EP2929071B1 - Procédé de production d'un article façonné cellulosique - Google Patents

Procédé de production d'un article façonné cellulosique Download PDF

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Publication number
EP2929071B1
EP2929071B1 EP13801568.0A EP13801568A EP2929071B1 EP 2929071 B1 EP2929071 B1 EP 2929071B1 EP 13801568 A EP13801568 A EP 13801568A EP 2929071 B1 EP2929071 B1 EP 2929071B1
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EP
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Prior art keywords
xylan
molecular weight
weight
pulp
viscose
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EP13801568.0A
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German (de)
English (en)
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EP2929071A1 (fr
Inventor
Gabriele Schild
Andrea Borgards
Herbert Sixta
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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Priority to PL13801568T priority Critical patent/PL2929071T3/pl
Priority to SI201330615A priority patent/SI2929071T1/sl
Publication of EP2929071A1 publication Critical patent/EP2929071A1/fr
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath

Definitions

  • the invention relates to a process for producing cellulosic shaped bodies by the viscose process.
  • the invention relates to the production of fibers and filaments.
  • the fibers produced by this process are known by the generic term viscose fibers and modal fibers.
  • the modal process differs from the standard viscose process by changed composition of the dope, additional modifiers in the dope and modified Spinnbadzusammen arrangement.
  • the pulp used in the viscose process must meet certain criteria to allow appropriate fiber qualities.
  • the pulp used in the viscose process has an alpha-cellulose content of greater than 90% and has only low proportions of secondary compounds, such as xylan and other hemicelluloses (such as, for example, mannan). These compounds are for the most part degraded during the alkalization of the pulp at the beginning of the viscose process and dissolved out ( Fig. 1 ). Hemicelluloses remaining in the pulp are depolymerized in pre-maturity together with the cellulose and therefore have a much lower content average molecular weight than in the starting pulp. This applies both to the use of chemical pulps and to the use of paper pulps.
  • FIG. 2 the distinctly lower molecular weight of the hemicelluloses is evident, which are introduced with the pulp in the viscose process and then subject to degradation in mash and pre-maturity.
  • molecular weight distributions are represented by hemicelluloses extracted from a softwood and a hardwood pulp without degradation.
  • the WO 95/00698 describes a process in which, during the production of Kraft pulp, a substantial amount of hemicellulose is first removed from the production stream and re-deposited on the pulp in a later stage.
  • the WO 2005/118950 describes the separation of beta-cellulose from caustic obtained by pressing after a cold or hot alkaline extraction (CCE, HCE) of a pulp.
  • the object of the present invention is achieved in one aspect by a process for the production of a cellulosic molded body by the viscose method by shaping a spinning mass comprising cellulose xanthate, which is characterized in that the cellulose xanthate xylan in a proportion of at least 1 wt.%, Based on cellulose , preferably 1 wt.% To 20 wt.%, Particularly preferably 3 wt.% To 15 wt.% Is added.
  • the invention relates to a obtained by the viscose cellulosic molding with a proportion of high molecular weight xylan with an average degree of polymerization (DP) of from 75 to 350, preferably from 110 to 220, of at least 0.5% by weight, based on cellulose, preferably from 2% by weight to 8% by weight.
  • DP average degree of polymerization
  • the xylan is added to the cellulose xanthate.
  • the subsequent steps of the viscose process spininning, regeneration, etc.
  • no significant degradation or dissolution of the xylan takes place more, so that it remains largely in the resulting molded body.
  • the xylan is preferably added in the form of an alkaline solution.
  • the alkaline solution may have a xylan content of 1 to 60 g / l.
  • the xylan can be added to the cellulose xanthate as a constituent of an alkaline solution.
  • an alkaline solution is known to be used.
  • the xylan to be added.
  • the xylan originates from a pressing liquor produced during the pressing off of alkalized pulp at the beginning of the viscose process.
  • the pulp is alkalized at the beginning of the viscose process.
  • an alkaline press liquor is obtained which contains a high proportion of xylan dissolved out by alkalization from the pulp.
  • this press liquor is used as the dissolving liquor to dissolve the cellulose xanthogenate, the xylan previously dissolved out of the pulp is returned to the process, thus increasing its yield.
  • This xylan is relatively low molecular weight.
  • One skilled in the art would expect that addition of low molecular weight xylan would adversely affect the strength properties of the resulting fiber.
  • At least part of the added xylan is a high molecular weight xylan having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220.
  • DP average degree of polymerization
  • the xylan derived from the caustic in the alkalization of the pulp by the viscose process is comparatively low molecular weight due to the alkalization during the degradation (cf. FIG. 2 ). It has been shown that viscose fibers by adding such low molecular weight xylans in their properties such as strength and elongation do not fall behind conventional viscose fibers.
  • the high molecular weight xylan is added in a proportion of 1% to 20%, preferably 3% to 15%, based on cellulose.
  • the high molecular weight xylan may preferably originate from a hemicellulose-rich material stream obtained in the course of an extraction step in the production of a pulp.
  • the pressed liquor obtained by pressing off the pulp after extraction by appropriate methods such as membrane filtration as in WO 2005/118050 , concentrated, so it creates a stream with a high proportion of high molecular weight xylan.
  • this lye can be added directly to the cellulose xanthate as a solution or as a part thereof.
  • the present invention also relates to a cellulosic molded body obtained by the viscose process with a high molecular weight xylan content having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220, of at least 0.5% based on cellulose, preferably 2% to 8 %.
  • DP average degree of polymerization
  • the molding according to the invention is novel since, without the addition of high molecular weight xylan to the cellulose xanthate according to the invention, no high molecular weight xylan is contained in the resulting molding in the conventional viscose process due to the degradation and dissolution of xylan.
  • the cellulosic shaped body according to the invention is preferably in the form of a fiber, e.g. Staple fiber or filament fiber.
  • the invention also relates to the use of the cellulosic molding according to the invention in absorbent products.
  • the lye may contain low molecular weight and / or high molecular weight xylans.
  • the lye can be added together with a possibly also used dissolving water.
  • the Loughlauge contained between 1 and 66 g / l of dissolved xylan.
  • the xylan was added to the xanthogenate with the alkaline Lettelauge after xanthogenation and homogeneously mixed.
  • the xylan had the following molecular weight distribution: ⁇ b> Table 1: ⁇ / b> Molecular weight of the xylan used from a CCE liquor Mw kg / mol Mn kg / mol PDI DP xylan 22 13 1.7 167
  • Figure 3 illustrates the molecular weight distribution of high molecular weight xylan as prepared from a CCE liquor of coniferous and hardwood pulps, respectively. It can be clearly seen that the xylan obtained after application of a CCE stage has a much higher average molecular weight than the xylan already degraded in the mash of the viscose process.
  • the xylan was added to the xanthate from a conventional beech sulfite pulp and therefore was not present during the sulfidation, but only in the subsequent process step, the dissolution of the xanthate.
  • the xylan is thus not xanthogenated, but dissolved in NaOH.
  • the fibers were spun out in the laboratory. Fibers were thus produced with a significantly higher content of xylan (see Table 2 below).
  • a pulp (beech sulfite pulp) was mixed with about 18% NaOH, pressed and subjected to a pre-ripeness at about 34 ° C for 19 hours.
  • the Lettelauge contained 0% xylan.
  • the resulting dope was conventionally spun into fibers having the properties shown in Table 2, Example 1.
  • the present in the fibers (low molecular weight) xylan of 0.6 and 0.7% comes from the pulp used.
  • Example 2 To a xanthate according to Example 1, a Lettelauge was added with 8.5 g / l high molecular weight xylan. The resulting dope was spun into fibers having the properties shown in Table 2, Example 2. The xylan uptake was 63% of the high molecular weight xylan present in the L Harborlauge, which corresponds to a proportion of high molecular weight xylan of 0.7% based on the fiber.
  • Example 3 To a xanthate according to Example 1 was added a Lettelauge with 22.0 g / l high molecular weight xylan. The resulting dope was spun into fibers having the properties shown in Table 2, Example 3. The xylan uptake was 79.2% of the high molecular weight xylan present in the L Harborlauge, which corresponds to a high molecular weight xylan content of 2.7% based on the fiber.
  • Example 2 To a xanthate according to Example 1, a Lettelauge with 39.0 g / l high molecular weight xylan was added. The resulting dope was spun into fibers having the properties shown in Table 2, Example 4. The xylan uptake was 77.2% of the high molecular weight xylan present in the L Harborlauge, which corresponds to a high molecular weight xylan content of 4.8% based on the fiber.
  • the molecular weight distributions of the xylan-enriched fiber and that of the CCE-xylan used were determined by size exclusion chromatography ( FIG. 5 ).
  • the area of the xylan peak there is clearly a shoulder on the fiber that suggests an accumulation of added xylan in the fiber.
  • a curve is obtained from a standard viscose fiber, as in FIG. 6 shown.
  • the in the Figures 5 and 6 reported xylan content of 5.5% refers to the total content of xylan in the fiber (ie xylan from pulp used plus added high molecular weight xylan).
  • Example 2 To a xanthate according to Example 1, a Lettelauge was added with 31.7 g / l xylan. The resulting dope became fibers having the properties given in Table 2, Example 5 Spun shown properties. The xylan uptake was 60.2% of the high molecular weight xylan present in the L Harborlauge, which corresponds to a high molecular weight xylan content of 6.9% based on the fiber.
  • Example 2 To a xanthate according to Example 1, a Lettelauge with 66.3 g / l xylan was added. The resulting dope was spun into fibers. The xylan uptake was 54.4% of the high molecular weight xylan present in the L Harborlauge, which corresponds to a high molecular weight xylan content of 10.0% based on the fiber.
  • the xylan-containing solubilizer was added to the cellulose xanthate along with solvent water. Obviously due to this, there was a partial precipitation of the xylan in the spinning mass, so that the quality of the spinning solution (filter value, etc.) and also those of the spun fibers lagged behind those of Examples 2 to 5.
  • the xylan supply in the dope was 5.67% based on cellulose. Of these, 30.0% were spun into the fiber. A fiber with 2.2% xylan was obtained.
  • the high molecular weight xylan was taken up to an unexpectedly high level by the fiber.
  • the uptake into the viscose fiber was 63% to 79% of the xylan offered in the Léelauge. From the filter value and the number of particles, it becomes clear that the quality of the dope and the processability by no means suffer from the addition of this copolymer.
  • xylan which is introduced into the process with only a chemical or paper pulp, is degraded and as a result is removed by 63 to 80% during the mash and spin bath (see Table 3 below).
  • the filter value and particle content of the Viskosespinnmasse are - especially at a high input of xylan from a pulp - significantly reduced.
  • Table 3 Loss of wood pulp entering xylan in the viscose process cellulose Process Xylan in pulp [%] Filter value [-] Particle content [ppm] Xylan in dope / fiber [%] Xylan loss [%] Chemical pulp Beech sulfite 3.1 364 15.6 0.6 80.6 Paper pulp Eucalyptus kraft 22.1 8th 671 8.1 63.3 Paper pulp Poplar force 19.8 69 118 7.3 63.1
  • the water retention capacity WRV could also be increased significantly by the incorporation of xylan into the viscose fiber (see Table 2 and FIG. 4 ).
  • the uptake of water and the ability to adsorb water could not only be increased, but also selectively adjusted via the xylan content of the fiber.
  • the abscissa (xylan content) in the FIG. 4 again refers to the total content of xylan in the fiber.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Claims (11)

  1. Procédé de fabrication d'un corps moulé cellulosique d'après le procédé Viscose par formage d'une masse filée contenant du xanthogénate de cellulose, caractérisé en ce que le xanthogénate de cellulose est additionné de xylane en une proportion d'au moins 1 % en poids, par rapport à la cellulose, de préférence de 1 % en poids à 20 % en poids, particulièrement préférentiellement de 3 % en poids à 15 % en poids.
  2. Procédé selon la revendication 1, caractérisé en ce que le xylane est additionné sous la forme d'une solution alcaline.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le xylane est additionné au xanthogénate de cellulose sous la forme d'un composant d'une lessive soluble alcaline.
  4. Procédé selon l'une des revendications 2 ou 3, caractérisé en ce que le xylane provient d'une lessive de pressage résultant de l'extraction par pression de la matière cellulosique alcalinisée au début du procédé Viscose.
  5. Procédé selon la revendication 4, caractérisé en ce que le xanthogénate de cellulose est additionné d'une lessive de pressage résultant de l'extraction par pression de la matière cellulosique alcalinisée au début du procédé Viscose.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'au moins une partie du xylane additionné est un xylane de poids moléculaire élevé ayant un degré de polymérisation moyen (DP) de 75 à 350, de préférence de 110 à 220.
  7. Procédé selon la revendication 6, caractérisé en ce que le xylane de poids moléculaire élevé est ajouté en une proportion de 1 % en poids à 20 % en poids, de préférence de 3 % en poids à 15 % en poids, par rapport à la cellulose.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que le xylane de poids moléculaire élevé provient d'un courant de matière riche en hémicellulose résultant au cours de l'étape d'extraction lors de la fabrication d'une matière cellulosique.
  9. Corps moulé cellulosique obtenu d'après le procédé Viscose, comprenant une proportion d'un xylane de poids moléculaire élevé présentant un degré moyen de polymérisation (DP) de 75 à 350, de préférence de 110 à 220, d'au moins 0,5 % en poids par rapport à la cellulose, de préférence de 2 % en poids à 8 % en poids.
  10. Corps moulé cellulosique selon la revendication 9 sous la forme d'une fibre.
  11. Utilisation d'un corps moulé cellulosique selon l'une des revendications 9 ou 10 dans des produits absorbants.
EP13801568.0A 2012-12-06 2013-12-04 Procédé de production d'un article façonné cellulosique Active EP2929071B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL13801568T PL2929071T3 (pl) 2012-12-06 2013-12-04 Sposób wytwarzania celulozowego elementu kształtowego
SI201330615A SI2929071T1 (sl) 2012-12-06 2013-12-04 Postopek za izdelavo celuloznega oblikovanca

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50564/2012A AT514001B1 (de) 2012-12-06 2012-12-06 Verfahren zur Herstellung eines cellulosischen Formkörpers
PCT/EP2013/075575 WO2014086883A1 (fr) 2012-12-06 2013-12-04 Procédé de production d'un article façonné cellulosique

Publications (2)

Publication Number Publication Date
EP2929071A1 EP2929071A1 (fr) 2015-10-14
EP2929071B1 true EP2929071B1 (fr) 2017-02-01

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EP13801568.0A Active EP2929071B1 (fr) 2012-12-06 2013-12-04 Procédé de production d'un article façonné cellulosique

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EP (1) EP2929071B1 (fr)
CN (1) CN104919097B (fr)
AT (1) AT514001B1 (fr)
ES (1) ES2622567T3 (fr)
PL (1) PL2929071T3 (fr)
SI (1) SI2929071T1 (fr)
WO (1) WO2014086883A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3536833A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibres de lyocell sans mannane
EP3536831A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell comportant une nouvelle section transversale
EP3536852A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre cellulosique et de type lyocell a degre de blanc reglable
EP3536850A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Pulpe et articles en lyocell avec un taux en cellulose réduit
EP3536832A1 (fr) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Fibre lyocell présentant des propriétés de désintégration améliorées
CN109913967A (zh) * 2019-03-19 2019-06-21 阿拉尔市富丽达纤维有限公司 一种利用低聚合度浆粕制备粘胶纤维的工艺

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932751A (en) * 1931-09-11 1933-10-31 Brown Co Preparation of cellulose xanthate from sheeted cellulose fiber
US2364392A (en) * 1942-10-17 1944-12-05 Du Pont Production of alkali metal cellulose xanthate
IT1121810B (it) * 1979-06-15 1986-04-23 Snia Viscosa Procedimento migliorate per la preparazione di viscosa e procedimento di filatura della viscosa cosi'ottenuta
DE3000306A1 (de) * 1980-01-05 1981-07-09 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von viskose
US6686039B2 (en) * 1999-02-24 2004-02-03 Weyerhaeuser Company Use of thinnings and other low specific gravity wood for lyocell pulps
US6685856B2 (en) * 1999-02-24 2004-02-03 Weyerhaeuser Company Use of thinnings and other low specific gravity wood for lyocell products method
AT503610B1 (de) * 2006-05-10 2012-03-15 Chemiefaser Lenzing Ag Verfahren zur herstellung eines zellstoffes
AT503611B1 (de) * 2006-05-10 2009-05-15 Chemiefaser Lenzing Ag Verfahren zur herstellung eines zellstoffes
US20080001325A1 (en) * 2006-06-30 2008-01-03 Mengkui Luo Method for Processing High Hemicellulose Pulp in Viscose Manufacture

Also Published As

Publication number Publication date
WO2014086883A1 (fr) 2014-06-12
AT514001B1 (de) 2016-03-15
CN104919097A (zh) 2015-09-16
EP2929071A1 (fr) 2015-10-14
SI2929071T1 (sl) 2017-06-30
AT514001A1 (de) 2014-09-15
PL2929071T3 (pl) 2017-08-31
ES2622567T3 (es) 2017-07-06
CN104919097B (zh) 2017-11-03

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