EP1268556A1 - Procede et dispositif pour produire en continu une suspension cellulosique dans un aminoxyde aqueux - Google Patents

Procede et dispositif pour produire en continu une suspension cellulosique dans un aminoxyde aqueux

Info

Publication number
EP1268556A1
EP1268556A1 EP00979396A EP00979396A EP1268556A1 EP 1268556 A1 EP1268556 A1 EP 1268556A1 EP 00979396 A EP00979396 A EP 00979396A EP 00979396 A EP00979396 A EP 00979396A EP 1268556 A1 EP1268556 A1 EP 1268556A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
suspension
amine oxide
zone
cellulose material
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.)
Withdrawn
Application number
EP00979396A
Other languages
German (de)
English (en)
Inventor
Ralf-Uwe Bauer
Uwe Kind
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.)
Alceru Schwarza GmbH
Original Assignee
Alceru Schwarza GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alceru Schwarza GmbH filed Critical Alceru Schwarza GmbH
Publication of EP1268556A1 publication Critical patent/EP1268556A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • 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

Definitions

  • the invention relates to a process for the continuous production of a suspension of cellulose in a water tertiary amine oxide for use in the Lyocell process.
  • the invention also relates to a device for performing this method.
  • a cellulose suspension to produce in aqueous N-methylmorpholine-N-oxide (NMMO) by mixing the comminuted cellulose directly with the aqueous, for example 75% by mass NMMO in a ring layer mixer.
  • the suspension formed is dissolved in a separate film truder.
  • a disadvantage of the annular layer mixer is that only a comminuted, essentially dry cellulose can be used. If the cellulose contains water, the layer formation in the mixer is made more difficult by the mixing with the separately added NMMO solution. The water must be thermally separated. The soluble constituents of the pulp get into the spinning solution and lead to disadvantageous properties of the cellulose products. Since the suspension is transported as a layer, the throughput related to the cross-section of the apparatus is low.
  • the present invention has for its object to provide a method and an apparatus for the continuous production of a suspension of cellulose in an aqueous tertiary amine oxide with reduced equipment expenditure for the formation of suspensions and cellulose activation for use in the Lyocell process.
  • the throughput of the cellulose material which is based on the volume of the shear zone, is to be increased and the manufacturing time of the suspension is to be reduced. Further advantages result from the following description.
  • the invention accordingly proceeds from a process for the continuous production of a suspension of cellulose and an aqueous tertiary amine oxide for use in the lyocell process, in which (a) cellulose and an amine oxide-free aqueous phase have a mass ratio in the range from 1: 3 to 1 : 40 forms a cellulose suspension, (b) the cellulose suspension is dewatered to a material with a cellulose content in the range from 20 to 80% by mass, and (c) the moist cellulose material is mixed with as much water-containing amine oxide and is passed through a horizontal shear zone, that after the mixture there is a suspension with an ammoxide content in the liquid phase in the range from 70 to 80% by mass, the suspension essentially completely filling the available cross section of the shear zone.
  • stage (c) finely divided aqueous amine oxide is added to the moist cellulose material in a falling zone which is only partially filled by the cellulose material, and the cellulose material mixed with the amine oxide is introduced into the shear zone.
  • stage (c) finely divided aqueous amine oxide is added to the moist cellulose material in a falling zone which is only partially filled by the cellulose material, and the cellulose material mixed with the amine oxide is introduced into the shear zone.
  • the first part of the shear zone is omitted, through which the cellulose material is required and homogenized in the absence of NMMO.
  • the water-containing amine oxide is not introduced into the shear zone, which is essentially completely filled by the suspension, but into the upstream drop zone.
  • the cellulose material only partially fills the drop zone, so that with the feeding of the ammoxide, a pre-distribution of the ammoxide in the moist cellulose material is achieved.
  • This pre-distribution of the ammoxide makes it possible to shorten the shear zone adjoining the falling zone to form a uniform suspension for the subsequent solution formation. Compared to the method according to DE 198 37 210.8, this shortens the shear zone by about 1/3 and saves investment costs by 10 to 15%.
  • the water-containing amine oxide is dusted into the drop zone.
  • the falling particles of the moist cellulose material are coated with the water-containing amine oxide, and there is a good premix which allows the subsequent homogenization section to be shortened in the shaving apparatus. Dust-N-methylmorphol-N-oxide monohydrate is preferred in the fall zone.
  • step (a) above the supplied pulp (roll or sheet form) can be whipped with water in a pulper or homogenizer.
  • the reactivity or accessibility of the cellulose chains for the amine oxide can be improved by adding enzymes.
  • Dewatering in stage (b) can be achieved using a belt press, screw press, roller filter or centrifuge. It is preferable to dewater to a cellulose content in the range of 45 to 55% by mass. The slightly fluctuating water content after dewatering can be evened out on the transport to the weighing device. Since the water-containing amine oxide used is often a reprocessed solution prepared from a used waste bath, Fall bath regeneration can aim at the formation of an ammoxide concentrate of the required concentration.
  • the short-term and short shear zone ensures sufficient comminution and homogenization of the cellulose particles, which is not possible with the known ring-layer mixer.
  • a water-containing amine oxide with a molar ratio of amine oxide to water in the range from 1: 1 to 1: 2.2 can be used according to the invention.
  • the most concentrated ammoxide, namely in particular NMMO monohydrate, will be used in water-containing cellulose which, for example, has been broken down with water and / or pretreated enzymatically or thermally before the suspension according to the invention.
  • the preparation of the mash is conveniently carried out at a temperature in the range from 75 to 100 ° C. At these temperatures, the cellulose breakdown and the decomposition of the ammoxide are low; on the other hand, the homogenization and uniform mixing of the moist cellulose with the ammoxide are favored by the elevated temperature.
  • the temperature-controlled suspension can be brought to a solution in a subsequent step by evaporation of water under vacuum without a significant change in temperature.
  • the mashing is carried out in a continuous pass and the suspension is continuously drawn off at the end of the shear zone and passed into a loose stage. Since the process runs continuously, the suspension formed can run continuously into the batch stage without the need for an intermediate container.
  • the process can be carried out with the addition of additives such as stabilizers. These additives can also be found in be added to the falling zone together with the amine oxide.
  • the invention is also based on a device comprising (a) a mixing apparatus with mixing elements, supply nozzle for cellulose and aqueous suspension medium and discharge nozzle for the suspension, (b) a separator connected to the mixer for partial separation of the suspension medium from the cellulose and ( c) a shaving apparatus with horizontal shafts equipped with shearing tools, a loading device for the cellulose material from the separating apparatus at one end of the shaving apparatus and a discharge pipe for the suspension at the other end of the shaving apparatus.
  • This device is characterized according to the invention in that the loading device is a downpipe for the formation of a drop zone and is provided with nozzles directed into its interior for the introduction of the water-containing ammoxide into the cellulose material. While according to DE 198 37 210.8 the loading device of the shear apparatus e funnel for introducing the cellulose material present as bulk material is the shear apparatus, according to the invention the loading device is provided for the formation of a falling zone which the pulp material particles fall through and therefore offers the possibility of these particles to spray and wet with the aqueous am oxide so that a premix of the moist cellulose material and the aqueous ammoxide is formed in the drop zone, which is drawn as such into the shaving apparatus.
  • the loading device can be a vertical tube, which can be cylindrical or conical in the direction of the shearing apparatus, narrowing or widening.
  • the mixing of the cellulose particles with aqueous amine oxide is therefore more advanced than when the ammoxide is fed into the shaving apparatus in the process according to DE 198 37 210.8.
  • the length of the apparatus can therefore be shortened considerably without the swelling state of the cellulose particles in the suspension being impaired thereby.
  • At least one slide equipped with nozzles is preferably arranged in the feed pipe.
  • the aqueous ammoxide is emitted into the downpipe via this pipe. It is advantageous here that the particles or particle aggregates of the moist cellulose material falling through the tube are as small as possible.
  • the partially dewatered cellulose material can be passed through a shredder before entering the downpipe.
  • the at least one ring line is expediently connected to a heated inlet line. This prevents the aqueous ammoxide from becoming solid within the lines and nozzles.
  • a horizontal multi-shaft reactor such as a multi-screwless machine with self-cleaning heat exchange surfaces, a reactor with 2 to 8 co-rotating, intermeshing screws or a multi-chamber mixer can be used as a shear apparatus.
  • the drawing shows schematically a plant for performing the inventive method.
  • a mixing container 1 is fed continuously through pipe 2 with cellulose and through pipe 3 with water as a suspending agent.
  • the aqueous pulp suspension formed in the container 1 passes via the line 4 to a belt press 5, on which it is dewatered to a liquid content of 50%.
  • the moist pulp material obtained on the screen belt press passes as a fleece through a weighing device 6 in a funnel-shaped downpipe 7 which, in the embodiment shown, has an Rmtechnisch 8 on the inside with nozzles 9 directed into the interior of the tube.
  • the Rmg réelle 8 is fed with a heated supply line 10 with water NMMO.
  • the moist cellulose material falls through the tube 7 and is thereby wetted and loaded with the emitted aqueous ammoxide, so that at the lower end of the downpipe 7 there is a mixture of water-containing cellulose material and amine oxide which also contains air cushions.
  • the downpipe 7 is followed by a multi-shaft apparatus 11 in which the mixture drawn into the apparatus is further mixed by the shearing and conveying elements (not shown) arranged on the shafts 12 and conveyed to the outlet pipe 13.
  • the air entrained with the mixture through the downpipe 7 and some water vapor are drawn off through the nozzle 14.
  • a connecting device which is constructed similarly to the multi-shaft device 11, connects to the outlet pipe 13.
  • the cellulose solution is formed in it at elevated temperature.
  • the apparatus 11 as well as the dissolver, not shown, are provided with a heating jacket (not shown), so that the desired mixing or. Dissolving temperature can be maintained.
  • NMMO monohydrate is added at a rate of 127.3 kg / h via nozzles in the chute.
  • the cellulose / water suspension is mixed uniformly with the NMMO monohydrate.
  • a mash is obtained with an NMMO content of 76%, so that in a subsequent evaporation stage a spinning solution with a 12.9% cellulose content can be prepared.
  • the quality assessment of the spinning solution formed from the suspension was carried out using a microscope V 300, from Hund, Wetzlar, with an evaluation unit (video camera and printer from JVC).
  • the number of undissolved cellulose particles in the spinning sample is given in each case 1 cm 2 .
  • the following quality rating applies: number of undissolved cellulose particles / cm 2 rating
  • the spinning solution of this example contained no undissolved particles / cm 2 .
  • the cellulose solution is well suited for direct processing into fibers, filament yarns and foils using the dry-wet spinning process.
  • the invention is not restricted to the embodiment shown in FIG. 1.
  • the aqueous amine oxide can not only be injected vertically or obliquely up or down to the direction of fall from the circumference (jacket) of the fall zone, but also parallel and / or obliquely to the direction of fall at the inlet 7 of the downpipe. When inserting the circumference, this is expediently carried out in the upper half of the downpipe 9.
  • the feed speed of the downpipe is preferably matched to the conveying speed of the multi-shaft apparatus in such a way that a bed is present in the lowermost part of the downpipe 7 before it enters the multi-shaft apparatus 11 that as little air as possible is drawn into the multi-shaft apparatus,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé pour produire en continu une suspension cellulosique dans un aminoxyde tertiaire aqueux, destinée à être utilisée dans un procédé de Lyocell, selon lequel: a) une suspension cellulosique est préparée à partir de cellulose et d'une phase aqueuse exempte d'aminoxyde dans un rapport de masse de l'ordre de 1:3 à 1:40, (b) la suspension cellulosique est déshydratée jusqu'à obtention d'une matière dont le teneur en cellulose se situe entre 20 et 80 % en masse, et (c) la matière cellulosique humide est mélangée avec une quantité suffisante d'aminoxyde aqueux et acheminée à travers une zone de cisaillement horizontale, en vue d'obtenir, après mélange, une suspension dont la teneur en aminoxyde dans la phase liquide se situe entre 70 et 80 % en masse, la suspension remplissant pratiquement entièrement la section de transport disponible dans la zone de cisaillement. L'invention est caractérisée en ce qu'à l'étape (c) un aminoxyde aqueux finement divisé est ajouté à la matière cellulosique humide dans une zone de chute remplie seulement partiellement par la matière cellulosique, et en ce que la matière cellulosique contenant l'aminoxyde est alors acheminée dans la zone de cisaillement. L'invention concerne également un dispositif pour réaliser ledit procédé, qui nécessite relativement peu d'appareillage pour la préparation de la suspension. Le débit de la matière cellulosique, rapporté au volume de la zone de cisaillement, peut être augmenté.
EP00979396A 2000-03-20 2000-09-29 Procede et dispositif pour produire en continu une suspension cellulosique dans un aminoxyde aqueux Withdrawn EP1268556A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10013777 2000-03-20
DE10013777A DE10013777C2 (de) 2000-03-20 2000-03-20 Verfahren und Vorrichtung zur kontinuierlichen Herstellung einer Suspension von Cellulose in einem wässrigen Aminoxid
PCT/DE2000/003413 WO2001070819A1 (fr) 2000-03-20 2000-09-29 Procede et dispositif pour produire en continu une suspension cellulosique dans un aminoxyde aqueux

Publications (1)

Publication Number Publication Date
EP1268556A1 true EP1268556A1 (fr) 2003-01-02

Family

ID=7635632

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00979396A Withdrawn EP1268556A1 (fr) 2000-03-20 2000-09-29 Procede et dispositif pour produire en continu une suspension cellulosique dans un aminoxyde aqueux

Country Status (6)

Country Link
US (1) US7115187B1 (fr)
EP (1) EP1268556A1 (fr)
CN (1) CN1235912C (fr)
AU (1) AU2001216916A1 (fr)
DE (1) DE10013777C2 (fr)
WO (1) WO2001070819A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10200406A1 (de) * 2002-01-08 2003-07-24 Zimmer Ag Spinnvorrichtung und -verfahren mit turbulenter Kühlbeblasung
DE10204381A1 (de) * 2002-01-28 2003-08-07 Zimmer Ag Ergonomische Spinnanlage
DE10213007A1 (de) * 2002-03-22 2003-10-09 Zimmer Ag Verfahren und Vorrichtung zur Regelung des Raumklimas bei einem Spinnprozess
DE102004024030A1 (de) 2004-05-13 2005-12-08 Zimmer Ag Lyocell-Verfahren mit polymerisationsgradabhängiger Einstellung der Verarbeitungsdauer
US20060266427A1 (en) * 2005-05-26 2006-11-30 Wyeth Pharmaceuticals. Mixing apparatus
US9206528B2 (en) * 2008-02-08 2015-12-08 List Holding Ag Method and device for the production of molded bodies
AT512601B1 (de) * 2012-03-05 2014-06-15 Chemiefaser Lenzing Ag Verfahren zur Herstellung einer Cellulosesuspension
DE202022101351U1 (de) 2022-03-14 2022-04-14 Thüringisches Institut für Textil- und Kunststoff-Forschung Rudolstadt e.V. Hochgefüllte prekeramische Fasern als Basismaterial für die Herstellung von Knochenersatzkörpern

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413631A (en) * 1993-05-24 1995-05-09 Courtaulds (Holding) Limited Formation of a cellulose-based premix
AT402411B (de) * 1995-04-19 1997-05-26 Chemiefaser Lenzing Ag Anlage sowie integriertes folien- und faserwerk zur herstellung cellulosischer folien und fasern
AT402410B (de) * 1995-04-19 1997-05-26 Chemiefaser Lenzing Ag Verfahren zur herstellung einer cellulosesuspension
DE19837210C1 (de) * 1998-08-17 1999-11-11 Alceru Schwarza Gmbh Verfahren zur Herstellung einer Cellulosesuspension

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0170819A1 *

Also Published As

Publication number Publication date
AU2001216916A1 (en) 2001-10-03
WO2001070819A1 (fr) 2001-09-27
DE10013777C2 (de) 2002-06-20
CN1235912C (zh) 2006-01-11
DE10013777A1 (de) 2001-10-04
US7115187B1 (en) 2006-10-03
CN1451018A (zh) 2003-10-22

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