EP3762537A1 - Cellulose et corps moulé en lyocell à teneur réduite en cellulose - Google Patents

Cellulose et corps moulé en lyocell à teneur réduite en cellulose

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Publication number
EP3762537A1
EP3762537A1 EP19708327.2A EP19708327A EP3762537A1 EP 3762537 A1 EP3762537 A1 EP 3762537A1 EP 19708327 A EP19708327 A EP 19708327A EP 3762537 A1 EP3762537 A1 EP 3762537A1
Authority
EP
European Patent Office
Prior art keywords
content
pulp
hemicellulose
lyocell
cellulose
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP19708327.2A
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German (de)
English (en)
Other versions
EP3762537B1 (fr
Inventor
Verena Silbermann
Martina OPIETNIK
Gabriele Schild
Susanne MÖDERL
Magdalena Körbler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
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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
    • 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
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • 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
    • 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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
    • 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
    • D21C9/001—Modification of pulp properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated cellulose

Definitions

  • the present invention describes special pulp compositions which make it possible to produce a lyocell fiber with a reduced cellulose content in a technically stable manner, as well as the lyocell fiber produced therefrom.
  • Lyocell fibers are used in a variety of applications. Purified cellulose is often used as a raw material, with a very low content of cellulose endings.
  • Pulp is obtained from wood, which consists only to 40-44 wt.% Of cellulose. Since in general a high content of cellulose in the pulp of more than 95% by weight is required for the production of lyocell mold bodies, a large part of the raw material is lost for the material utilization during the cooking and bleaching. In this connection, a large number of possibilities are known, in particular to purposefully reduce the proportion of hemicelluloses, both in the pulp production on the way of the wood to the pulp or to the lyocell end product:
  • bleaching usually for the elimination of residual lignin and / or for optical brightening, but also destroys hemicellulose components
  • WO 98/16682 describes a preparation process for a cellulosic composition suitable for fiber production.
  • a starting mixture which is considered not suitable for fiber production (but only for paper production) is processed so that the hemicellulose content, in particular the content of xylan decreases.
  • WO 99/47733 describes lyocell fibers and WO 2010/132151 A2 discloses a pulp with a cellulose having a low degree of polymerization.
  • WO 2010/132151 A2 discloses a pulp with a cellulose having a low degree of polymerization.
  • efforts have been made to broaden the raw material base for lyocell products by using celluloses with an increased level of lignin and / or hemicelluloses.
  • the present invention provides a pulp according to claim 1, a lyocell product according to claim 9, and the methods according to claims 16 and 18.
  • Preferred embodiments of the invention are given in the subclaims and the following detailed description of the invention.
  • the present invention provides the following aspects, as well as the preferred embodiments recited in the subclaims as well as in the description.
  • Pulp suitable for the production of Lyocellform stressesn, with a content of cellulose of 90 wt .-% or less, preferably 85 wt .-% or less and a content of hemicelluloses of at least 7 wt .-%, characterized in that the Ratio of present in the hemicellulose C5 / xylane to C6 / mannan fraction (C5 / C6 ratio) in the range of 125: 1 to 1: 3.
  • pulp according to embodiment 1 and / or 2 wherein the proportion of hemicelluloses is 10% by weight or more.
  • the hemicelluloses are in the native state, chemically modified by processing processes or chemically modified or functionalized in a separate process step.
  • Pulp according to at least one of the preceding embodiments with a lignin content of more than 1 wt .-%. Pulp according to at least one of the preceding embodiments, wherein the cellulose content is further reduced by the presence of lignin, accessory constituents from the wood and / or the addition of metallic compounds.
  • Pulp according to at least one of the preceding embodiments having a xylan content of 9% by weight or more and / or a mannan content of 6% by weight or more.
  • a pulp according to Embodiment 7 having a xylene content of 9% by weight or more and a mannan content of 1% by weight or less.
  • a lyocell molded body prepared by using the pulp according to any one of Embodiments 1 to 8. The lyocell molded body according to Embodiment 9, wherein the shaped body is selected from fibers, filaments, staple fibers, nonwoven knits, films and powders in spherical form.
  • Lyocellform moments according to at least one of embodiments 9 and / or 10, wherein the shaped body is a fiber, a filament or a staple fiber having a cellulose content of less than 90 wt .-%, a hemicellulose content of more than 5 wt .-% and a C5 / C6 ratio of 125: 1 to 1: 3, preferably 25: 1 to 1: 2.
  • Lyocellform analyses according to at least one of embodiments 9 to 11, wherein the hemicellulose content is more than 10 wt .-%.
  • Lyocellform stresses according to at least one of embodiments 9 to 12, wherein the shaped body is a fiber, a filament or a staple fiber with a WRV of greater than 70%, preferably greater than 75%, in particular greater than 80%.
  • Lyocellform stresses according to at least one of embodiments 9 to 14, with a lignin content of more than 0 wt .-% up to 5 wt .-%.
  • a process for the preparation of a lyocell-shaped body comprising dissolving a pulp with a cellulose content of 90% by weight or less, preferably 85% by weight or less and a hemicellulosic content of at least 7% by weight, characterized in that the ratio of C5 / xylan to C6 / mannan fraction (C5 / C6 ratio) present in the hemicellulose ranges from 125: 1 to 1: 3, in a suitable solvent, and forming the solution into a lyocell molded article.
  • the method of embodiment 16, wherein the lyocell molded article is obtained by a lyocell spinning process.
  • Figure 1 shows the correlation of crystallinity and water retention of lyocell fibers of the present invention and standard lyocell fiber.
  • Figure 2 shows the ratio of xylan to mannan in sulfite pulp as a function of H-factor when using beech wood.
  • Fig. 3 shows the ratio of xylan to mannan in sulfite pulp as a function of H-factor when using spruce wood.
  • the main constituents of non-cellulosic material in the raw material wood are the hemicelluloses (mainly polyoses from the sugar monomers xylose, arabinose, mannose, galactose, glucose and rhamnose), lignin and accessory components.
  • Cellulose It represents the skeletal substance of the cell walls in the wood and serves mainly the tensile strength.
  • the long molecular chains of glucose units are assembled in so-called fibrils several times in a helical structure. This helical arrangement in the cell wall ensures a good bending strength of the tree, e.g. at a wind load or wood z. B. in a roof construction.
  • Cellulose is hydrophilic but not water-soluble due to its high crystallinity.
  • Lignin binder for the solid composite of cellulose in the form of an amorphous matrix.
  • lignin is mainly responsible for the compressive strength, on the other hand, is less flexible and hydrophobic in contrast to cellulose. It is responsible for the stamina of the tree. Plants that do not store lignin only reach low stature heights. Lignin is biologically relatively stable and biologically degradable only slowly.
  • Hemicellulose in the context of the present invention are components present in wood in the form of short-chain polymers of C5 and / or C6 sugars. In contrast to cellulose, they have side groups and can therefore form crystals only to a much lesser extent. Their basic building blocks are mannose, xylose, glucose, rhamnose, galactose.
  • the side groups preferably consist of arabinose groups, acetyl groups and galactose residues, as well as O-acetyl groups and 4-O-methylglucuronic acid side groups. It is known that mannans are preferably associated with cellulose, while xylans are more likely to associate with lignin.
  • the composition of hemicelluloses varies greatly depending on the type of wood used. In the process of manufacturing pulp, side chains are partially separated and the polymer chains split. In the context of this invention, the term hemicelluloses encompasses those in their native structure as well as those modified by their processing and also those which have been adjusted by specific chemical modification for the particular intended use. Also included are short chain celluloses and other polyoses with a DP of up to 500.
  • Accessory ingredients are organic and inorganic non-ligninous wood pulp, cellulose and hemicellulose, and commonly include salts and low molecular weight organic compounds having up to about 100 atoms, such as tannins, resins, fats and waxes , Tanning and humic substances, terpenes, terpenoids and phenolic compounds, pectins, suberines, polyphenols and polyoses.
  • a proportion of hemicelluloses of at least 7 wt .-% is present, wherein that the ratio of sugars with five carbon atoms such.
  • B. xylan to sugars with six carbon atoms such. Mannan (hereinafter called C5 / C6 ratio) is in the range of 125: 1 to 1: 3.
  • the large-scale production of lyocell products can be realized with such a pulp, although the cellulose content in the pulp is lowered.
  • the pulps used here which are preferably used in the context of the present invention, show, as already stated, a relatively high content of hemicelluloses with the composition defined here.
  • the pulps preferably used in the context of the present invention also show further differences, which are listed below.
  • the pulps preferably used in the context of the present invention show a rather fluffy view. This results after milling (during the preparation of starting materials for the production of spinning solutions for the lyocell process) in a particle size distribution with a high proportion of larger particles. As a result, the bulk density is much lower, compared to standard pulps with a low hemicellulose content. Such a low bulk density requires adaptations in terms of metering parameters (e.g., metering using at least two reservoirs) in the preparation of the spinning solutions.
  • the pulps preferably used in the context of the present invention show an impregnation behavior with respect to NMMO, which, in comparison with standard cell materials, shows that impregnation is more difficult here.
  • the pulp used for the production of lyocell products preferably fibers, as described herein, exhibits a SCAN viscosity in the range from 300 to 440 ml / g, in particular 320 to 420 ml / g, more preferably 320 to 400 ml / g.
  • the SCAN viscosity is determined in accordance with SCAN-CM 15:99 using a Cupriethylendiaminaims, a method which is known in the art and which can be carried out with commercially available devices, such as with the device Auto PulpIVA PSLRheotek, available from the company PSL-Reotek.
  • the SCAN viscosity is on important parameter influencing in particular the processing of pulps in the production of spinning solutions. Even if two pulps show great agreement with respect to their composition, etc., different SCAN viscosities result in completely different behavior during processing.
  • a direct solution spinning process such as the lyocell process
  • the pulp is dissolved in NMMO as such.
  • NMMO as such.
  • the specifications for the viscosity of a raw pulp are typically in a small target window for the lyocell process. Otherwise problems can occur during production.
  • the pulp viscosity is preferably as previously described.
  • Lower viscosities lead to a worsening of the mechanical properties of the lyocell products.
  • Higher viscosities may in particular lead to an increased viscosity of the spinning solution, so that spinning is slower overall.
  • With lower spinning speeds lower draw ratios are obtained, which again can have a significant influence on the fiber structure and the fiber properties (Cabohydrate Polymers 2018, 181, 893-901). This would require process adaptations that would lead to a capacity reduction.
  • the use of pulps with the viscosities defined herein, on the other hand, allows for easy processing and the production of high quality products.
  • lyocell process refers to a direct dissolution process of wood pulp cellulose or other cellulose based feedstocks in a polar solvent (eg N-methylmorpholine -n-oxide (NMMO, NMO) or ionic liquids).
  • a polar solvent eg N-methylmorpholine -n-oxide (NMMO, NMO) or ionic liquids.
  • NMMO N-methylmorpholine -n-oxide
  • ionic liquids eg N-methylmorpholine -n-oxide (NMMO, NMO) or ionic liquids.
  • this tech is technology used by a group of cellulosic staple fibers to manufacture, Austria used under the brand name TENCEL ® or TENCEL TM), the very widespread in the textile industry or the nonwoven Industry commercially available from Lenzing AG, Lenzing.
  • Other cellulosic molds obtained by the lyocell technology have already been manufactured.
  • the cellulose solution is usually extruded in a so-called dry-wet-spinning method, using a molding tool, and the molded solution obtained, for example, after passing an air-gap into a precipitation bath where the molded body is obtained by the precipitation of the cellulose.
  • the shaped article is washed and optionally dried, after further treatment steps.
  • a process for the production of lyocell fibers is described, for example, in US 4246221, WO 93/19230, WO 95/02082 or WO 97/38153.
  • the fiber properties are greatly influenced by the type and by the assembly of the polymers. It is also known that cellulosic fibers produced by the lyocell process have a very high crystallinity of about 44 to 47%, while fibers from the viscose process have a crystallinity of about 29 to 34%.
  • the crystallinity describes the alignment of the cellulosic polymers to each other and thus, for example, their ability to absorb, swell and store water.
  • the polymer chains are more ordered in the non-crystalline regions of the lyocell fibers than in the viscose fibers. As a result, ordinary lyocell fibers swell less and are less suitable for highly absorbent products than viscose fibers.
  • celluloses according to the invention By using the celluloses according to the invention with reduced cellulose content, a completely different type of aggregation of the polymers and thus a different structure of the lyocell fibers is unexpectedly made possible.
  • Their crystallinity is significantly lower, typically 40% or less, such as 39% or less and, for example, in the range of 38% to 30%, such as in the range of 37 to 33%.
  • the values for WRV for fibers in accordance with the present invention, isolated or in combination with the other preferred embodiments described herein, preferably in combination with the values for the crystallinity of the fiber described herein, are preferably 70% or more, especially 75 % or more, like 80% or more, eg from 70 to 85%. It is known from the literature that xylans also form a crystal structure, provided that their side chains were split off in the course of the production process and they are precipitated from a pure xylan solution (Fengel, Wegener p 113, Fengel D, Wegener G (1989) : Wood, Chemistry, Ultrastructure, Reactions, Walter de Gruyter Verlag). The same applies to Mannan (ibid., P.119).
  • the polymers including the cellulose are present in a mixture in the dope and are thus spun out and precipitated. Furthermore, the hemicelluloses still have side groups, since the glucuronic acid side groups of xylan are comparatively stable under the conditions of acid digestion (Sixta H (Ed.) (2006): Handbook of Pulp Vol. 1, Wiley VCH P. 418).
  • the hemicelluloses thus fulfill all conditions to disrupt the crystallization of the cellulose and thus form a more disordered structure compared to standard lyocell fibers. Thus, those skilled in the art would expect that higher hemicellulose content and reduced cellulose content would give useless products, especially fibers.
  • the qualities of the new Lyocell fibers with a reduced proportion of those of conventional cellulose TENCEL ® fibers are similar. It is clear that under which the TENCEL ® fibers, the fiber strengths are easily measured in the examples as strength and working capacity. At the same time, the cellulose content could be significantly reduced, recorded in the examples as glucan value. The uptake of other wood constituents reduces the crystallinity by up to 21% and the absorbency increases significantly by up to 27%, measured in the examples as crystallinity index and water retention capacity.
  • the crystallinities are lyocell fibers of the new invention is between those of conventional ® TENCEL fibers and nonwovens Lenzing Viscose ® fibers, at the same time, the WRV is in the range of Lenzing Viscose ®.
  • the WRV increases more than would be explained by the decreasing crystallinity of the fibers.
  • the other ingredients as in particular Hemicelluloses, but also lignin and accessory components from the wood not only ensure a significant increase in yield, ie improved sustainability, but also a significant improvement in product properties, such as water retention capacity.
  • the pulp of the invention is characterized by a reduced cellulose content, a minimum amount of hemicelluloses and a certain C5 / C6 ratio with regard to the composition of the hemicellulose.
  • the pulp which may also be a mixture of different pulps (as long as the essential conditions are met), a pulp of a Hemicelluloseanteil of from 7 to 50 wt .-%, preferably 7 to 30 wt. %, more preferably 15 to 25 wt%, such as 10 to 20 wt%.
  • the pulp to be used according to the invention is furthermore preferably a pulp which has a xylan content of at least 9% by weight, preferably a fraction of at least 10% by weight.
  • the proportion of mannan can, in combination or independently, be chosen within a wide range, as long as the ratio defined according to the invention is fulfilled. Suitable mannan contents are in the range of 0.1 to 10% by weight, such as from 0.1 to 9% by weight and in embodiments from 0.1 to 6% by weight, from 0.1 to 4% by weight. %, from 5 to 10% by weight, from 6 to 10% by weight, etc.
  • the Mannangehalt in the range of 0.1 to 1 wt .-%, preferably in combination with a xylan content of at least 9 wt. -%, preferably at least 10 wt .-%. In other embodiments, the Mannangehalt is higher, preferably in the range of 6 wt .-% or more.
  • the cellulose content in the pulp is in a range of equal to or less than 90% by weight to 50% by weight, preferably in the range of 90% Wt% to 60 wt%, such as from 85 wt% to 70 wt%.
  • the weight ratio of cellulose to hemicellulose may range from 1: 1 to 20: 1.
  • the level of accessory constituents may be more than 0.05% by weight, preferably more than 0.2% by weight, more preferably more than 0.5% by weight. It has unexpectedly been found that with such proportions of accessory constituents in the pulp of the invention, the effect can be promoted that the C5 / C6 ratio also in the produced lyocell products, in particular fibers, stable and the hemicellulose content is not essential changed (ie the content does not decrease in the lyocell product or only slightly in comparison to the pulp).
  • such a high retention capacity is achieved by the inventive C5 / C6 ratio that at the same time a proportion of metal compounds, generally present as their oxides and hydroxides of up to 25 wt .-% based on the Weight of the lyocell product (eg, Mg (OH) 2 0 of the AI (OH) 3ZU flame retardant), which further substantially reduces the cellulose content.
  • metal compounds are in particular PO 2, Al 2 O 3, MgO, SiO 2, CeO 2, Mg (OH) 2, Al (OH) 3, BN, ZnO and originate in part from the mineral constituents of the wood or can be used as functional additives (flame retardancy, Matting agent, biocide ...) are added.
  • lyocell fibers having a cellulose content reduced to less than 70% can be produced which not only meet the practical requirements in comparison with the known lyocell fibers (mechanical strengths, etc.), but also due to the new properties resulting according to the invention even better for some applications.
  • the investigations have shown that fibers in the proposed composition have, in particular, an increased water retention capacity and a rapid biodegradability during composting.
  • the ratio of C5 / C6 sugars of the non-cellulosic polymers has been shown to be an important factor for adjusting the fiber composition and its resulting properties. Through targeted adjustment of this ratio, also in combination with the content of hemicelluloses, desired product properties can be adjusted in a targeted manner.
  • the person skilled in the art is aware of how he can control or adjust the C5 / C6 ratio. This can be achieved by a mixture of different pulps such. As softwood pulps with a higher Mannananteil be achieved with hardwood pulps with a higher xylan content. Attempts have confirmed another very effective way to adjust accordingly. By a targeted adjustment of cooking parameters such. As the H-factor, the ratio of C5 to C6 sugars can be controlled. This is shown in Figures 2 and 3. The H factor is considered to be an essential parameter for the control of sulfite boiling (Sixta (Vol. 1 2006) p. 432). He summarizes cooking temperature and cooking time as one size.
  • Figure 2 shows the influence of H factor in sulfite boiling on the Hemicellulose ratio in hardwood using the example of beech.
  • H factor For deciduous trees, xylan content is inherently higher.
  • xylan degrades more than mannan.
  • the ratio C5 / C6 decreases.
  • Another way to adjust the pulp composition according to the invention is the admixing of C5 and / or C6 sugars, which were previously obtained in other processes or process steps, such as. B. in an alkaline extraction, be it a cold alkali extraction or an E-stage or the like.
  • an alkaline extraction be it a cold alkali extraction or an E-stage or the like.
  • the viscose process takes place in the aqueous medium and the hemicelluloses are correspondingly alkali-soluble, so the cellulose xanthogenate and the dissolved hemicelluloses can be mixed together and spun together.
  • the solution of the pulp in the lyocell process takes place in NMMO or similar solvents, so here no alkaline or aqueous solutions can be added. You would dilute the solvent and reduce the solubility or even lead to unwanted precipitation.
  • the hemicelluloses can not be added in the form of solutions in spinning solution production, but must be introduced differently in the process.
  • One possibility is the addition in the pulp manufacturing process, so that the mixture can then be dried with the pulp.
  • the exact consideration of the hemicellulose composition is a crucial point for the industrial production of lyocell moldings, in particular fibers.
  • a co-utilization of hemicellulose in the fiber structure is only possible if the proportion of the C5 fraction is correlated with the proportion of the C6 fraction.
  • the ratio of xylan to mannan is between 18: 1 to 1: 3, preferably 9: 1 to 1: 2.
  • such a mixing ratio allows the incorporation of 0.5-5% by weight of lignin (and / or other accessory Constituents) into the fiber structure without adversely affecting the desired properties.
  • the fibers provided according to the invention have conventional fiber titers, such as 7 dtex or less, for example 2.2 dtex or less, such as 1.3 dtex, or less, possibly even lower, such as 0.9 dtex or less, in Dependence on the desired application.
  • fiber titers such as 7 dtex or less, for example 2.2 dtex or less, such as 1.3 dtex, or less, possibly even lower, such as 0.9 dtex or less, in Dependence on the desired application.
  • For applications in the Nonwovens are particularly titers of 1, 5 to 1, 8 dtex typical, while for textile applications lower titers, such as 1, 2 to 1, 5 dtex are suitable.
  • the present invention also includes fibers having even lower titers, as well as fibers having significantly higher titers, such as 10 dtex or less, such as 9 dtex or less, or even 7 dtex or less.
  • Suitable lower limits for fiber titers are values of 0.5 dtex or more, such as 0.8 dtex or more, and in embodiments, 1, 3 dtex or more.
  • the upper and lower limits disclosed herein may be combined and the regions formed thereby, such as from 0.5 to 9 dtex, are also included.
  • the present invention enables the production of fibers with titers, which allows use in the entire spectrum of fiber applications, including textile applications as well as nonwoven applications.
  • the determination of the crystallinity index is carried out by means of Raman spectroscopy. This method is calibrated with data from the X-ray wide-angle method (WAX) and was used by Röder et al. (2009) (Röder T, Moosbauer J, Kliba G, Schiader S, Zucker Toor G, and Sixta H (2009): Comparative Characterization of Man-Made Regenerated Cellulose Fibers. Lenzinger Berichte Vol. 87, pp. 98 ff.).
  • WAX X-ray wide-angle method
  • the sample is allowed to swell at 20 ⁇ 0.1 ° C overnight. After further dilution, the sample is centrifuged in a centrifuge according to Zellcheming leaflet IV / 33/57 at 3000 times the gravitational acceleration. The water retention capacity is then calculated as follows: ⁇ (Weight of moist sample - weight of dry sample),
  • Table 1 shows the results of setting the C5 / C6 ratio for two species of wood, using the example of H-factor variation in magnesium bisulfite digestion.
  • Table 1 Adjustment of the xylan-mannan ratio in the magnesium bisulfite boiling of Fagus sylvatica (beech) and Picea abies (spruce) using the H-factor.
  • Table 3 summarizes the salaries of the sugar monomers of the starting pulps for lyocell fiber production.
  • Table 4 shows mechanical characteristics for standard fibers (lyocell and viscose) compared with characteristics obtained with lyocell fibers made with pulps of the invention. The results clearly demonstrate the advantages of the present invention.
  • the new lyocell fibers according to the invention thus combine the respective advantageous properties of hitherto commercially available lyocell or viscose fibers.
  • 'Abeile 4 properties of conventional cellulose and reduced lyocell fibers as compared to a standard viscose fiber.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention décrit des compositions de cellulose spéciales qui permettent de fabriquer une fibre Lyocell à teneur réduite en cellulose de manière stable à l'échelle industrielle, ainsi que la fibre Lyocell fabriquée à partir desdites compositions.
EP19708327.2A 2018-03-06 2019-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit Active EP3762537B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18160123.8A EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit
PCT/EP2019/055593 WO2019170763A1 (fr) 2018-03-06 2019-03-06 Cellulose et corps moulé en lyocell à teneur réduite en cellulose

Publications (2)

Publication Number Publication Date
EP3762537A1 true EP3762537A1 (fr) 2021-01-13
EP3762537B1 EP3762537B1 (fr) 2023-10-25

Family

ID=61569169

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18160123.8A Withdrawn EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit
EP19708327.2A Active EP3762537B1 (fr) 2018-03-06 2019-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18160123.8A Withdrawn EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit

Country Status (10)

Country Link
US (1) US20210002825A1 (fr)
EP (2) EP3536850A1 (fr)
CN (1) CN111788348B (fr)
CA (1) CA3092615C (fr)
CL (1) CL2020002286A1 (fr)
ES (1) ES2968528T3 (fr)
FI (1) FI3762537T3 (fr)
TW (1) TWI746936B (fr)
WO (1) WO2019170763A1 (fr)
ZA (1) ZA202006048B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI814782B (zh) * 2018-03-06 2023-09-11 奧地利商蘭仁股份有限公司 溶劑紡絲之纖維素纖維
CN113109205A (zh) * 2021-03-29 2021-07-13 杭州融凯盛科技有限公司 一种快速检测莱赛尔纤维成型状态方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246221A (en) 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
ATA53792A (de) 1992-03-17 1995-02-15 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer formkörper, vorrichtung zur durchführung des verfahrens sowie verwendung einer spinnvorrichtung
WO1994008217A1 (fr) 1992-10-05 1994-04-14 Hans Paluschinski Appareil pour le prelevement d'echantillons de boues et d'eaux usees et procede de prelevement de ces echantillons
US5413631A (en) 1993-05-24 1995-05-09 Courtaulds (Holding) Limited Formation of a cellulose-based premix
US5456748A (en) 1993-05-24 1995-10-10 Courtaulds Fibres (Holdings) Ltd. Premix storage hopper
AT401271B (de) 1993-07-08 1996-07-25 Chemiefaser Lenzing Ag Verfahren zur herstellung von cellulosefasern
GB9412501D0 (en) * 1994-06-22 1994-08-10 Courtaulds Fibres Holdings Ltd Manufacture of fibre
AT402410B (de) 1995-04-19 1997-05-26 Chemiefaser Lenzing Ag Verfahren zur herstellung einer cellulosesuspension
AT409130B (de) 1995-04-25 2002-05-27 Chemiefaser Lenzing Ag Verwendung einer vorrichtung zum halten und abgeben einer homogenen cellulosesuspension
GB9607456D0 (en) 1996-04-10 1996-06-12 Courtaulds Fibres Holdings Ltd Spinning of filaments
AT404594B (de) 1996-08-01 1998-12-28 Chemiefaser Lenzing Ag Verfahren zur herstellung einer cellulosesuspension
US6471727B2 (en) 1996-08-23 2002-10-29 Weyerhaeuser Company Lyocell fibers, and compositions for making the same
US6210801B1 (en) * 1996-08-23 2001-04-03 Weyerhaeuser Company Lyocell fibers, and compositions for making same
US6331354B1 (en) 1996-08-23 2001-12-18 Weyerhaeuser Company Alkaline pulp having low average degree of polymerization values and method of producing the same
US6306334B1 (en) * 1996-08-23 2001-10-23 The Weyerhaeuser Company Process for melt blowing continuous lyocell fibers
US6057438A (en) * 1996-10-11 2000-05-02 Eastman Chemical Company Process for the co-production of dissolving-grade pulp and xylan
US20020084045A1 (en) * 1998-11-12 2002-07-04 Dimitris Ioannis Collias Compositions for improving physical strength properties and humidity resistance of paper products
US6686040B2 (en) 1999-02-24 2004-02-03 Weyerhaeuser Company Use of thinnings and other low specific gravity wood for lyocell products
DE102004024029A1 (de) * 2004-05-13 2005-12-08 Zimmer Ag Lyocell-Verfahren und -Vorrichtung mit Steuerung des Metallionen-Gehalts
DE102004024030A1 (de) * 2004-05-13 2005-12-08 Zimmer Ag Lyocell-Verfahren mit polymerisationsgradabhängiger Einstellung der Verarbeitungsdauer
US8802229B2 (en) 2007-06-29 2014-08-12 Weyerhaeuser Nr Company Lyocell fibers
US9845575B2 (en) * 2009-05-14 2017-12-19 International Paper Company Fibrillated blend of lyocell low DP pulp
AT514001B1 (de) 2012-12-06 2016-03-15 Chemiefaser Lenzing Ag Verfahren zur Herstellung eines cellulosischen Formkörpers
US20150184338A1 (en) * 2013-12-31 2015-07-02 Weyerhaeuser Nr Company Treated kraft pulp compositions and methods of making the same
US9222223B1 (en) 2014-06-30 2015-12-29 Weyerhaeuser Nr Company Esterified cellulose pulp compositions and related methods
US20160040360A1 (en) * 2014-08-05 2016-02-11 Celanese Acetate Llc Processes for pretreating and purifying a cellulosic material
US10239905B2 (en) * 2017-01-30 2019-03-26 The United States Of America As Represented By The Secretary Of Agriculture Low temperature and efficient fractionation of lignocellulosic biomass using recyclable organic solid acids

Also Published As

Publication number Publication date
CL2020002286A1 (es) 2021-02-05
ZA202006048B (en) 2022-03-30
CN111788348A (zh) 2020-10-16
BR112020017780A2 (pt) 2020-12-22
CA3092615C (fr) 2022-11-29
TW201942444A (zh) 2019-11-01
US20210002825A1 (en) 2021-01-07
ES2968528T3 (es) 2024-05-10
EP3762537B1 (fr) 2023-10-25
EP3536850A1 (fr) 2019-09-11
RU2020132856A3 (fr) 2022-04-12
FI3762537T3 (fi) 2024-01-17
WO2019170763A1 (fr) 2019-09-12
RU2020132856A (ru) 2022-04-06
CA3092615A1 (fr) 2019-09-12
TWI746936B (zh) 2021-11-21
CN111788348B (zh) 2023-03-28

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