WO2004065424A1 - Procede de production d'un corps cellulosique poreux - Google Patents

Procede de production d'un corps cellulosique poreux Download PDF

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Publication number
WO2004065424A1
WO2004065424A1 PCT/AT2004/000013 AT2004000013W WO2004065424A1 WO 2004065424 A1 WO2004065424 A1 WO 2004065424A1 AT 2004000013 W AT2004000013 W AT 2004000013W WO 2004065424 A1 WO2004065424 A1 WO 2004065424A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
aqueous medium
porous
cellulosic
supercritical solvent
Prior art date
Application number
PCT/AT2004/000013
Other languages
German (de)
English (en)
Inventor
Heinrich Firgo
Hartmut Rüf
Karl Michael Hainbucher
Hedda Weber
Original Assignee
Lenzing Aktiengesellschaft
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 Lenzing Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Priority to EP04703120A priority Critical patent/EP1585772A1/fr
Publication of WO2004065424A1 publication Critical patent/WO2004065424A1/fr

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing a porous cellulosic body, a porous cellulosic body and its use and a porous carbon body which can be produced from the cellulosic body by pyrolysis and its use.
  • porous bodies according to the invention are so-called aerogels.
  • aerogels are highly porous solids with very low density.
  • aerogels are materials in which the pore and network structure is completely or largely preserved when the pore fluid of a gel is replaced by air.
  • a gel consists of a sponge-like, three-dimensional network, the pores of which are filled with a liquid.
  • aerogels in which the network structure remains essentially unchanged during drying, conventionally drying (increasing the temperature and / or reducing the pressure) gives strongly shrunk bodies, which are called xerogels.
  • the shrinkage of the gel is caused by the capillary forces at the liquid / gaseous interface of the evaporating pore liquid.
  • aerogels The unique optical, thermal, acoustic and mechanical properties of aerogels are caused by the combination of a solid matrix with air-filled pores in the nanometer range.
  • the majority of industrially produced aerogels are inorganic in nature and consist of silica and metal oxides.
  • organic aerogels are also known (for example US Department of Energy, US 4,873,218).
  • a cellulose xanthate solution or cellulose acetate, which is hydrolyzed, is generally assumed.
  • Viscose solution of cellulose xanthate in dilute sodium hydroxide solution
  • a water-immiscible organic solvent such as chlorobenzene
  • the cellulosic bodies obtained in this way have porosities (volume fraction water) of 90%.
  • the water can (according to: J. Stamberg et al., Acta Polymerica 30 (1979) Issue 12, 734-739) be replaced by various organic solvents, and the degree of porosity remains almost unchanged.
  • the highest porosity value of a dried cellulose body known to the applicant is a value of 83.6%, which is described in Peska et al., Cell. Chem. Techn. 21 (1978) pp. 419-428.
  • DD 1 18,887 corresponds to US 4,055,510
  • WO 91/09878 corresponds to US 5,527,902
  • DD 118,887 contains the statement that only cellulose balls with a low pore volume of less than 30% are dimensionally stable and can be dried without special measures to maintain the porosity.
  • a hydrolyzable cellulose derivative such as e.g. Cellulose acetate dissolved in a water-miscible organic solvent, the solution divided into drops and introduced into a precipitation bath (e.g. water), the beads separated, washed, the cellulose derivative hydrolyzed to cellulose and washed again.
  • a precipitation bath e.g. water
  • the drying with supercritical carbon dioxide mentioned in Example 1 is used exclusively for the preparation of a pattern suitable for characterization by means of electron microscopy.
  • a disadvantage of many processes known from the prior art are ecological problems, such as the use of chlorinated organic solvents, the emission of toxic sulfur compounds in the viscose process or the use of copper-containing solvents for the cellulose.
  • WO 99/31 141 contains the description of a process with the following steps:
  • the solution becomes a jet with a diameter in the range from 40 ⁇ m to
  • N-Methylmo ⁇ holin-N-oxide is used as a solvent for cellulose in the examples.
  • example 2 beads with an average diameter of 2.2 mm are obtained. After pyrolysis of the beads, which also contain a proportion of Al 2 O, and subsequent sintering, the beads have a diameter of 1.1 mm. In another example (example 4), the undried beads have an average diameter of 3.13 mm. After drying (not described in detail), the diameter is only 0.8 mm. It can therefore be assumed that the porosity of these pearls has drastically reduced during drying.
  • the method according to the invention for the production of porous cellulosic bodies comprises the steps Production of a cellulose solution in a tertiary amine oxide, in particular N-methylmo ⁇ holin-N-oxide, the cellulose used having an average degree of polymerization of 150 to 2000 and the solution having a cellulose concentration of 0.1 to 5% by weight, production of a body the cellulose solution
  • Precipitation of the body in a precipitant whereby a precipitated cellulosic body is obtained, the precipitant being an aqueous medium or a cellulose-precipitating, water-miscible, non-aqueous medium which is non-aqueous
  • Solvent is miscible and is characterized in that if an aqueous medium is used as the precipitant in the precipitated cellulosic body, tertiary amine oxide contained in the precipitated cellulose is washed out with the aqueous medium, the aqueous medium is exchanged for a liquid exchange medium which is miscible with a supercritical solvent and which is moist with the exchange medium cellulosic body is treated with the supercritical solvent, whereby the porous cellulosic body is obtained or that, if a non-aqueous medium is used as a precipitant, tertiary amine oxide contained in the precipitated cellulosic body is washed out with the non-aqueous medium which is washed with the non-aqueous medium. aqueous medium moist cellulosic body is treated with the supercritical solvent, whereby the porous cellulosic body is obtained.
  • cellulosic means cellulose, cellulose derivatives soluble in tertiary amine oxides and mixtures of cellulose and / or soluble cellulose derivatives and other polymers soluble in NMMO, such as, for example, polyamides.
  • NMMO N-methylmo ⁇ holin-N-oxide
  • Carbon dioxide is preferably used as the supercritical solvent in the process according to the invention.
  • Organic solvents which are suitable as precipitants for the purposes of the present invention are water-miscible, act as precipitants in relation to cellulose in amine oxide solutions, are able to dissolve NMMO, should cause the primary gel swelling of the cellulose to be as high as possible and should be good with supercritical carbon dioxide be miscible.
  • Acetone can also be used as the non-aqueous medium or as the liquid exchange medium.
  • the aqueous medium which can be used as a precipitant, can consist of water or of mixtures of water with other solvents (provided the cellulose-precipitating effect is retained).
  • the precipitant (aqueous medium or non-aqueous medium) can additionally contain further components, such as e.g. Parts of solvent (amine oxide) included.
  • an alcohol or acetone-moist gel is covered in an autoclave with excess alcohol / acetone (to prevent premature drying), then the temperature and the CO 2 pressure are slowly increased and for some time at values above the critical point of C0 2 (31, 1 ° C / 73.8 bar) held until the solvent in the cellulose body is removed quantitatively. The pressure and temperature are then adjusted so that the CO 2 is slowly removed in the gaseous state.
  • the cellulose solution is processed in a manner known per se, e.g. by extrusion through a molding tool or by casting into a corresponding mold, formed into a shaped body.
  • the molded body can be, for example, a fiber, a film, a block or a plate.
  • spherical or pearl-shaped particles can also be produced from the cellulose solution by dropping the solution or, for example, using the technology described in WO 99/31 141.
  • particles can be produced from the solution by means of the jet cutter technology (from Genialab) and by means of vibration nozzles.
  • a powder can also be produced from a large number of porous cellulose particles.
  • a further preferred embodiment of the method according to the invention is characterized in that the cellulosic body is treated with a crosslinking agent, such as e.g. described in WO 91/09878.
  • porous cellulosic body produced by the process according to the invention can also be subjected to pyrolysis.
  • the method according to the invention it is possible for the first time to provide a porous cellulosic body with a porosity in the dry state of 85% and more.
  • the body obtained by treatment with the supercritical solvent is thus a highly porous airgel.
  • the cellulosic body according to the invention preferably has a porosity of 90% and more, particularly preferably of 95% and more.
  • the porosity is defined as follows for the purposes of the present invention: The cellulosic body obtained is measured in a microscope and the volume is calculated therefrom. The cellulosic body is weighed, which gives the density of the body (mass / volume).
  • the formula (1 - density of the body / 1, 6) * 100 gives the porosity of the body, ie the percentage of voids in the body. In the case of a large number of bodies (eg pearls), the average is taken from several measurements.
  • the invention further relates to a porous cellulosic body which can be obtained by the process according to the invention.
  • This body differs from known porous cellulosic bodies produced by the amine oxide process, e.g. described in WO 99/31 141 and WO 02/057319, characterized in that the porosity is significantly higher in the dry state.
  • cellulosic bodies according to the invention can be used in particular as insulation material, for example in thermal or acoustic insulation. Furthermore, the cellulosic bodies according to the invention can be used as a dielectric in the electrical and electronics industry, for impedance matching in acoustic applications, as a means for absorbing and cleaning gases, as a carrier for catalysts and / or as a means for storing energy sources, such as e.g. Hydrogen.
  • the invention further relates to a porous carbon body which can be obtained from the cellulosic body according to the invention by means of pyrolysis.
  • the carbon airgel resulting after pyrolysis of the cellulose component is suitable as an electrode material for batteries, accumulators, capacitors and fuel cells and for high-temperature insulation.
  • Such carbon aerogels in analogy to carbon nanotubes, represent efficient hydrogen stores.
  • a cellulose solution with 1% by weight> cellulose (cellulose Solucell with a viscosity according to SCAN CM 15:88 500) / 82% by weight NMMO / 17% by weight H 2 O was prepared in a manner known per se. This solution was dropped in water as a precipitant Washed out solvent with water and then exchanged the water for ethanol.
  • the ethanol-moist bodies (spheres with a diameter of approximately 3 mm) were placed in an autoclave, covered with additional ethanol, heated to 50 ° C. and 130 bar of CO 2 were added for 2.5 hours.
  • the CO 2 was kept in circulation, which was reduced in the cycle of pressure in two stages, each with a liquid at 60 and 40 bar, then the C0 2 has been re-compressed to 130 bar. After the two and a half hours mentioned, the CO 2 was then discharged at 50.degree.
  • Cellulose balls with the same diameter (approx. 3 mm) as the moist starting product were obtained.
  • the density of the cellulose balls was 0.042 g / cm 3 ; according to the above calculation formula, this means that the pore volume is 97.4%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé de production d'un corps cellulosique poreux, ce procédé comprenant les étapes suivantes : production d'une solution de cellulose dans un aminoxyde tertiaire, en particulier du N-méthylmorpholine-N-oxyde, la cellulose utilisée possédant un indice de polymérisation moyen compris entre 150 et 2000 et la solution présentant une concentration en cellulose comprise entre 0,1 et 5 % en poids ; production d'un corps à partir de cette solution de cellulose ; précipitation de ce corps dans un agent précipitant de façon à obtenir un corps cellulosique précipité, ledit agent précipitant étant un milieu aqueux ou un milieu non aqueux miscible avec l'eau et précipitant la cellulose, lequel milieu non aqueux pouvant par ailleurs dissoudre l'aminoxyde tertiaire et étant miscible avec un solvant surcritique. Le procédé selon l'invention se caractérise en ce que, lorsque l'agent précipitant utilisé est un milieu aqueux, l'aminoxyde tertiaire contenu dans le corps cellulosique précipité est éliminé par lavage au moyen du milieu aqueux, ledit milieu aqueux est remplacé par un milieu de substitution liquide miscible avec un solvant surcritique, puis le corps cellulosique mouillé avec ledit milieu de substitution est traité avec ledit solvant surcritique de façon à obtenir le corps cellulosique poreux ou, lorsque l'agent précipitant utilisé est le milieu non aqueux, l'aminoxyde tertiaire contenu dans le corps cellulosique précipité est éliminé par lavage au moyen du milieu non aqueux, puis le corps cellulosique mouillé avec le milieu non aqueux est traité avec le solvant surcritique de façon à obtenir le corps cellulosique poreux.
PCT/AT2004/000013 2003-01-20 2004-01-19 Procede de production d'un corps cellulosique poreux WO2004065424A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04703120A EP1585772A1 (fr) 2003-01-20 2004-01-19 Procede de production d'un corps cellulosique poreux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0007103A AT412404B (de) 2003-01-20 2003-01-20 Verfahren zur herstellung eines porösen cellulosischen körpers
ATA71/2003 2003-01-20

Publications (1)

Publication Number Publication Date
WO2004065424A1 true WO2004065424A1 (fr) 2004-08-05

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Application Number Title Priority Date Filing Date
PCT/AT2004/000013 WO2004065424A1 (fr) 2003-01-20 2004-01-19 Procede de production d'un corps cellulosique poreux

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Country Link
EP (1) EP1585772A1 (fr)
AT (1) AT412404B (fr)
TW (1) TW200418558A (fr)
WO (1) WO2004065424A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006049179A1 (de) * 2006-10-18 2008-04-30 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aerogelfasern
DE102010011808A1 (de) 2010-03-18 2011-11-17 Blue Globe Energy Gmbh Poröser Cellulose-Festkörper, dessen Herstellung und Verwendung als Zellwachstumssubstrat
DE102013111459A1 (de) * 2013-10-17 2015-04-23 Elringklinger Ag Akustisch wirksame Abschirmteile und Abdeckungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553132A (en) * 1968-02-26 1971-01-05 Celanese Corp Heat and flame resistant pyrolyzed cellular material and process of making same
WO1999031141A2 (fr) * 1997-12-14 1999-06-24 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Procede de production de cellulose sous forme de perles poreuses regulieres, perles de cellulose ainsi obtenues et leur utilisation
WO2002057319A2 (fr) * 2001-01-19 2002-07-25 Thüringisches Institut für Textil-und Kunststoff-Forschung E.V. Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE434848B (sv) * 1976-04-22 1984-08-20 Purdue Research Foundation Forfaringssett for framstellning av porosa cellulosaperlor
US5169687A (en) * 1988-09-16 1992-12-08 University Of South Florida Supercritical fluid-aided treatment of porous materials
DE19755353C1 (de) * 1997-12-14 1999-04-29 Thueringisches Inst Textil Verfahren zur Herstellung regulärer, poröser Perlcellulosen und ihre Verwendung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553132A (en) * 1968-02-26 1971-01-05 Celanese Corp Heat and flame resistant pyrolyzed cellular material and process of making same
WO1999031141A2 (fr) * 1997-12-14 1999-06-24 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Procede de production de cellulose sous forme de perles poreuses regulieres, perles de cellulose ainsi obtenues et leur utilisation
WO2002057319A2 (fr) * 2001-01-19 2002-07-25 Thüringisches Institut für Textil-und Kunststoff-Forschung E.V. Procede de production de perles de cellulose regulieres et monodispersees, et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PESKA J ET AL: "REGENERATED CELLULOSE IN THE BEAD FORM. AFTERTREATMENTS AND THEIR EFFECTS ON THE POROUS STRUCTURE OF CELLULOSE", CELLULOSE CHEMISTRY AND TECHNOLOGY, BUCHAREST, RU, vol. 21, no. 4, 1 July 1978 (1978-07-01), pages 419 - 428, XP002040620 *
See also references of EP1585772A1 *
TEWARI P H ET AL: "AMBIENT-TEMPERATURE SUPERCRITICAL DRYING OF TRANSPARENT SILICA AEROGELS", MATERIALS LETTERS, NORTH HOLLAND PUBLISHING COMPANY. AMSTERDAM, NL, vol. 3, no. 9/10, 1 July 1985 (1985-07-01), pages 363 - 367, XP000579672, ISSN: 0167-577X *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006049179A1 (de) * 2006-10-18 2008-04-30 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aerogelfasern
DE102006049179B4 (de) * 2006-10-18 2016-07-07 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aerogelfasern, Verfahren zu deren Herstellung sowie deren Verwendung
DE102010011808A1 (de) 2010-03-18 2011-11-17 Blue Globe Energy Gmbh Poröser Cellulose-Festkörper, dessen Herstellung und Verwendung als Zellwachstumssubstrat
DE102013111459A1 (de) * 2013-10-17 2015-04-23 Elringklinger Ag Akustisch wirksame Abschirmteile und Abdeckungen

Also Published As

Publication number Publication date
AT412404B (de) 2005-02-25
TW200418558A (en) 2004-10-01
EP1585772A1 (fr) 2005-10-19
ATA712003A (de) 2004-07-15

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