WO2015095902A1 - Procédé de production de particules de carbone - Google Patents

Procédé de production de particules de carbone Download PDF

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Publication number
WO2015095902A1
WO2015095902A1 PCT/AT2014/000224 AT2014000224W WO2015095902A1 WO 2015095902 A1 WO2015095902 A1 WO 2015095902A1 AT 2014000224 W AT2014000224 W AT 2014000224W WO 2015095902 A1 WO2015095902 A1 WO 2015095902A1
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WO
WIPO (PCT)
Prior art keywords
particles
cellulose
heat treatment
lyocell
carbon
Prior art date
Application number
PCT/AT2014/000224
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German (de)
English (en)
Inventor
Gisela Goldhalm
Josef Innerlohinger
Martin Häubl
Original Assignee
Lenzing Ag
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.)
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Publication date
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Publication of WO2015095902A1 publication Critical patent/WO2015095902A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents

Definitions

  • the present invention relates to a process for the preparation of
  • Precursor non-cylindrical cellulose particles with cellulose II structure can be used.
  • Carbon particles are used, among other things, for the production of electrodes in modern energy storage media, where high charge and discharge rates are important, for example for batteries and supercapacitors in vehicles with electric drive or start-stop function.
  • lyocell was assigned by BISFA to cellulose fibers made from solutions in an organic solvent without formation of a derivative.
  • the solvent used is a tertiary amine oxide, preferably N-methylmorpholine-N-oxide (NMMO).
  • NMMO N-methylmorpholine-N-oxide
  • Tertiary amine oxides have long been known as alternative solvents for cellulose. From US Pat. No. 2,179,181 it is known, for example, that tertiary amine oxides are able to dissolve pulp without derivatization and that cellulosic shaped bodies such as, for example, fibers can be produced from these solutions.
  • US 3,447,939 cyclic amine oxides as
  • EP 356 419 B1 describes the preparation of solutions and EP 584 318 B1 describes the spinning of such solutions of cellulose in
  • lyocell fibers as a carbonization precursor is also described in the article "Tencel carbon precursor”, Lenzinger Berichte, 90, 2012, 58-63.
  • Electrodes made of carbon powder or activated carbon powder are manufactured using two principally different methods:
  • Activated carbon powder mixed with binder eg PTFE
  • binder eg PTFE
  • Aluminum foil is coated with this suspension and dried.
  • the dried layer is often subsequently densified by hot calendering.
  • lyocell fibers are said to have particular suitability for the production of electrode material.
  • the uniform fiber shape should ensure a high packing density. It has now been found that this is true for the application of the dry method of electrode production in the laboratory, but not for the large-scale applied slurry method. If the slurry method is carried out with fibrous powder, extremely fragile, brittle electrodes are produced whose calendering and densification is possible only when very high binder quantities are used. Although this material has high electrical capacities, it can not be used on an industrial scale.
  • the object of this prior art therefore was to find a carbonized material which, on the one hand, permits a high electrical capacitance during electrode production and, on the other hand, results in mechanically stable electrodes.
  • the solution to the above-described problem consists in a process for the production of carbon particles from precursors with cellulose II structure, non-cylindrical cellulose particles with cellulose II structure being used as precursor.
  • the carbon particles are often also called
  • Cellulose II molded articles can be produced, for example, by comminution of commercially available lyocell fibers, were non-cylindrical
  • Cellulose particles with cellulose II structure in particular those which had been prepared by the Lyocell compiler, so far not readily available.
  • the non-cylindrical cellulose particles are prepared by a special Lyocell method.
  • the advantages of the invention are, in particular, the combination of high activability by lyocell structure of cellulosic precursors and large-scale processability to electrodes, with high gravimetric electrical capacitances by the inherent lyocell structure, with recovery of stable electrodes by means of slurry method with high electrode density and thus high volumetric capacity.
  • particles or granules compared to fibers in the carbonization or activation process particles are easier to promote, since they have no compressible behavior in the promotion and no
  • Fibers can also be more easily introduced into a complete atmosphere of inert gas or activating gas. Fibers transport a large amount of air through their high trapped volume must be displaced with nitrogen before the thermal treatment; This costs time and resources. For particles the effort is much lower.
  • WO 2009/036480 describes suitable three-dimensional cellulosic shaped bodies and a lyocell method for their production. This method is characterized in that the cellulose solution free-flowing, that is without substantial shearing of the cellulose solution under their
  • Cellulose particles have a cellulose-II structure with a particle size in the range of 1pm to 5000 ⁇ , preferably 5pm to 2000 ⁇ , more preferably 10 to 200 ⁇ and are also characterized in that they have an approximately spherical particle shape with irregular surface and a crystallinity in the range of 15% to 45% according to the Raman method.
  • Manufacturing steps a. Dissolving a cellulosic raw material, for example pulp, to obtain a solution containing 10 to 15% by weight of cellulose;
  • step b Extrusion of in step a. obtained cellulose solution without air gap directly into a precipitation bath;
  • the laundry mentioned in point d. is preferably multi-stage and in the
  • the cellulosic shaped bodies produced in this way have an optically detectable core-shell structure.
  • Cuprammonium process into consideration; It is also possible to dissolve the cellulose in NaOH or suitable ionic liquids.
  • the method described here is not limited to specific solvents or processes, but by using different methods, the structure of the resulting particles can be additionally influenced.
  • preference is given to the lyocell process which is fundamentally known to the person skilled in the art and is described, inter alia, in EP 0356419.
  • the shaping takes place, in which - especially in the precipitation process - care must be taken to ensure that no fibrous structures are formed. This is not a trivial requirement because
  • Cellulose solution is first brought into the desired shape without significant shearing and then the regeneration conditions are selected accordingly. It is essential that the cellulose solution directly, d. H. without an air gap, is extruded into a precipitation bath and the comminution of the solution strand takes place in a manner which results in substantially equal particles.
  • Suitable aggregates for this step are, for example, underwater or stranded granulators, which in addition to spherical particles also produce cylinders, angular ellipsoids and ovoids. The aforementioned units also meet the additional
  • the particles produced are supposed to have as uniform a size as possible, with the
  • Granules of different sizes can be made from Lyocell dope, for example, with an EUP50 type underwater granulator from Econ.
  • the beads produced can be separated from the process water via a mechanical centrifugal dryer.
  • solid-liquid separations may be e.g. by hydrocyclone, pusher centrifuges or by sieves
  • Granulators are available in a variety of sizes on the market, and due to the simplicity of the process of granulation of dope, upscaling on an industrial scale is relatively easy. Thus, e.g. with a single pelletizer of the type EUP 3000 about 5000 tons of pellets are produced per year. Furthermore, there are much larger machines available from other manufacturers.
  • cellulose strands can also be produced with special Lyocell nozzles with nozzle hole diameters of 0.5 to 5 mm, which are fed to a strand pelletizer after a washing cycle.
  • the viscosity of the cellulose solution also has a great influence on the properties of the particles obtained, since these normally also have the viscosity
  • the precipitation bath is preferably aqueous (with a viscosity in the range of 1 Pa * s), but the viscosity of the precipitation bath can be increased significantly by adding thickeners (polymers). A smaller difference in viscosity leads to a thinner coat.
  • the invention is a
  • Viscosity difference between cellulose solution and precipitation bath of at least 600 Pa.s, preferably in the range 750-1200 Pa.s. (based on the zero viscosity).
  • the thickness of the shell is decisively influenced by the NMMO concentration difference when the cellulose solution enters the precipitation bath. The larger this is, the thicker the coat gets
  • the thickness of the jacket is also influenced by the temperature difference when the cellulose solution enters the precipitation bath. The larger this is, the thicker the jacket of the granules produced according to the invention becomes.
  • the preferred process principle for washing out the moldings on an industrial scale is the countercurrent washing in order to keep the necessary amount of wash water and the recovery costs within limits.
  • 10 to 12 washing stages are necessary for this.
  • increasing the wash water temperature is advantageous.
  • a washing water temperature of 60 ° C. to 100 ° C. is preferred here.
  • an alkaline step is additionally necessary, wherein preferably pH values of 9-13 are used.
  • the cellulose II molded bodies produced by this second process variant are characterized in that they have an optically detectable core-shell structure, wherein the shell has a higher density and a lower crystallinity than the core and the core has a sponge-like structure.
  • the sheath has a relative density of 65% to 85% and the core has a relative density of 20% to 60%, based in each case on compact cellulose.
  • the jacket thickness between 50 ⁇ and 200 ⁇ .
  • the ratio of shell thickness to total diameter of the molding can be between 1: 5 and 1:50. Due to the production, the ratio of the semiaxes of the ellipsoidal shaped body 3: 1 will not exceed.
  • cellulose particles of the invention having such a shape, i. ellipsoidal shaped bodies with a ratio of the semi-axes of less than or equal to 3: 1 are referred to as "spherical granules".
  • the spherical granules thus obtained can be coarsely or finely ground depending on the desired final size.
  • non-cylindrical cellulose particles having a cellulose II structure is used, this being intended in particular to differentiate from the cellulose II particles known in the above cited prior art, which are made of lyocell or viscose fibers by comminution and therefore always have a cylindrical shape (see Figs. 1 and 2). In particular from Fig. 2 shows that even at very fine
  • a cylindrical shape should also be understood to mean one with a lobed cross-section, as is the case when viscose fibers are comminuted (see, for example, FIG. 2 in Lenzinger Berichte, 90, 2012, 58-63).
  • the cellulosic shaped bodies produced by the processes described above can be used to produce carbon particles, at least one heat treatment step being necessary.
  • Heat treatment in an inert gas atmosphere is carried out in one
  • the activating atmosphere consists essentially of water vapor or carbon dioxide.
  • a preferred embodiment consists in the use of said cellulosic moldings for carbonization and activation, wherein at least the following process steps are necessary:
  • Optimization in a subsequent second heat treatment step may be added to comminution steps.
  • a preferred solution to the above-described problem consists, for example, in a process for the production of carbon particles from precursors with cellulose II structure, non-cylindrical cellulose particles having cellulose II structure being used as precursor,
  • the cellulose particles are optionally subjected to a fire protection pretreatment
  • step d. obtained particles takes place.
  • a particularly preferred solution of the above-described object consists in a process for the production of carbon particles from precursors with cellulose II structure, non-cylindrical cellulose particles having cellulose II structure being used as precursor,
  • the cellulose particles are subjected to a fire protection pretreatment
  • a further preferred solution of the above-described object consists in a process for the production of carbon particles from precursors with cellulose II structure, non-cylindrical cellulose particles having cellulose II structure being used as precursor,
  • the cellulose particles are optionally subjected to a fire protection pretreatment
  • a further possible solution to the above-described problem consists in a process for the production of carbon particles from precursors with cellulose II structure, non-cylindrical cellulose particles having cellulose II structure being used as precursor, the cellulose particles being subjected to fire protection pretreatment, preferably by impregnation one aqueous solution of a phosphate, and finally a heat treatment in activating atmosphere takes place.
  • fire protection pretreatment preferably by impregnation one aqueous solution of a phosphate
  • a heat treatment in activating atmosphere takes place.
  • relatively large carbon particles are obtained since no comminution steps take place.
  • a crushing step can also be added to obtain correspondingly smaller carbon particles.
  • Fig. 3 shows an inventive crushed, carbonized and activated ball granules
  • Fig. 4 shows an inventive carbonized and activated, not further crushed ball granules, in which the core-shell structure of the original precursor is still clearly visible.
  • the fire protection pretreatment can either be a thermal oxidation at temperatures of 150 ° C - 400 ° C under an air atmosphere or a
  • Impregnation with a solution of a fire retardant e.g.
  • Phosphates for example Diammoniumhydrogenphosphat (DAHP) or aqueous potassium hydroxide (KOH).
  • DAHP Diammoniumhydrogenphosphat
  • KOH aqueous potassium hydroxide
  • the fire retardant is selected from the group containing diammonium hydrogen phosphate (DAHP) and potassium hydroxide (KOH).
  • DAHP diammonium hydrogen phosphate
  • KOH potassium hydroxide
  • the carbonization may be batch or continuous in an inert atmosphere such as e.g. Nitrogen be performed.
  • Essential elements here are the heating rate, the maximum temperature, the
  • the activation step can be carried out either directly with the precursor or with already carbonized particles.
  • a pretreatment with e.g. Phosphates increase the formation of active surface area (see Example 1).
  • As with the carbonization are essential elements of the
  • the activating atmosphere during the heat treatment consists essentially of water vapor or carbon dioxide.
  • the thermal activation will preferably be carried out in an inert gas stream.
  • the activation can be done in the rotary kiln, the rotation should ensure a uniform activation.
  • a measure of the active surface area may be the BET value in m 2 / g.
  • Possibility to characterize the carbon particles is the measurement of the electrical capacitance by means of cyclic voltammetry of two-electrode or three-electrode cells at 1 or 1, 5 V with a scan rate of 20mV / s.
  • Another aspect of the present invention is the use of cellulosic cellulose non-cylindrical cellulose particles to produce carbon particles by the method described above.
  • the non-cylindrical carbon particles produced in this way can be used, inter alia, for the production of electrodes in modern energy storage media which require high charging and discharging rates, for example for batteries and supercapacitors in vehicles with electric drive or start-stop function.
  • the carbon particles produced according to the invention are suitable.
  • Other uses include uses as a filter medium, especially for the filtration of gases, air and liquids as well as storage medium for gases, such as hydrogen.
  • Example 1 Activation of lyocell fibers with and without pretreatment
  • Precursors used Commercially available Tencel® fiber 1, 7 dtex / 38 mm cut length
  • Pretreatment Impregnation of the lyocell fibers with an aqueous solution of diammonium hydrogen phosphate (2% by weight, based on cellulose), followed by drying at 70 ° C. under reduced pressure.
  • Example 1 shows that both the yield and the active surface are increased by the pretreatment. By a longer residence time in the carbonation, although the active surface is increased, but the yield decreases. This finding is unchanged from Lyocell fibers to non-cylindrical lyocell particles as a precursor transferable.
  • Example 2 Activation of lyocell fibers and lyocell pellets in
  • lyocell fibers as well as various lyocell pellets produced by the method described above were pretreated, carbonated and activated under the same conditions.
  • the electrical capacitance of the products was determined by cyclic voltammetry at 1.5 V with a scan rate of 20 mV / s in a two-electrode cell with the following
  • Tested Precursors Commercially available Tencel® fiber 1, 7 dtex / 38 mm cut length, Lyocell granules unmilled 1 mm in diameter, coarse milled Lyocell granules (100 pm average
  • Particle size finely ground lyocell granules (8 pm average particle size).
  • the lyocell pellets were prepared as described in the above Description shown method produced. The determination of the particle size was carried out with a laser diffraction meter.
  • Example 2 show that lyocell pellets show a similar good activability as lyocell fibers under the same conditions.

Abstract

L'invention concerne un procédé de production de particules de carbone à partir de précurseurs à structure de cellulose II, des particules de cellulose non cylindriques à structure de cellulose II servant de précurseurs.
PCT/AT2014/000224 2013-12-23 2014-12-15 Procédé de production de particules de carbone WO2015095902A1 (fr)

Applications Claiming Priority (2)

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ATA983/2013 2013-12-23
ATA983/2013A AT515234A1 (de) 2013-12-23 2013-12-23 Verfahren zur Herstellung von Carbonpartikeln

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2179181A (en) 1936-04-21 1939-11-07 Soc Of Chemical Ind Cellulose solutions and process of making same
US3447939A (en) 1966-09-02 1969-06-03 Eastman Kodak Co Compounds dissolved in cyclic amine oxides
EP0356419A2 (fr) 1988-08-16 1990-02-28 Lenzing Aktiengesellschaft Procédé pour produire des solutions de cellulose
EP0584318B1 (fr) 1992-03-17 1996-05-15 Lenzing Aktiengesellschaft Procede de fabrication d'elements moules cellulosiques
US20070178310A1 (en) 2006-01-31 2007-08-02 Rudyard Istvan Non-woven fibrous materials and electrodes therefrom
WO2008100573A1 (fr) * 2007-02-14 2008-08-21 University Of Kentucky Research Foundation Inc. Procédés de formation de charbons actifs
WO2009036480A1 (fr) 2007-09-21 2009-03-26 Lenzing Ag Poudre de cellulose et son procédé de préparation
WO2012125839A1 (fr) * 2011-03-15 2012-09-20 University Of Kentucky Research Foundation Particules de carbone

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5102855A (en) * 1990-07-20 1992-04-07 Ucar Carbon Technology Corporation Process for producing high surface area activated carbon

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2179181A (en) 1936-04-21 1939-11-07 Soc Of Chemical Ind Cellulose solutions and process of making same
US3447939A (en) 1966-09-02 1969-06-03 Eastman Kodak Co Compounds dissolved in cyclic amine oxides
EP0356419A2 (fr) 1988-08-16 1990-02-28 Lenzing Aktiengesellschaft Procédé pour produire des solutions de cellulose
EP0356419B1 (fr) 1988-08-16 1992-12-16 Lenzing Aktiengesellschaft Procédé pour produire des solutions de cellulose
EP0584318B1 (fr) 1992-03-17 1996-05-15 Lenzing Aktiengesellschaft Procede de fabrication d'elements moules cellulosiques
US20070178310A1 (en) 2006-01-31 2007-08-02 Rudyard Istvan Non-woven fibrous materials and electrodes therefrom
WO2008100573A1 (fr) * 2007-02-14 2008-08-21 University Of Kentucky Research Foundation Inc. Procédés de formation de charbons actifs
US20080254972A1 (en) 2007-02-14 2008-10-16 Rudyard Lyle Istvan Methods of forming activated carbons
WO2009036480A1 (fr) 2007-09-21 2009-03-26 Lenzing Ag Poudre de cellulose et son procédé de préparation
WO2012125839A1 (fr) * 2011-03-15 2012-09-20 University Of Kentucky Research Foundation Particules de carbone

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Tencel carbon precursor", LENZINGER BERICHTE, vol. 90, 2012, pages 58 - 63
"Tencel carbon precursor", LENZINGER BERICHTE, vol. 90, 2012, pages 58 - 63, XP002738647 *
JINGQUAN HAN ET AL: "Characterization of cellulose II nanoparticles regenerated from 1-butyl-3-methylimidazolium chloride", CARBOHYDRATE POLYMERS, vol. 94, no. 2, 1 May 2013 (2013-05-01), pages 773 - 781, XP055184187, ISSN: 0144-8617, DOI: 10.1016/j.carbpol.2013.02.003 *
LENZING AG: "Die Weltsensation - TENCEL (R) in Pulverform", 18 June 2009 (2009-06-18), XP002738646, Retrieved from the Internet <URL:http://www.lenzing.com/en/fibers/news/press-releases/detail/datum/2006/06/17/die-weltsensation-tencelR-in-pulverform.html> [retrieved on 20150420] *
LENZINGER BERICHTE, vol. 90, 2012, pages 58 - 63
ZHANG ET AL: "Facile synthesis of spherical cellulose nanoparticles", CARBOHYDRATE POLYMERS, APPLIED SCIENCE PUBLISHERS, LTD. BARKING, GB, vol. 69, no. 3, 10 May 2007 (2007-05-10), pages 607 - 611, XP022068683, ISSN: 0144-8617, DOI: 10.1016/J.CARBPOL.2007.01.019 *

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