholz bzw. 173 °C bei Nadelholz zu kommen; die exakten Angaben sind in der Tabelle aufgeführt. Heating time: The time it takes to get from 80 ° C to 161 ° C for hardwood or 173 ° C for softwood; the exact details are listed in the table.
    • Verweilzeit:Die Zeit, bei der der Aufschluß der Holzschnitzel in dem Autoklaven des Zellstoffkochers nach Erreichen der Endtemperatur von 161 °C bei Laubholz und 173 °C bei Nadelholz stattfindet; die exakten Angaben sind in der Tabelle aufgeführt. Dwell time: The time at which the wood chips are broken down in the autoclave of the pulp cooker after reaching the final temperature of 161 ° C for hardwood and 173 ° C for softwood; the exact details are listed in the table.
    Generelle Beschreibung der Laborversuche:General description of the laboratory tests:

    Die nach der Anlieferung zunächst eingefrorenen Holzschnitzel wurden innerhalb von 48 h wieder aufgetaut.The wood chips that were initially frozen after delivery were thawed again within 48 hours.

    Danach wurden sie über eine sorgfältige Siebung in verschiedene Fraktionen ausgetrennt, und deren Trockengewicht wurde nach SCAN-CM 39 : 88 (24 h, 105 °C) bestimmt. Für den anschließenden Aufschluß der Holzschnitzel wurde jeweils eine definierte Zusammensetzung aus den Fraktionen der Siebung herangezogen. After that, they were carefully screened into different ones Fractions separated, and their dry weight was determined according to SCAN-CM 39: 88 (24 h, 105 ° C). For the subsequent digestion of the wood chips each a defined composition from the fractions the screening.

    Dazu wurden je 300 g Holzschnitzel - bezogen auf Trockengewicht - in den Autoklaven vorgelegt und mit Weißlauge (der eigentlichen Kochlauge als Aufschlußlösung, welche als Hauptkomponenten NaOH und Na2S enthält) und Schwarzablauge (dem Filtrat aus der Zellstoffwäsche, welches in verdünnter Form NaOH und Na2S enthält) von einer finnischen Zellstoffmühle versetzt, um die vorstehend erwähnten Aufschlußbedingungen einzustellen (effektives Alkali, Flüssigkeit/Holz-Verhältnis, Sulfidität).For this purpose, 300 g of wood chips - based on dry weight - were placed in the autoclave and with white liquor (the actual cooking liquor as the digestion solution, which contains NaOH and Na 2 S as the main components) and black liquor (the filtrate from the cellulose washing, which is in dilute form NaOH and Na 2 S contains) added by a Finnish pulp mill to adjust the above-mentioned digestion conditions (effective alkali, liquid / wood ratio, sulfidity).

    Danach wurden 0,04 % der in der Tabelle angegebenen oberflächenaktiven Verbindungen als 2 %ige Lösungen in destilliertem Wasser zugegeben.Thereafter, 0.04% of the surfactants listed in the table became Compounds as 2% solutions in distilled water added.

    Nach Beendigung der Verkochung wurde der Zellstoff aus den jeweils 6 Autoklaven gewaschen (16 h mit ca. 45 °C warmem Wasser), zentrifugiert und homogenisiert.After the boil had ended, the pulp was removed from the 6 autoclaves each washed (16 h with approx. 45 ° C warm Water), centrifuged and homogenized.

    Es folgte die Bestimmung der Gesamtausbeute an Zellstoff, bevor 10 Min. lang in einem Wennberg-Zerfaserer aufgeschlagenen und nach erneutem Sieben über einem Sieb mit 0,35 mm Maschenweite (Manttä-Sieb) der Anteil an unaufgeschlossenen Faserstoffen (rejects) bestimmt wurde.This was followed by the determination of the overall yield of pulp, before being beaten in a Wennberg fiberizer for 10 minutes and after sieving again over a sieve with 0.35 mm Mesh size (Manttä sieve) the proportion of undigested Fibers (rejects) was determined.

    Die Angabe an gesiebter Zellstoffausbeute (Gesamtausbeute minus rejects) erfolgte in Prozent, bezogen auf ofengetrocknete Einwaage an Holzschnitzel.The indication of sifted pulp yield (total yield minus rejects) was in percent, based on oven-dried Weighing in wood chips.

    Beschreibung der verwendeten Tenside:Description of the surfactants used: Verwendete TensideSurfactants used

    Als Organosiliciumtenside wurden folgende Produkte verwendet:

  • 1. Siliconöl Wacker® LO66 (von Wacker-Chemie GmbH, München) Siliconöl Wacker® LO66 wird durch Umsetzung der Organosiliciumverbindung der Formel (XVII) H3CSiO[Si(CH3)HO]1,4SiCH3 mit dem Allylpolyglykol der Formel (XVIII) H2C=CH-CH2O[CH2CH2O]6,5CH3 in Gegenwart eines Platinkatalysators hergestellt. Die dabei entstehende Organosiliciumverbindung wird durch die Formel (IXX) H3CSiO[Si(CH3)YO]1,4SiCH3 wobei Y die Formel (XX) (CH2)3O[CH2CH2O]6,5CH3 aufweist, gekennzeichnet.
  • 2. Wacker® SPG 120 VP (von Wacker-Chemie GmbH, München) Wacker® SPG 120 VP stellt eine 50 % ige Lösung eines siloxanmodifizierten Glycosids in Wasser/Isopropanol dar, wobei der Wirkstoff durch Umsetzung der organosiloxanverbindung der Formel (XVII) mit dem Allylpolyglykol der Formel (XXI) H2C=CH-CH2O[CH2CH2O]1-(Glycosidyl)1,8 in Gegenwart eines Platinkatalysators hergestellt wird.Die dabei entstehende Organosiliciumverbindung wird durch die Formel (IXX), wobei Y die Formel (XXII) (CH2)3O(CH2CH2O)1(Glycosidyl)1,8 aufweist, gekennzeichnet.Zum Vergleich wurden die in US-A-5,250,152 beschriebenen organischen Tenside B1 und B2 herangezogen.
  • 3. Organisches Tensid B1: Das organische Tensid B1 stellt eine 1:1-Mischung aus ethoxyliertem Isostearylalkohol (Isostearyl (EO) 10OH) und ethoxyliertem Oleylalkohol (Oleyl[EO]20OH) dar.
  • 4 . Organisches Tensid B2: Das organische Tensid B2 stellt eine 1:1-Mischung aus Di-n-nonylphenolethoxylaten mit unterschiedlichen EO-Anteilen dar. Die beiden Phenolderivate werden mit den Formeln (XXIII) und (XXIV) gekennzeichnet.
    Figure 00170001
    Figure 00180001
    • The following products were used as organosilicon surfactants:
  • 1. Wacker® LO66 silicone oil (from Wacker-Chemie GmbH, Munich) Wacker® LO66 silicone oil is obtained by reacting the organosilicon compound of the formula (XVII) H 3 CSiO [Si (CH 3 ) HO] 1.4 SiCH 3 with the allyl polyglycol of the formula (XVIII) H 2 C = CH-CH 2 O [CH 2 CH 2 O] 6.5 CH 3 made in the presence of a platinum catalyst. The resulting organosilicon compound is represented by the formula (IXX) H 3 CSiO [Si (CH 3 ) YO] 1.4 SiCH 3 where Y is the formula (XX) (CH 2 ) 3 O [CH 2 CH 2 O] 6.5 CH 3 has marked.
  • 2. Wacker® SPG 120 VP (from Wacker-Chemie GmbH, Munich) Wacker® SPG 120 VP is a 50% solution of a siloxane-modified glycoside in water / isopropanol, the active ingredient being reacted with the organosiloxane compound of formula (XVII) Allyl polyglycol of formula (XXI) H 2 C = CH-CH 2 O [CH 2 CH 2 O] 1 - (glycosidyl) 1.8 in the presence of a platinum catalyst. The resulting organosilicon compound is represented by the formula (IXX), where Y is the formula (XXII) (CH 2 ) 3 O (CH 2 CH 2 O) 1 (glycosidyl) 1.8 For comparison, the organic surfactants B1 and B2 described in US-A-5,250,152 were used.
  • 3. Organic surfactant B1: The organic surfactant B1 is a 1: 1 mixture of ethoxylated isostearyl alcohol (isostearyl (EO) 10 OH) and ethoxylated oleyl alcohol (Oleyl [EO] 20 OH).
  • 4th Organic surfactant B2: The organic surfactant B2 is a 1: 1 mixture of di-n-nonylphenol ethoxylates with different EO contents. The two phenol derivatives are identified by the formulas (XXIII) and (XXIV).
    Figure 00170001
    Figure 00180001
    •

    Ergebnisse der Zellstoffaufschlußversuche im Labor:Results of the pulping experiments in the laboratory:

    Mit den Organosiliciumtensiden und den rein organischen Tensiden B1 und B2 wurden 3 Zellstoff-Aufschlußversuche in dem vorstehend beschriebenen Zellstoffkocher bei unterschiedlichen Bedingungen durchgeführt.With the organosilicon surfactants and the purely organic ones Surfactants B1 and B2 were used in 3 pulping experiments the pulp cooker described above with different Conditions carried out.

    Bei all den Verkochungen führte der Aufschluß mit dem Silicontensid SPG 120 VP zu den höchsten, gesiebten Zellstoffausbeuten.With all the boilings, the digestion with the Silicone surfactant SPG 120 VP for the highest, sieved cellulose yields.

    Daneben führten die Laborversuche mit LO66 zu Zellstoffqualitäten mit den niedrigsten Kappazahlen und relativ geringen "rejects".

    Figure 00190001
    In addition, the laboratory tests with LO66 led to pulp qualities with the lowest kappa numbers and relatively low "rejects".
    Figure 00190001

    Claims (3)

    1. Process for producing pulp from fibrous materials, wherein the fibrous materials are reacted with a chemical digesting solution in the presence of organosilicon compounds, characterized in that the organosilicon compounds are selected from organopolysiloxane compounds which are composed of units of the general formulae (I) to (VII) R3SiO½ R2SiO RSiO3/2 SiO4/2 R2R'SiO½ RR'SiO R'SiO3/2 where
      R
      represents univalent hydrocarbon radicals having from 1 to 18 carbon atoms,
      R'
      represents univalent radicals of the general formulae (VIII), (IX), (X) or (XI)
      -R1-[O(CR2 2)a]bOR3
      Figure 00230001
      -R1-[O(CR2 2)a]bZ -R1-[NR2(CH2)a]dNHR2 in which
      R1
      represents divalent C1- to C18-hydrocarbon radicals,
      R2
      represents hydrogen atoms or univalent C1- to C6-alkyl radicals,
      R3
      represents hydrogen atoms, univalent C1- to C6-acyl radicals, C1- to C6-hydrocarbon radicals, or OSO3X,
      X
      represents hydrogen atoms, alkali metal ions or ammonium ions which may or may not be substituted by C1- to C18-hydrocarbon radicals,
      Z
      represents glycosidyl radicals composed of from 1 to 10 monosaccharide units,
      a
      represents the values 1, 2, 3, 4 or 5,
      b
      represents integer values from 0 to 200,
      c
      represents the values 0 or 1 and
      d
      represents the values 0, 1, 2, 3 or 4, with the proviso that the organopolysiloxane compounds have at least one unit of the general formulae (V) to (VII), or from organosilanes of the general formula (XII) R3SiR'
      in which
      R'
      represents univalent radicals of the abovementioned general formula (VIII) and
      R
      has the abovementioned meanings.
    2. Process according to Claim 1, wherein at least 95 % of the units of the organopolysiloxane are units of the general formulae (II), (VI) and (I).
    3. Process according to Claim 1 or 2, wherein from 0.001 to 1 part by weight of organosilicon compound is used per 100 parts by weight of dry fibrous materials.
    EP95939246A 1994-11-10 1995-11-09 Cellulose extraction process Expired - Lifetime EP0791099B1 (en)

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    DE4440186 1995-11-09

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    US7390415B2 (en) * 2002-07-22 2008-06-24 Cytec Technology Corp. Method and compositions for preventing or reducing aluminosilicate scale in alkaline industrial processes
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    US5250152A (en) 1991-02-20 1993-10-05 Betz Paperchem, Inc. Ethoxylated alcohol and dialkylphenol surfactants as Kraft pulping additives for reject reduction and yield increase
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