WO2002057319A2 - Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation - Google Patents

Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation Download PDF

Info

Publication number
WO2002057319A2
WO2002057319A2 PCT/DE2002/000145 DE0200145W WO02057319A2 WO 2002057319 A2 WO2002057319 A2 WO 2002057319A2 DE 0200145 W DE0200145 W DE 0200145W WO 02057319 A2 WO02057319 A2 WO 02057319A2
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
coagulant
beads
tempered
solvent
Prior art date
Application number
PCT/DE2002/000145
Other languages
German (de)
English (en)
Other versions
WO2002057319A3 (fr
Inventor
Frank-Günter NIEMZ
Dieter Vorbach
Original Assignee
Thüringisches Institut für Textil-und Kunststoff-Forschung E.V.
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 Thüringisches Institut für Textil-und Kunststoff-Forschung E.V. filed Critical Thüringisches Institut für Textil-und Kunststoff-Forschung E.V.
Publication of WO2002057319A2 publication Critical patent/WO2002057319A2/fr
Publication of WO2002057319A3 publication Critical patent/WO2002057319A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
    • 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
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives

Definitions

  • the invention relates to the production of regular, porous cellulose beads with a particle diameter in the range up to 5000 microns, in which a cellulose solution is deformed into drops by a nozzle and dripped through an air gap into a liquid medium.
  • the invention also relates to cellulose beads with a wide range of variations with regard to porosity and the areas of use resulting therefrom.
  • the cellulose xanthate solutions obtained are sprayed into an acidic precipitation bath or regenerated after dispersion in another solvent by neutralization with acid or by thermal decomposition of the xanthate complex.
  • the different loads caused by thin acids, sulfur compounds and the resulting neutralization salts not only represent an environmental hazard, but also have a considerable impact on the manufacturing costs.
  • Another way to preserve cellulose pearls is the dissolution of highly substituted organosoluble cellulose esters, e.g. B. in halogenated hydrocarbons, the dispersion of the solution obtained and the evaporation of the volatile solvent.
  • highly substituted organosoluble cellulose esters e.g. B. in halogenated hydrocarbons
  • the dispersion of the solution obtained and the evaporation of the volatile solvent.
  • the beads obtained have a low porosity, which limits their further use as a carrier material. That is why additional pore formers are used at the solution stage.
  • Motozato et al. a. Hydrocarbons, proposed in JP 63-68645 long-chain carboxylic acid esters and carboxylic acids for this purpose.
  • the complexity of these processes is a major disadvantage.
  • DE 19522181 describes a process for the production of spherical cellulose acetate microarticles in which a solvent mixture free of halogenated hydrocarbons is used to dissolve the cellulose acetate. After dispersing in the aqueous medium, evaporation of the solvents, removal of the dispersing agent, washing, cleaning and saponification, cellulose beads are formed.
  • the complexity and complexity of the process are disadvantageous
  • a better way to make cellulose solutions for making cellulose beads is to dissolve cellulose directly in solvents.
  • Proposed solvents such as B. Cuoxam u. ⁇ . (DE 1792230, US 3597350) or calcium rhodanide melts (JP 80-44312) are difficult to handle or present considerable problems when producing higher-concentration solutions.
  • a suitable method for obtaining cellulose beads via the direct dissolution of cellulose is described in DE 19755352 and DE 19755353.
  • a solution of the cellulose in a tertiary amine oxide, for example N-methylmorpholine-N-oxide, is then prepared.
  • the solution is deformed into a jet by pressure, then cut by a rotating cutting jet, the resulting particles are taken up in a dispersing agent and separated from the dispersing agent after cooling, solidified by precipitation to form regular beads and then separated from the liquid precipitant / Separates solvent mixture.
  • the cellulose solution is sheared directly in the dispersing agent and further solidified and aftertreated analogously, as already explained in the previous property right.
  • the object of the invention is to develop a process for producing regular, porous cellulose beads which is technically simple and as continuous as possible is feasible and the production of monodispersed cellulose beads with a wide range of porosity is guaranteed. Furthermore, little or non-toxic auxiliaries should be used in the manufacturing process. Other disadvantages to be found in the previous descriptions should also be avoided.
  • this object is achieved by a) dissolving a cellulose with an average molecular weight of 15,000 to 170,000 in a solvent to give a 0.3 to 10% (mass) solution, b) pressing the cellulose solution through a capillary, wherein the capillary geometry allows the formation of drops, c) the drop created by gravity passes through an air gap into a liquid medium, where its shape relaxes into a ball, the resulting ball solidifies or, when it sinks directly or after passing through a boundary layer, due to precipitation solidified with a solvent-miscible precipitant to form regular, monodisperse beads, d) in a subsequent wash, the beads are completely washed out of the solvent and, if appropriate, any adhering medium from step c) and, if appropriate, dried and further processed.
  • cellulose beads obtained are distinguished by a geometric uniformity which is not the case with any of the prior art processes. ren is achieved.
  • This process can also be used to produce cellulose beads with diameters greater than 1000 ⁇ .
  • the larger geometric dimensions, coupled with the very high uniformity, guarantee a wide range of industrial applications, e.g. B. as adsorbent in biotechnology, as a carrier material for biocatalysts, cell cultures, nutrient solutions or use as an ion exchanger.
  • Embodiments of the method are defined by subclaims 2 to 28. In the following, explanations and examples are given for explanation.
  • the spinning solution [1] is pressed through a capillary [2], which is heated separately in the lower part by a heat transfer medium.
  • the spinning solution consists of a solvent and cellulose.
  • the spinning solution can contain organic or inorganic substances with a maximum particle size of 100 ⁇ m. Such substances are, for example, titanium dioxide, barium sulfate, graphite, carboxymethyl cellulose, polyethylene glycols, chitin, chitosan, alginic acid and alginates, polysaccharides, dyes, activated carbon, commercially available carbon blacks, commercially available ceramic powder.
  • [8a] can be applied.
  • the air flow can be applied.
  • Contain additives for example water vapor, surfactant-containing or coagulating aerosols. Furthermore, the solution drop [4] gets into a column [9] which contains a precipitant [13], which is done with a pump [14] and a
  • Heat exchanger [15] is equipped. Furthermore, the
  • the dripping precipitation bath is collected in the sump [21a] and returned to the column [9] via a pump [22]. Furthermore, the beads in the direction of movement of the sieve belt are treated with washing water [18], which consists of one or more sections [23].
  • the wash water can be pumped in a circle in the sump [21b] using a pump [24]. Different sections can be connected via a cascade [25] in the countercurrent principle pearl - washing water.
  • this cascade connection can, for. B. can be expanded via the feed [19], so that a closed circuit is formed.
  • the circuit is closed via the solvent recovery stage (not shown) between streams [20] and [19].
  • the solvent can also be extracted batchwise using the known batch process.
  • the solvent-free cellulose beads [26] can be dried continuously or in batches or can be made up even further afterwards.
  • a 4% (Ma.) Solution of regenerated cellulose in aqueous N-methylmorpholine-N-oxide (NMMO) was pressed through a glass capillary with an internal diameter at the outlet of 800 ⁇ m.
  • the wall thickness of the capillary was 400 ⁇ m.
  • the lower part of the capillary was heated to a temperature of 140 ° C.
  • the solution dripping from the capillary fell through an air gap of 20 mm into a heptane bath heated to 20 ° C.
  • the height of the bath was 50 cm.
  • a heavily diluted NMMO water bath was located under the heptane. The solution drops were precipitated in this after passing the heptane and the separating layer heptane - water bath.
  • the height of the water bath was 50 cm.
  • the beads were then freed of residual NMMO by water washing.
  • the resulting beads were absolutely round and, after measuring 50 beads with an average diameter of 2.52 mm with maximum deviations of + 0.03 mm, showed very good geometric uniformity.
  • the water retention capacity determined was 2400% based on cellulose.
  • Example 2 The procedure was analogous to Example 1, but the cellulose-NMMO solution contained, besides 2.5% by mass of cellulose, 12.5% by mass of A1 2 0 3 (1.2 ⁇ m powder CT 1200 SG from Alcoa).
  • Example 2 The procedure was analogous to Example 1. The following variations were carried out: Use of a bicomponent capillary in such a way that the supply of two solutions differing in their composition took place via separate channels which were arranged coaxially one inside the other.
  • the first solution corresponded to that described in Example 1, the second solution contained 2.5% Printex L soot in addition to 2.5% LV dissolving pulp.
  • the soot-laden solution was fed to the inner capillary.
  • the procedure was analogous to Example 1, the following being varied:
  • the NMMO cellulose solution contained 2.5% LV disolving pulp from MoDo.
  • a temperature of 90 ° C was applied to the capillary.
  • the heptane was replaced by commercially available rapeseed oil. This oil bath was brought to a temperature of 80 ° C.
  • the cellulose beads obtained were round and had a diameter of 3.13 + 0.03 mm.
  • the water retention capacity was 3900%. After a subsequent drying, the diameter of the beads was measured to be 0.8 mm.
  • Example 5 The procedure was analogous to Example 1, the following being varied:
  • the NMMO cellulose solution contained 3% cotton linters.
  • a metal capillary with an inside diameter of 200 ⁇ m at the outlet was used.
  • the wall thickness of the capillary was 200 ⁇ m.
  • a temperature of 150 ° C was applied to the capillary.
  • the air gap between capillary and liquid was blown with a laminar air flow of 0.3 m / s at 130 ° C.
  • the heptane was replaced by a silicone oil with a specific gravity of 0.97 (25 ° C) g / ml. This oil bath was brought to a temperature of 60 ° C.
  • the cellulose beads obtained were round and had a diameter of 1.65 mm.
  • the water retention capacity was 3350%.
  • the procedure was analogous to Example 1, but with the following modifications:
  • the NMMO cellulose solution contained 3% LV disolving pulp from MoDo. It was blown in the 15 mm wide air gap with 95 ° C air at 0.2 m / s. The lower part of the glass capillary was heated to 95 ° C. The heptane was completely exchanged for NMMO-containing water so that the height of the water bath was 100 cm. The temperature of the water bath was 60 ° C.
  • the round beads obtained had an average diameter of 4.14 mm with a variance of 1.5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne un procédé permettant la production de perles de cellulose régulières et poreuses ayant un diamètre de particule allant jusqu'à 5000 νm, dans lequel une solution de cellulose est mise sous forme de gouttelettes par l'intermédiaire d'un capillaire, lesdites gouttes passant par gravité à travers un interstice pour arriver dans un milieu liquide où elles prennent une forme sphérique. Le milieu liquide utilisé peut être un système organique et/ou minéral à une ou plusieurs composantes, tel que du N-méthyl morpholine-N-oxyde aqueux. Les perles de cellulose obtenues peuvent être utilisées en tant que matière de départ destinée à subir des traitements chimiques ultérieurs, en tant qu'adsorbant en biotechnologie, en tant que matériau de support pour des catalyseurs biologiques, des cultures cellulaires, des solutions nutritives, en tant qu'échangeur d'ions ou que catalyseur tels qu'un catalyseur d'automobile ou en tant que matière de charge dans des réacteurs chimiques.
PCT/DE2002/000145 2001-01-19 2002-01-18 Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation WO2002057319A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10102334.0 2001-01-19
DE10102334A DE10102334C2 (de) 2001-01-19 2001-01-19 Verfahren zur Herstellung von regulären, monodispersen Celluloseperlen und ihre Verwendung

Publications (2)

Publication Number Publication Date
WO2002057319A2 true WO2002057319A2 (fr) 2002-07-25
WO2002057319A3 WO2002057319A3 (fr) 2002-09-19

Family

ID=7671105

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2002/000145 WO2002057319A2 (fr) 2001-01-19 2002-01-18 Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation

Country Status (2)

Country Link
DE (1) DE10102334C2 (fr)
WO (1) WO2002057319A2 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004065424A1 (fr) * 2003-01-20 2004-08-05 Lenzing Aktiengesellschaft Procede de production d'un corps cellulosique poreux
WO2009036479A1 (fr) * 2007-09-21 2009-03-26 Lenzing Ag Suspension de cellulose et son procédé de préparation
WO2009065891A1 (fr) * 2007-11-22 2009-05-28 Basf Se Production de particules sphériques à partir de solutions contenant un solvant miscible à l'eau selon le procédé de granulation sous l'eau
EP2305740A1 (fr) * 2009-09-30 2011-04-06 Ems-Patent Ag Procédé destiné à la fabrication de particules de polymère
US9163095B2 (en) 2007-09-21 2015-10-20 Lenzing Aktiengesellschaft Cellulose powder and processes for its production
EP3050902A4 (fr) * 2013-09-27 2017-02-15 Kaneka Corporation Procédé de production de perles de cellulose poreuses par utilisation d'une solution aqueuse alcaline, support pour immobilisation de ligands, et adsorbant
US9822188B2 (en) 2013-10-15 2017-11-21 Lenzing Ag Cellulose suspension, method for the production and use thereof
US10093790B2 (en) 2013-10-15 2018-10-09 Lenzing Aktiengesellschaft Three-dimensional cellulose molded body, method for the production thereof and use of the same
CN108704616A (zh) * 2018-05-28 2018-10-26 苏州佑君环境科技有限公司 一种改性壳聚糖氟离子吸附剂的制备方法
US10316467B2 (en) 2013-11-26 2019-06-11 Lenzing Aktiengesellschaft Process for pretreating reclaimed cotton fibers to be used in the production of molded bodies from regenerated cellulose
US10370778B2 (en) 2015-02-06 2019-08-06 Lenzing Aktiengesellschaft Recycling of man-made cellulosic fibers
EP4048422A1 (fr) * 2019-10-25 2022-08-31 Lenzing Aktiengesellschaft Procédé destiné à la récupération de solvant à partir de particules cellulosiques contenant un solvant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT413287B (de) * 2003-11-25 2006-01-15 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer fasern
WO2020046936A1 (fr) * 2018-08-30 2020-03-05 Dow Global Technologies Llc Appareil et procédé de granulation de matériaux à faible viscosité

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543928A (en) * 1946-06-08 1951-03-06 Olin Ind Inc Method of producing cellulose pellets
DE2005408A1 (fr) * 1969-02-07 1970-09-03 Pharmacia Fine Chemicals Ab
EP0303259A2 (fr) * 1987-08-10 1989-02-15 Asahi Kasei Kogyo Kabushiki Kaisha Particule de cellulose multi-cellulaire et procédé pour sa préparation
DE19755353C1 (de) * 1997-12-14 1999-04-29 Thueringisches Inst Textil Verfahren zur Herstellung regulärer, poröser Perlcellulosen und ihre Verwendung
WO2000053833A1 (fr) * 1999-03-08 2000-09-14 Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Procede de production de corps moules

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4205882A1 (de) * 1992-02-26 1993-09-02 Basf Ag Verfahren zur erzeugung teilchenfoermiger poly(meth)acrylimid-polymerisate
DE4338212C2 (de) * 1993-11-10 1996-01-18 Nukem Gmbh Verfahren und Vorrichtung zur Herstellung von aus Kunststoff bestehenden Partikeln

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543928A (en) * 1946-06-08 1951-03-06 Olin Ind Inc Method of producing cellulose pellets
DE2005408A1 (fr) * 1969-02-07 1970-09-03 Pharmacia Fine Chemicals Ab
EP0303259A2 (fr) * 1987-08-10 1989-02-15 Asahi Kasei Kogyo Kabushiki Kaisha Particule de cellulose multi-cellulaire et procédé pour sa préparation
DE19755353C1 (de) * 1997-12-14 1999-04-29 Thueringisches Inst Textil Verfahren zur Herstellung regulärer, poröser Perlcellulosen und ihre Verwendung
WO2000053833A1 (fr) * 1999-03-08 2000-09-14 Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Procede de production de corps moules

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004065424A1 (fr) * 2003-01-20 2004-08-05 Lenzing Aktiengesellschaft Procede de production d'un corps cellulosique poreux
WO2009036479A1 (fr) * 2007-09-21 2009-03-26 Lenzing Ag Suspension de cellulose et son procédé de préparation
US8827192B2 (en) 2007-09-21 2014-09-09 Lenzing Aktiengesellschaft Cellulose suspension and processes for its production
US9163095B2 (en) 2007-09-21 2015-10-20 Lenzing Aktiengesellschaft Cellulose powder and processes for its production
WO2009065891A1 (fr) * 2007-11-22 2009-05-28 Basf Se Production de particules sphériques à partir de solutions contenant un solvant miscible à l'eau selon le procédé de granulation sous l'eau
EP2305740A1 (fr) * 2009-09-30 2011-04-06 Ems-Patent Ag Procédé destiné à la fabrication de particules de polymère
US10221211B2 (en) 2013-09-27 2019-03-05 Kaneka Corporation Process for producing porous cellulose beads using alkali aqueous solution
EP3050902A4 (fr) * 2013-09-27 2017-02-15 Kaneka Corporation Procédé de production de perles de cellulose poreuses par utilisation d'une solution aqueuse alcaline, support pour immobilisation de ligands, et adsorbant
US10457705B2 (en) 2013-09-27 2019-10-29 Kaneka Corporation Carrier for ligand immobilization
US10093790B2 (en) 2013-10-15 2018-10-09 Lenzing Aktiengesellschaft Three-dimensional cellulose molded body, method for the production thereof and use of the same
US9822188B2 (en) 2013-10-15 2017-11-21 Lenzing Ag Cellulose suspension, method for the production and use thereof
US10513564B2 (en) 2013-10-15 2019-12-24 Lenzing Aktiengesellschaft Cellulose suspension, method for the production and use thereof
US10316467B2 (en) 2013-11-26 2019-06-11 Lenzing Aktiengesellschaft Process for pretreating reclaimed cotton fibers to be used in the production of molded bodies from regenerated cellulose
US10370778B2 (en) 2015-02-06 2019-08-06 Lenzing Aktiengesellschaft Recycling of man-made cellulosic fibers
CN108704616A (zh) * 2018-05-28 2018-10-26 苏州佑君环境科技有限公司 一种改性壳聚糖氟离子吸附剂的制备方法
EP4048422A1 (fr) * 2019-10-25 2022-08-31 Lenzing Aktiengesellschaft Procédé destiné à la récupération de solvant à partir de particules cellulosiques contenant un solvant

Also Published As

Publication number Publication date
DE10102334A1 (de) 2002-08-01
WO2002057319A3 (fr) 2002-09-19
DE10102334C2 (de) 2003-12-04

Similar Documents

Publication Publication Date Title
EP2190882B1 (fr) Procédé de préparation des particules de cellulose
WO2002057319A2 (fr) Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation
EP0966486B1 (fr) Procede de production de cellulose sous forme de perles poreuses regulieres
DE3852233T2 (de) Multizellulare Zellulosepartikel und Verfahren zu ihrer Herstellung.
AT402410B (de) Verfahren zur herstellung einer cellulosesuspension
DE69816768T2 (de) Cellulose Mikrokugeln und Verfahren zu deren Herstellung
AT518612A1 (de) Polysaccharid-Suspension, Verfahren zu ihrer Herstellung und ihre Verwendung
DE3205289A1 (de) Verfahren zur herstellung von poroesen koerpern mit einstellbarem gesamtporenvolumen, einstellbarer porengroesse und einstellbarer porenwandung
DE69725544T2 (de) Verfahren zur Herstellung von Cellulosekügelchen
WO2006066291A1 (fr) Corps moule en cellulose et procede de fabrication dudit corps
EP0994166B1 (fr) Préparation pigmentaire
EP0750007B1 (fr) Procédé de préparation de microparticules sphériques à base d'acétate de cellulose
WO2013030399A1 (fr) Procédé d'extrusion
DE60004944T2 (de) Verfahren zur Herstellung eines sphärischen Kieselgels
EP0807698A2 (fr) Procédé et dispositif pour la préparation d'une structure fibrillaire à base de dérivés de cellulose
EP2108065B1 (fr) Procédé de fabrication de corps façonnés à partir de protéines avec des liquides ioniques
DE19755353C1 (de) Verfahren zur Herstellung regulärer, poröser Perlcellulosen und ihre Verwendung
AT515180B1 (de) Dreidimensionaler cellulosischer Formkörper, Verfahren zu seiner Herstellung und seine Verwendung
DE19755352C1 (de) Verfahren zur Herstellung von regulären, porösen Perlcellulosen aus Celluloselösungen und die Verwendung der Perlcellulosen
WO2024170630A1 (fr) Corps moulé en fibres de carbone
DE10221537A1 (de) Verfahren zur Herstellung sphärischer, hybridischer Formkörper aus löslichen Polymeren
DD259533A3 (de) Verfahren zur herstellung geformter cellulosekoerper aus alkalischen cellulosecarbamatloesungen
DD295861B5 (de) Verfahren zur Herstellung perlfoermiger Celluloseprodukte
DD289206A5 (de) Verfahren zur herstellung grobporiger asymmetrischer hohlmembranen aus acrylnitrilpolymeren
DD295861A5 (de) Verfahren zur Herstellung perlförmiger Celluloseprodukte

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AL AU BA BG BR CA CN CO CR CU CZ DZ EC EE GE HR HU ID IL IN IS JP KE KP KR LT LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL RO SG SI SK TN TT UA US UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AL AU BA BG BR CA CN CO CR CU CZ DZ EC EE GE HR HU ID IL IN IS JP KE KP KR LT LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL RO SG SI SK TN TT UA US UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP