EP2889401A1 - Regenerated cellulose fibre - Google Patents
Regenerated cellulose fibre Download PDFInfo
- Publication number
- EP2889401A1 EP2889401A1 EP13199757.9A EP13199757A EP2889401A1 EP 2889401 A1 EP2889401 A1 EP 2889401A1 EP 13199757 A EP13199757 A EP 13199757A EP 2889401 A1 EP2889401 A1 EP 2889401A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- fiber
- organosolv
- fibers
- viscose
- 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
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 14
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 5
- 229920005610 lignin Polymers 0.000 claims abstract description 117
- 239000000835 fiber Substances 0.000 claims abstract description 80
- 229920000297 Rayon Polymers 0.000 claims description 31
- 229920001732 Lignosulfonate Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
- 239000004917 carbon fiber Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920005611 kraft lignin Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229920001503 Glucan Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- HCBIBCJNVBAKAB-UHFFFAOYSA-N Procaine hydrochloride Chemical compound Cl.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 HCBIBCJNVBAKAB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
Classifications
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
-
- 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
-
- 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
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
Definitions
- the present invention relates to a regenerated cellulose fiber produced by the viscose process (hereinafter also referred to as “viscose fiber”), to the production and use thereof.
- the present invention relates to a regenerated cellulosic fiber containing lignin.
- Viscose fibers are already used in carbonized insulating moldings and nonwovens.
- carbonaceous starting materials precursors
- precursors are pyrolyzed in an oven at temperatures of 500-1800 ° C with exclusion of oxygen.
- This foreign atoms such as nitrogen, oxygen and hydrogen are split off in gaseous form.
- What remains is almost exclusively carbon, which has a graphite-like layer structure.
- the carbonation yield of viscose is theoretically 44%, but in reality only 15-20%. Thus, 80 to 85% of the fiber mass is lost during the carbonization. By improving the carbon yield, the carbonation process would be much more economical.
- the WO 2012/156443 A1 describes precursor fibers for producing carbon fibers containing lignin.
- the fibers are spun from a solution containing a lignin and a fiber-forming polymer from the group of polyacrylonitrile or polyacrylonitrile copolymers.
- Example 2 of this document describes the spinning of a solution containing chemical cellulose, kraft lignin and polyacrylonitrile.
- the WO 2013/020919 deals with the production of precursor fibers from carbon fibers.
- the fiber is a mixture of polyacrylonitrile, a glucan and lignin. Both in the case of WO 2012/156443 A1 as well as the WO 2013/020919
- the fibers are spun from a solution in an organic solvent.
- the EP 2 524 980 describes the production of precursor fibers from carbon fibers.
- the fibers contain at least 10% lignin and one or more fiber-forming polymers, such as cellulose, and are spun from an organic solvent.
- the object underlying the present invention is achieved by a regenerated cellulose fiber containing Organosolv lignin.
- the lignins differ in their monomer composition, type of bonds and their molecular weight depending on the plant species, origin and season. In addition, each digestion process produces lignins with other properties.
- Organosolv lignin By the "Organosolv method" the skilled person understands a wood pulping with the aid of aqueous organic solvents, in particular ethanol, at high pressure and high temperature.
- aqueous organic solvents in particular ethanol
- the resulting lignin in this process is called Organosolv lignin.
- the cellulose fiber of the invention may have a content of Organosolv lignin of 5% to 90%, preferably 10% to 70%, particularly preferably 20% to 50%, based on fiber.
- Organosolv lignin 5% to 90%, preferably 10% to 70%, particularly preferably 20% to 50%, based on fiber.
- (regenerated) cellulosic fiber or "viscose fiber” will also encompass fibers containing up to 90% lignin as long as it is made by the viscose process, ie from an alkaline solution containing cellulose xanthate and spun into an acid spin bath , getting produced.
- the fiber of the invention may preferably contain another lignin different from organosolv lignin. Because organosolv lignin is less soluble than common lignins, e.g. Kraft-lignin or lignosulfonates is more difficult to obtain by replacing a portion of the Organosolv lignin by another lignin the production of the fiber according to the invention and the carbon fiber resulting therefrom carbonization can be made even more favorable.
- organosolv lignin is less soluble than common lignins, e.g. Kraft-lignin or lignosulfonates is more difficult to obtain by replacing a portion of the Organosolv lignin by another lignin the production of the fiber according to the invention and the carbon fiber resulting therefrom carbonization can be made even more favorable.
- the further lignin is preferably selected from the group consisting of kraft lignin, lignosulfonate and mixtures thereof.
- the further lignin is preferably uncrosslinked.
- the content of further lignin in the fiber may be from 5% to 85%, preferably from 10% to 70%, particularly preferably from 20% to 50%, based on fiber.
- the ratio of organosolv lignin to further lignin may be from 4: 1 to 1: 4, preferably 3: 1 to 1: 3.
- the cellulosic fiber of the present invention is characterized by substantially no further fiber-forming polymer, such as cellulose and lignin. Polyacrylonitrile or polyacrylonitrile copolymers containing.
- the cellulose fiber according to the invention may have a titer of 0.5 dtex to 30 dtex, preferably 1 dtex to 4 dtex.
- the cellulose fiber according to the invention is preferably used for the production of carbon fibers. Further fields of use are e.g. Hygiene and medical applications (due to the increased water retention capacity of the fiber).
- the present invention also relates to a process for producing the cellulosic fiber of the invention, comprising the step of adding organosolv lignin and optionally another lignin to a spun viscose or a precursor thereof.
- precursors of a spinning viscose are in particular starting substances of the viscose process, such as e.g. Pulp, or intermediates such as e.g. Alkali cellulose or cellulose xanthogenate understood.
- the lignin was mixed in a proportion of 50% based on the total amount of fiber-forming polymer (cellulose + lignin) in a standard viscose.
- the lignin was when spinning each in the form of a solution with 30% lignin in 5% NaOH before.
- the lignin-containing viscoses were spun according to standard conditions.
- the target denier of the fibers was 3.3 dtex, the draw was 25%.
- the resulting fibers were washed out in a conventional manner.
- the lignin contents in the finished fiber were first measured by the Klason method (Tappi Test Methods 2001-2002, T 222 om-02 Tappi Press). According to this method, the acid-insoluble lignin ("Klason lignin”) is detected gravimetrically. In addition, the acid-soluble lignin is determined photometrically (Tappi UM 250, wavelength: 205 nm, absorption coefficient: 110 L / (g.cm)). The photometric determination using these parameters is the usual method in the art, although it is known that the results obtained with respect to the different lignin types can vary slightly. For the purposes of the present invention, it is thus defined that the determination of the acid-soluble lignin content must be made using these parameters.
- the lignosulfonate is thus washed out due to the very good solubility already during the spinning of the fiber and in the subsequent wash to a large extent. Only 11% lignin (absolute) was found in the fiber, so 77% of the lignin offered was washed out. Organosolv lignin shows the highest retention. The fiber contains 38% lignin, while 23% of the offered lignin was washed out. A medium retention shows the force lignin with a content of absolutely 27% lignin in the fiber, while 45% (relatively) were washed out.
- the fiber had a titer of 3.24 dtex.
- the maximum tensile force in cN was 6.71, the elongation 18.79%.
- the fiber had a denier of 3.66 dtex.
- the maximum tensile force in cN was 5.72, the elongation 17.95%.
- Example 2 Analogously to Example 1, a mixture of 35% uncrosslinked Organsolv lignin of the type batch K002 (manufacturer: Fraunhofer Institute CBP) and 15% of the lignosulfonate used in Example 1, in each case based on the total amount of fiber-forming polymer (cellulose + lignin), a viscose blended and the resulting solution spun into fibers.
- the mixture showed very good spinning stability.
- the fiber had a titer of 2.72 dtex.
- the maximum tensile force in cN was 2.78, the elongation 17.12%.
- the water retention was 123%.
- the fibers are distinguished by a dark brown color.
- the fibers prepared according to Example 1 with (nominal) 50% addition of lignin show a very smooth surface with mainly C-shaped cross-sections. These cross sections are in the FIG. 1 shown.
- lignin-containing fibers show a significantly higher absorption (higher water retention capacity) compared to a normal viscose fiber, making them ideal for use in hygiene products.
- the (inter alia) containing lignosulfonate fiber according to Example 4 contains sulfonic acid groups which act as ion exchangers.
- organosolv lignin or a mixture of organosolv lignin and lignosulfonate-containing viscose fibers prepared according to Examples 1, 2 and 4 were carbonized (Gero oven, 20 ° C. to 1800 ° C., heating rate 10 K / min under a nitrogen atmosphere). The carbon yield was compared to that of a standard viscose 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)
- Inorganic Fibers (AREA)
Abstract
Die vorliegende Erfindung betrifft eine regenerierte Cellulosefaser, enthaltend Organosolv-Lignin. Die erfindungsgemäße Faser weist bevorzugt einen Gehalt an Organosolv-Lignin von 5% bis 90%, bevorzugt 10% bis 70%, besonders bevorzugt 20% bis 50%, bezogen auf Faser, auf. Weiters bevorzugt kann die Faser ein weiteres, von Organosolv-Lignin unterschiedliches Lignin enthalten.The present invention relates to a regenerated cellulose fiber containing Organosolv lignin. The fiber according to the invention preferably has a content of organosolv lignin of 5% to 90%, preferably 10% to 70%, particularly preferably 20% to 50%, based on fiber. More preferably, the fiber may contain another lignin different from organosolv lignin.
Description
Die vorliegende Erfindung betrifft eine nach dem Viskoseverfahren hergestellte regenerierte Cellulosefaser (im folgenden auch "Viskosefaser" genannt), deren Herstellung und Verwendung.The present invention relates to a regenerated cellulose fiber produced by the viscose process (hereinafter also referred to as "viscose fiber"), to the production and use thereof.
Insbesondere betrifft die vorliegende Erfindung eine regenerierte Cellulosefaser, welche Lignin enthält.In particular, the present invention relates to a regenerated cellulosic fiber containing lignin.
Viskosefasern werden bereits in carbonisierten Isolationsformteilen und -vliesen eingesetzt. Bei der Carbonisierung werden kohlenstoffhaltige Ausgangsmaterialien (Precursoren) in einem Ofen bei Temperaturen von 500-1800 °C unter Sauerstoffausschluss pyrolysiert. Dabei werden Fremdatome wie Stickstoff, Sauerstoff und Wasserstoff gasförmig abgespalten. Übrig bleibt dabei fast ausschließlich Kohlenstoff, der eine graphitähnliche Schichtstruktur aufweist. Die Carbonisierungsausbeute von Viskose liegt theoretisch bei 44%, in der Realität aber bei nur 15-20%. Man verliert bei der Carboniserung also 80 bis 85% der Fasermasse. Durch Verbesserung der Kohlenstoffausbeute würde der Carbonisierungsprozess wesentlich wirtschaftlicher.Viscose fibers are already used in carbonized insulating moldings and nonwovens. In the carbonization carbonaceous starting materials (precursors) are pyrolyzed in an oven at temperatures of 500-1800 ° C with exclusion of oxygen. This foreign atoms such as nitrogen, oxygen and hydrogen are split off in gaseous form. What remains is almost exclusively carbon, which has a graphite-like layer structure. The carbonation yield of viscose is theoretically 44%, but in reality only 15-20%. Thus, 80 to 85% of the fiber mass is lost during the carbonization. By improving the carbon yield, the carbonation process would be much more economical.
Aus der
Als ein mögliches Einsatzgebiet der dort beschriebenen modifizierten Viskosefasern nennt die
Die
Auch die
Die
In der
Weitere Dokumente, die sich mit der Verwendung von Lignin, insbesondere in Ligninfasern oder Mischfasern enthaltend Lignin beschäftigen, sind beispielsweise:
Es besteht nach wie vor ein Bedürfnis zur Herstellung von Lignin enthaltenden Cellulosefasern. Solche Fasern wären insbesondere zur Herstellung von Carbonfasern geeignet, wobei aufgrund der Beimischung des kostengünstigen Rohstoffes Lignin die Carbonfaser kostengünstiger hergestellt werden kann.There is still a need for producing lignin-containing cellulosic fibers. Such fibers would be particularly suitable for the production of carbon fibers, which due to the admixture of the cost-effective raw material lignin carbon fiber can be produced more cheaply.
Die der vorliegenden Erfindung zugrundeliegende Aufgabe wird durch eine regenerierte Cellulosefaser, enthaltend Organosolv-Lignin, gelöst.The object underlying the present invention is achieved by a regenerated cellulose fiber containing Organosolv lignin.
-
Figur 1 zeigt die Querschnitte von Viskosefasern, in die (nominal) 50% Organosolv-Lignin eingelagert wurden.FIG. 1 shows the cross-sections of viscose fibers in which (nominal) 50% Organosolv lignin were incorporated. -
Figur 2 zeigt die Querschnitte von Viskosefasern, in die (nominal) 10% Organosolv-Lignin eingelagert wurden.FIG. 2 shows the cross-sections of viscose fibers in which (nominal) 10% Organosolv lignin were incorporated. -
Figur 3 zeigt die Querschnitte von Viskosefasern, in die (nominal) 35% Organosolv-Lignin und 15% Lignosulfonat eingelagert wurden.FIG. 3 shows the cross sections of viscose fibers in which (nominal) 35% organosolv lignin and 15% lignosulfonate were incorporated.
Bei der Herstellung von Zellstoff werden Holz (Hackschnitzel) oder andere Pflanzenfasern chemisch aufgeschlossen, indem das darin vorhandene Lignin herausgelöst wird, während die Struktur der Cellulose weitestgehend erhalten bleibt. Das gelöste Lignin unterscheidet sich stark von seiner nativen Form, da beim Aufschluss je nach Verfahren Depolymerisationen und Derivatisierungen mit den Chemikalien eintreten.
Die wichtigsten Zellstoffaufschlussverfahren sind das Sulfat-Verfahren (Produkt: Kraft-Lignin) und das Sulfit-Verfahren (Produkt: Lignosulfonate). Dabei werden jährlich mehr als 50 Millionen Tonnen Lignin als Nebenprodukt isoliert.In the production of pulp wood (wood chips) or other plant fibers are chemically digested by the lignin therein is dissolved out while the structure of the cellulose is largely retained. The dissolved lignin differs greatly from its native form, since depolymerizations and derivatizations with the chemicals occur during digestion, depending on the process.
The most important pulping processes are the sulphate process (product: kraft lignin) and the sulphite process (product: lignosulphonates). More than 50 million tonnes of lignin are isolated as a by-product every year.
Als makromolekularer Naturstoff unterscheiden sich die Lignine in ihrer Monomerzusammensetzung, Art der Bindungen und ihrem Molekulargewicht je nach Pflanzenart, Herkunft und Jahreszeit. Zusätzlich erzeugt jedes Aufschlussverfahren Lignine mit anderen Eigenschaften.As a macromolecular natural product, the lignins differ in their monomer composition, type of bonds and their molecular weight depending on the plant species, origin and season. In addition, each digestion process produces lignins with other properties.
Unter dem "Organosolv-Verfahren" versteht der Fachmann einen Holzaufschluss mit Hilfe von wässerigen organischen Lösungsmitteln, insbesondere Ethanol, bei hohem Druck und hoher Temperatur. Das bei diesem Verfahren anfallende Lignin wird als Organosolv-Lignin bezeichnet.By the "Organosolv method" the skilled person understands a wood pulping with the aid of aqueous organic solvents, in particular ethanol, at high pressure and high temperature. The resulting lignin in this process is called Organosolv lignin.
Es hat sich nun überraschenderweise gezeigt, dass entgegen der in
Die erfindungsgemäße Cellulosefaser kann einen Gehalt an Organosolv-Lignin von 5% bis 90%, bevorzugt 10% bis 70%, besonders bevorzugt 20% bis 50%, bezogen auf Faser, aufweisen. Diese Angaben verstehen sich auch im Folgenden als Gewichts-%. Weiters beziehen sich die Angaben auf den Ligningehalt einer fertigen Viskosefaser, d.h. der Faser nach den im Rahmen der Viskosefaserherstellung üblichen Nachbehandlungs- und insbesondere Waschschritten. Die Gehalte an Organosolv-Lignin sowie auch anderen Ligninen werden nach der in Beispiel 1 angegebenen Meßmethode ermittelt.The cellulose fiber of the invention may have a content of Organosolv lignin of 5% to 90%, preferably 10% to 70%, particularly preferably 20% to 50%, based on fiber. These figures are also understood below as weight%. Furthermore, the figures relate to the lignin content of a finished viscose fiber, i. the fiber according to the usual in the context of Viskosefaserherstellung aftertreatment and especially washing steps. The contents of Organosolv lignin as well as other lignins are determined by the measurement method given in Example 1.
Bevorzugt ist ein möglichst hoher Gehalt an Lignin, da sich bei der Herstellung von Carbonfasern gezeigt hat, dass Lignin eine höhere Kohlenstoffausbeute ermöglicht. Der Begriff "(regenerierte) Cellulosefaser" oder "Viskosefaser" soll im Folgenden auch Fasern umfassen, die bis zu 90% an Lignin enthalten, solange sie nach dem Viskoseverfahren, d.h. aus einer alkalischen Lösung, die Cellulosexanthogenat enthält und in ein saures Spinnbad versponnen wird, hergestellt werden.Preference is given to the highest possible content of lignin, since it has been found in the production of carbon fibers that lignin enables a higher carbon yield. The term "(regenerated) cellulosic fiber" or "viscose fiber" will also encompass fibers containing up to 90% lignin as long as it is made by the viscose process, ie from an alkaline solution containing cellulose xanthate and spun into an acid spin bath , getting produced.
Die erfindungsgemäße Faser kann bevorzugt ein weiteres, von Organosolv-Lignin unterschiedliches Lignin enthalten. Da Organosolv-Lignin im Vergleich zu gängigen Ligninen wie z.B. Kraft-Lignin oder Lignosulfonaten schwerer erhältlich ist, kann durch den Ersatz eines Teils des Organosolv-Lignins durch ein anderes Lignin die Herstellung der erfindungsgemäßen Faser sowie der daraus durch Carbonisierung entstehenden Carbonfaser noch günstiger ausgestaltet werden.The fiber of the invention may preferably contain another lignin different from organosolv lignin. Because organosolv lignin is less soluble than common lignins, e.g. Kraft-lignin or lignosulfonates is more difficult to obtain by replacing a portion of the Organosolv lignin by another lignin the production of the fiber according to the invention and the carbon fiber resulting therefrom carbonization can be made even more favorable.
Das weitere Lignin ist bevorzugt aus der Gruppe bestehend aus Kraft-Lignin, Lignosulfonat und Mischungen daraus ausgewählt. Auch das weitere Lignin ist bevorzugt unvernetzt.The further lignin is preferably selected from the group consisting of kraft lignin, lignosulfonate and mixtures thereof. The further lignin is preferably uncrosslinked.
Der Gehalt an weiterem Lignin in der Faser kann von 5% bis 85%, bevorzugt 10% bis 70%, besonders bevorzugt 20% bis 50%, bezogen auf Faser, betragen.The content of further lignin in the fiber may be from 5% to 85%, preferably from 10% to 70%, particularly preferably from 20% to 50%, based on fiber.
Das Verhältnis von Organosolv-Lignin zum weiteren Lignin kann von 4:1 bis 1:4, bevorzugt 3:1 bis 1:3 betragen.The ratio of organosolv lignin to further lignin may be from 4: 1 to 1: 4, preferably 3: 1 to 1: 3.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist die erfindungsgemäße Cellulosefaser dadurch gekennzeichnet, dass sie abgesehen von Cellulose und Lignin im wesentlichen kein weiteres faserbildendes Polymer, wie z.B. Polyacrylnitril oder Polyacrylnitril-Copolymere, enthält.In a preferred embodiment of the present invention, the cellulosic fiber of the present invention is characterized by substantially no further fiber-forming polymer, such as cellulose and lignin. Polyacrylonitrile or polyacrylonitrile copolymers containing.
Die erfindungsgemäße Cellulosefaser kann einen Titer von 0,5 dtex bis 30 dtex, bevorzugt 1 dtex bis 4 dtex, aufweisen.The cellulose fiber according to the invention may have a titer of 0.5 dtex to 30 dtex, preferably 1 dtex to 4 dtex.
Bevorzugt wird die erfindungsgemäße Cellulosefaser zur Herstellung von Carbonfasern verwendet. Weitere Einsatzgebiete sind z.B. Hygiene- und Medizinanwendungen (aufgrund des erhöhten Wasserrückhaltevermögens der Faser). Eine erfindungsgemäße Cellulosefaser, die zusätzlich zum Organosolv-Lignin Ligninsulfonat enthält, eignet sich aufgrund der in die Faser damit eingeführten Sulfonsäuregruppen (Lignosulfonat enthält 1,25 -2,5% Sulfonsäuregruppen) auch zum Ionenaustausch beispielsweise in der Wasserenthärtung oder auch beim Abbinden von Beton.The cellulose fiber according to the invention is preferably used for the production of carbon fibers. Further fields of use are e.g. Hygiene and medical applications (due to the increased water retention capacity of the fiber). A cellulose fiber according to the invention which, in addition to the Organosolv lignin, contains lignosulfonate, is also suitable for ion exchange, for example in water softening or in the setting of concrete, due to the sulfonic acid groups introduced into the fiber (lignosulfonate containing 1.25-2.5% sulfonic acid groups).
Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung der erfindungsgemäßen Cellulosefaser, umfassend den Schritt der Zugabe von Organosolv-Lignin und gegebenenfalls eines weiteren Lignins zu einer Spinnviskose oder einem Vorläufer davon.The present invention also relates to a process for producing the cellulosic fiber of the invention, comprising the step of adding organosolv lignin and optionally another lignin to a spun viscose or a precursor thereof.
Unter "Vorläufer" einer Spinnviskose werden insbesondere Ausgangssubstanzen des Viskoseverfahrens, wie z.B. Zellstoff, oder Zwischenprodukte wie z.B. Alkalicellulose oder Cellulosexanthogenat verstanden.By "precursors" of a spinning viscose are in particular starting substances of the viscose process, such as e.g. Pulp, or intermediates such as e.g. Alkali cellulose or cellulose xanthogenate understood.
Es wurden Pilotausspinnungen zur Herstellung von Viskosefasern, in die folgende unvernetzte Lignine eingesponnen wurden, durchgeführt:
- Kraft-Lignin (Hersteller: Sigma-Aldrich)
- Lignosulfonat (Hersteller: Carl Roth) und
- Organosolv-Lignin (Hersteller: Fraunhofer CBP Leuna Charge K002)
- Kraft lignin (manufacturer: Sigma-Aldrich)
- Lignosulfonate (manufacturer: Carl Roth) and
- Organosolv lignin (manufacturer: Fraunhofer CBP Leuna batch K002)
Das Lignin wurde jeweils in einem Anteil von 50% bezogen auf die Gesamtmenge an faserbildendem Polymer (Cellulose + Lignin) in eine Standardviskose eingemischt. Das Lignin lag beim Einspinnen jeweils in Form einer Lösung mit 30% Lignin in 5%iger NaOH vor.The lignin was mixed in a proportion of 50% based on the total amount of fiber-forming polymer (cellulose + lignin) in a standard viscose. The lignin was when spinning each in the form of a solution with 30% lignin in 5% NaOH before.
Die Lignin enthaltenden Viskosen wurden nach Standardbedingungen ausgesponnen. Der Zieltiter der Fasern betrug 3,3 dtex, die Verstreckung betrug 25%.The lignin-containing viscoses were spun according to standard conditions. The target denier of the fibers was 3.3 dtex, the draw was 25%.
Die erhaltenen Fasern wurden in üblicher Weise ausgewaschen.The resulting fibers were washed out in a conventional manner.
Die Lignin-Gehalte in der fertigen Faser wurden zunächst über die Klason-Methode (Tappi Test Methods 2001-2002. T 222 om-02. Tappi Press) gemessen. Nach dieser Methode wird das säure-unlösliche Lignin ("Klason-Lignin") gravimetrisch erfasst. Zusätzlich wird das säurelösliche Lignin photometrisch bestimmt (Tappi UM 250, Wellenlänge: 205 nm, Absorptionskoeffizient: 110 L/(g.cm)). Die photometrische Bestimmung anhand dieser Parameter ist die in der Fachwelt üblichen Methode, auch wenn bekannt ist, dass die damit erhaltenen Resultate hinsichtlich der verschiedenen Lignin-Typen leicht variieren können. Für die Zwecke der vorliegenden Erfindung wird somit definiert, dass die Bestimmung des Gehaltes an säurelöslichem Lignin unter Anwendung dieser Parameter zu erfolgen hat. Die folgenden Werte stellen jeweils den so ermittelten Gesamt-Lignin-Gehalt dar:
Das Lignosulfonat wird also aufgrund der sehr guten Löslichkeit schon während des Ausspinnens der Faser und in der nachfolgenden Wäsche zu einem großen Teil ausgewaschen. Lediglich 11% Lignin (absolut) wurden in der Faser gefunden, dementsprechend wurden 77% des angebotenen Lignins ausgewaschen. Das Organosolv-Lignin zeigt die höchste Retention. Die Faser enthält 38% Lignin, während 23% des angebotenen Lignins ausgewaschen wurden. Eine mittlere Retention zeigt das Kraft-Lignin mit einem Gehalt von absolut 27% Lignin in der Faser, während 45% (relativ) ausgewaschen wurden.The lignosulfonate is thus washed out due to the very good solubility already during the spinning of the fiber and in the subsequent wash to a large extent. Only 11% lignin (absolute) was found in the fiber, so 77% of the lignin offered was washed out. Organosolv lignin shows the highest retention. The fiber contains 38% lignin, while 23% of the offered lignin was washed out. A medium retention shows the force lignin with a content of absolutely 27% lignin in the fiber, while 45% (relatively) were washed out.
Ein unvernetztes Organosolv-Lignin der Type Lignin 139OL (Hersteller: Fraunhofer-Institut CBP) wurde analog zu Beispiel 1 in einem Anteil von 10% bezogen auf die Gesamtmenge an faserbildendem Polymer (Cellulose + Lignin) einer Viskose zugemischt und die entstehende Lösung zu Fasern gesponnen.An uncrosslinked Organosolv lignin of the type lignin 139OL (manufacturer: Fraunhofer Institute CBP) was mixed in a proportion of 10% based on the total amount of fiber-forming polymer (cellulose + lignin) of a viscose and spun the resulting solution into fibers ,
In der fertigen Faser wurden nach der oben beschriebenen Methode insgesamt 7,7% Lignin gefunden.In the finished fiber, a total of 7.7% lignin was found by the method described above.
Die Faser wies einen Titer von 3,24 dtex auf. Die Höchstzugkraft in cN betrug 6,71, die Dehnung 18,79%.The fiber had a titer of 3.24 dtex. The maximum tensile force in cN was 6.71, the elongation 18.79%.
Ein unvernetztes Organosolv-Lignin der Type Lignin 151OL (Hersteller: Fraunhofer-Institut CBP) wurde analog zu Beispiel 1 in einem Anteil von 10% bezogen auf die Gesamtmenge an faserbildendem Polymer (Cellulose + Lignin) einer Viskose zugemischt und die entstehende Lösung zu Fasern gesponnen.An uncrosslinked organosolv lignin of the type lignin 151OL (manufacturer: Fraunhofer Institute CBP) was mixed in a proportion of 10% based on the total amount of fiber-forming polymer (cellulose + lignin) a viscose and spun the resulting solution into fibers ,
In der fertigen Faser wurden nach der oben beschriebenen Methode insgesamt 7,3% Lignin gefunden.In the finished fiber, a total of 7.3% lignin was found by the method described above.
Die Faser wies einen Titer von 3,66 dtex auf. Die Höchstzugkraft in cN betrug 5,72, die Dehnung 17,95%.The fiber had a denier of 3.66 dtex. The maximum tensile force in cN was 5.72, the elongation 17.95%.
Analog zu Beispiel 1 wurde eine Mischung von 35% unvernetztes Organsolv-Lignin der Type Charge K002 (Hersteller: Fraunhofer-Institut CBP) und 15% des in Beispiel 1 verwendeten Lignosulfonates, jeweils bezogen auf die Gesamtmenge an faserbildendem Polymer (Cellulose + Lignin), einer Viskose zugemischt und die entstehende Lösung zu Fasern gesponnen.Analogously to Example 1, a mixture of 35% uncrosslinked Organsolv lignin of the type batch K002 (manufacturer: Fraunhofer Institute CBP) and 15% of the lignosulfonate used in Example 1, in each case based on the total amount of fiber-forming polymer (cellulose + lignin), a viscose blended and the resulting solution spun into fibers.
Die Mischung zeigte eine sehr gute Spinnstabilität.The mixture showed very good spinning stability.
In der fertigen Faser wurden nach der oben beschriebenen Methode insgesamt 35,4% Lignin gefunden. Die Auswaschung an Lignin betrug somit nur etwa 15% (absolut).In the finished fiber, a total of 35.4% lignin was found by the method described above. The leaching of lignin was thus only about 15% (absolute).
Die Faser wies einen Titer von 2,72 dtex auf. Die Höchstzugkraft in cN betrug 2,78, die Dehnung 17,12%. Das Wasserrückhaltevermögen betrugt 123%.The fiber had a titer of 2.72 dtex. The maximum tensile force in cN was 2.78, the elongation 17.12%. The water retention was 123%.
Die Fasern sind durch eine dunkelbraune Farbe ausgezeichnet.The fibers are distinguished by a dark brown color.
Die gemäß Beispiel 1 hergestellten Fasern mit (nominal) 50% Zugabe von Lignin zeigen eine sehr glatte Oberfläche mit hauptsächlich C-förmigen Querschnitten. Diese Querschnitte sind in der
Bei den gemäß Beispiel 2 hergestellten (nominale Einlagerung von 10% Organosolv-Lignin) findet man dagegen die typische Viskose-Wolkenform vor, siehe
Die gemäß Beispiel 3 hergestellten Fasern mit einer nominalen Einlagerung von 35% Organosolv-Lignin und 15% Lignosulfonat zeigen ebenfalls die typische Viskose-Wolkenform vor, siehe
Sämtliche der ligninhaltigen Fasern zeigen eine gegenüber einer normalen Viskosefaser deutlich höhere Absorption (höheres Wasserrückhaltevermögen), weswegen sie sich ideal für eine Anwendung in Hygieneprodukten eignen.All of the lignin-containing fibers show a significantly higher absorption (higher water retention capacity) compared to a normal viscose fiber, making them ideal for use in hygiene products.
Die (unter anderem) Lignosulfonat enthaltende Faser gemäß Beispiel 4 enthält Sulfonsäuregruppen, die als Ionenaustauscher wirken.The (inter alia) containing lignosulfonate fiber according to Example 4 contains sulfonic acid groups which act as ion exchangers.
Die gemäß Beispiel 1, 2 und 4 hergestellten, Organosolv-Lignin bzw. eine Mischung aus Organosolv-Lignin und Lignosulfonat enthaltenden Viskosefasern wurden carbonisiert (Gero-Ofen, 20 °C bis 1800 °C, Heizrate 10K/min unter Stickstoffatmosphäre). Die Kohlenstoffausbeute wurde mit der einer Standard-Viskosefaser verglichen.The organosolv lignin or a mixture of organosolv lignin and lignosulfonate-containing viscose fibers prepared according to Examples 1, 2 and 4 were carbonized (Gero oven, 20 ° C. to 1800 ° C., heating rate 10 K / min under a nitrogen atmosphere). The carbon yield was compared to that of a standard viscose fiber.
Die Ergebnisse sind in der folgenden Tabelle dargestellt:
Durch eine Einlagerung von 10% (real 7,8%) Organosolv-Lignin in Viskose lässt sich die Kohlenstoffausbeute bereits um etwa 2% erhöhen. Rein rechnerisch ergibt sich dabei für das Lignin eine reale Kohlenstoffausbeute von 40%.By incorporating 10% (7.8% in real terms) Organosolv lignin into viscose, the carbon yield can be increased by about 2%. Purely arithmetically, this results in a real carbon yield of 40% for the lignin.
Die 50% Organosolv-Lignin-Faser und die Mischviskosefaser aus 35% Organosolv-Lignin und 15% Lignosulfonat zeigen beide Kohlenstoffausbeuten um die 30%. Gegenüber normaler Viskose lässt sich die Kohlenstoffausbeute durch die Einlagerung von größeren Mengen Lignin also deutlich (um 80%) steigern. In diesem Fall liegt die rechnerische Ausbeute für das reine Lignin bei knapp 60%. Dies bedeutet, dass für den Hersteller von Carbonfaser große Einsparungen in der Fasermenge bei gleicher Kohlenstoffausbeute möglich sind.The 50% Organosolv lignin fiber and the mixed viscose fiber of 35% Organosolv lignin and 15% lignosulfonate both show carbon yields of around 30%. Compared with normal viscose, the carbon yield can be significantly increased (by 80%) through the incorporation of larger amounts of lignin. In this case, the calculated yield for pure lignin is just under 60%. This means that for the manufacturer of Carbon fiber large savings in the amount of fiber with the same carbon yield are possible.
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