EP1910592B1 - Method for producing carbon fibres - Google Patents

Method for producing carbon fibres Download PDF

Info

Publication number
EP1910592B1
EP1910592B1 EP06820934.5A EP06820934A EP1910592B1 EP 1910592 B1 EP1910592 B1 EP 1910592B1 EP 06820934 A EP06820934 A EP 06820934A EP 1910592 B1 EP1910592 B1 EP 1910592B1
Authority
EP
European Patent Office
Prior art keywords
template
precursor
approximately
carbon
fibrous
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.)
Not-in-force
Application number
EP06820934.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1910592A2 (en
Inventor
Lixin Luke Xue
Shuzhong Zhuang
Liqun Yu
John B. Paine Iii
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.)
Philip Morris Products SA
Original Assignee
Philip Morris Products SA
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 Philip Morris Products SA filed Critical Philip Morris Products SA
Publication of EP1910592A2 publication Critical patent/EP1910592A2/en
Application granted granted Critical
Publication of EP1910592B1 publication Critical patent/EP1910592B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/02—Manufacture of tobacco smoke filters
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/04—Tobacco smoke filters characterised by their shape or structure
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/062—Use of materials for tobacco smoke filters characterised by structural features
    • A24D3/063—Use of materials for tobacco smoke filters characterised by structural features of the fibers
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon
    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

Definitions

  • Carbon fibers have a wide variety of applications.
  • US 6 387 479 and US 6 277 771 teach their use in composite materials reinforcement.
  • US 6 037 400 teaches their use in electric wave prevention.
  • US 6 162 533 teaches their use in electrode construction.
  • Other uses are also well known as described in the prior art.
  • activated carbon fibers are used as filtration media for gas separations (including removal of gas phase constituents from cigarette smoke), catalyst adsorption, treatment of waste streams or contaminated vapors, and deodorization.
  • Carbon articles are currently made by carbonizing precursor materials such as petroleum pitches, polyacrylonitrile, cellulose, and phenolic resins.
  • precursor materials such as petroleum pitches, polyacrylonitrile, cellulose, and phenolic resins.
  • US 4 917 835 to Lear et al. discloses a process for the production of porous shaped phenolic based carbon materials.
  • poor rheological and mechanical properties of the carbon precursor materials have limited the production and processing of carbon fibers into desirable shapes.
  • poor mechanical properties of the precursors or the resulting carbon fibers also limit the formation of suitable media for filtration applications.
  • Carbon is known for use in cigarette filter elements due to its ability to filter or remove constituents from mainstream smoke.
  • activated carbon has the propensity to reduce the levels of certain gas phase components present in the mainstream smoke, resulting in a change in the organoleptic and toxicological properties of that smoke.
  • filter segments comprising activated carbon are described in US 2 881 770 to Tovey ; US 3 353 543 to Sproull et al ; US 3 101 723 to Seligman et al ; and US 4 481 958 to Ranier et al.
  • Certain commercially available filters have particles or granules of carbon, such as an activated carbon material, alone or dispersed within a cellulose acetate tow; other commercially available filters have carbon threads dispersed therein; while still other commercially available filters have so-called "plug-space-plug", “cavity filter” or “triple filter” designs.
  • a cigarette filter incorporating carbon fibers and/or other materials capable of absorbing and/or adsorbing gas phase components, while providing favorable, processing, handling, absorption/adsorption, dilution and, in the case of cigarette filters, drawing characteristics, so as to be acceptable to consumers.
  • no method currently exists to provide such a filter no method currently exists to provide such a filter.
  • commercially available activated carbons and molecular sieves are typically in granular and powdered forms. Materials in these forms do not maintain product cohesion, as granules or grains tend to settle after being packed inside a cigarette filter. It is therefore also desirable to form activated carbon fibers with improved product integrity.
  • a method for forming a carbon fiber comprising the steps of: mixing a carbon precursor with a fibrous template so that the carbon precursor i s formed within a void created by the template shape; curing the mixture to form a_precursor composite with a stable shape; carbonizing the precursor composite; and decomposing the fibrous template to yield a carbon fiber shaped by the void of the fibrous template.
  • activated carbon fibers may be developed with desirable cross-sectional shapes by developing their shapes from pre-formed templates.
  • Shaped carbon fibers may be created that have advantages in material reinforcement, electrical and other applications.
  • the templated activated carbon fibers formed using methods of the present invention may be provided with desired cross-sectional shapes that provide an efficient cigarette filter with higher TPM delivery, lower pressure drop and improved gas phase removal efficiency.
  • Preferred template shapes include, but are not limited. to, multilobal shaped such as trilobal shaped and quadrilobal shape, V-shaped, stylized I-shaped or nested stylized I-shaped, C-shaped, and irregular shaped.
  • Still further preferred embodiments of the present invention may be used to provide activated carbon fiber media formed with controlled fiber orientation and packing density, which are critical for achieving premium performance in various applications.
  • Preformed templates are provided with carbonaceous material and can be processed into woven or non-woven forms with desired fiber orientation and packing density.
  • Activated carbon filtration media with controlled fiber orientation and packing density can then be formed by curing, carbonizing and activating the carbon or carbonaceous precursor fibers.
  • the carbonizing step is performed in an inert media, under vacuum or a combination thereof.
  • Templated carbon fibers with controlled cross-sectional shapes provide cigarette filters that are effective at reducing main stream smoke gas phase components.
  • Cigarette 10 comprises first plug 12, space 14, second plug 16, tobacco 18 and paper 20.
  • the plug-space-plug filter abuts tobacco 18.
  • the end user sets fire to paper 20 and tobacco 18 at the end opposite the filter. Air and particulate mater is then drawn toward the filter by the user.
  • Space 14 may be filled with a material 22 such as carbon and may have voids, channels or openings 24.
  • FIG. 2 illustrates a plug-space filter arrangement.
  • the filter is similar to that shown in Fig. 1 , but cigarette 10 instead comprises plug 12, space 14, tobacco 18 and paper 20.
  • the plug-space filter abuts tobacco 18.
  • space 14 may be filled with a material such as carbon 22 and may have voids, channels or openings 24.
  • Templated carbon fibers are prepared by loading carbon precursor materials such as phenolic resins onto shaped fibrous templates made of low carbon yielding materials such as polypropylene that contain longitudinal channels as will be discussed in greater detail below with reference to Figs. 3 and 4 ; curing the loaded carbon precursors inside the channels of the templates to form composite fibrous precursors; carbonizing the composite fibrous precursors under an inert atmosphere or in a vacuum; and decomposing the shape controlling templates to form templated carbon fibers with controlled cross-sectional shapes as will be discussed in greater detail below with reference to Fig. 11 .
  • Fibrous template 26 may have a cross-section with a shape including, but not limited to, the shapes shown in Figs. 5-10 , which may be described as trilobal shaped, quadrilobal shaped, V-shaped, stylized I-shaped or nested stylized I-shaped, C-shaped, and irregular shaped, respectively.
  • Templates can be shaped and formed through extrusion, spinning or other shape forming process as taught, for example, in US 5 057 368 to Largman et al. Template 26 may be made from any polymeric material, and may leave only an insignificant amount of residue, for example, zero char yield, upon thermal decomposition.
  • a preferred material for template 26 is polypropylene (PP).
  • the cross-sectional shape of template 26 provides longitudinal channels 28 that may be continuous and that open to the surface of template 26.
  • the carbon precursor 30 may comprise solid particles, gels, foams, liquids or mixtures thereof, which yield carbon or carbonoid materials upon heating at a carbonization temperature in an inert atmosphere or under vacuum.
  • Suitable materials in these classes include, but are not limited to, phenolic resin, petroleum pitches, polyacrylonitrile, cellulose, cellulose derivatives, polyvinyl acetate (PVA) and their mixtures.
  • PVA polyvinyl acetate
  • Molecular sieves, zeolites, and silicates, or other additional inorganic materials may be included in the mixture to modify the pore-distribution of the final carbonoid products.
  • the phenolic resins proposed can be uncured or partially cured Novolak type with the presence of curing agents, or Resole (self-curing) type or mixtures thereof. In the mixture, comminuted partially cured resin as described in US 4 917 835 to Lear et al may be used as described or merely for binding components.
  • Precursor 30 is mixed with fibrous templates according to well known techniques, such as described in US 6 584 979 and US 5 772 768 both filed by Xue et al.
  • templates 26-26E have voids or channels 28.
  • Precursor 30 is loaded into the channels 28 by mixing shaped templates 26-26E with precursor 30 in a container (not shown).
  • Fig. 3 illustrates loading quadrilobal template 26A with precursor 30.
  • the template is first placed, dipped, dropped, or pulled through the container containing the precursor (not shown). Certain levels of agitation or rotation of the container may be necessary to achieve homogeneous impregnation of the channels as shown in related application US 10/294,346 .
  • the weight ratio of carbon precursor to polypropylene template is preferably within, but not limited to, the range of 0.25 and 2.
  • a certain amount of liquid solvent such as ethanol may be used to adjust the viscosity to allow homogeneous impregnation.
  • excess precursor 30 may be located outside of channel 28, which can be removed from the outside of template 26A by any well known removal method including, but not limited to, rinsing, washing in a solvent, wiping, draining or blowing.
  • the excess precursor 30 that resides outside channels 28 or on the template 26 may be removed by rubbing the filaments with a paper towel, pad, cloth or other suitable means, containing a solvent such as ethanol. After this process, precursor 30 remains within channel 28 as shown in Fig. 4 .
  • Curing conditions may be selected so that fibrous template 26 maintains structural and/or chemical integrity while the carbon precursor 30 is cured inside the template 26 to form a non-flowing resin.
  • the conditions may be selected based on the components in the carbon precursor, especially the uncured components used as binders.
  • PP templates and phenolic resin based carbon precursor can be used to practice the invention.
  • the precursor can be precursor can be used to practice the invention.
  • the precursor can be cured by heating under atmosphere in a temperature from approximately 120°C to 160°C for approximately 15 to 60 minutes. A certain level of acid may be added to phenolic precursors to accelerate the curing.
  • the cured composite fibrous precursors can be heated in an inert environment and/or under vacuum to decompose the template and allow the carbon precursor to yield templated carbon fibers 32, as shown in Fig. 11 .
  • carbonization can be achieved by heating the carbon precursor to a temperature within the range of approximately 600°C to approximately 950°C for approximately 30 minutes to four hours, though temperatures and times may be varied to achieve the desired result for any particular situation.
  • Fig. 11 illustrates the shaped carbon fibers 32 that remain after decomposing the template illustrated in Figs. 3 and 4 .
  • Shaped carbon fibers 32 derive their shapes from those of templates 26 and therefore may also be termed "templated carbon fibers".
  • Portions 34 may remain in the area between the extensions of 26A that cleaning did not remove.
  • Table 1 lists seven examples conducted using various templates and processing conditions to achieve differing resulting channels.
  • carbonization can be accomplished by heating the materials under nitrogen or argon flow at a temperature of approximately 850°C for approximately one to two hours, where a phenolic-based carbon precursor and PP template are used. Carbon yields are generally in the range of 10-40% by weight depending on the PP content of the composite precursors.
  • Table 1 Carbon Articles Processed in Accordance with the Present Invention Process Template Cavity Loading Curing 150°C Carbonizing 850°C Carbon Fiber Example Fiber ID/ ⁇ m Factor Min.
  • a polypropylene template was mixed with a phenolic resin based carbon precursor.
  • EtOH was used in phenolic precursor formulation to reduce viscosity.
  • Templates of 16 to 24 denier per filament (dpf) were used that comprised channels with inner diameter or inner dimension (ID) of approximately 10 ⁇ m to 60 ⁇ m.
  • ID inner diameter or inner dimension
  • the templates had a loading factor of between 0.38 and 1.6.
  • Curing took place at approximately 150°C for approximately 15 to 40 minutes.
  • a certain level of acid may be added to the phenolic precursor to accelerate this curing time.
  • Carbonizing was performed at approximately 850°C for approximately 1 to 2 hours. Carbon yields were generally in the range of 10 to 24% by weight depending on the polypropylene content of the composite precursor.
  • the carbon fibers derived their shape and outer diameter or outer dimension (OD) from the shape and ID of the template, respectively.
  • the range given for the OD and ID reflects the pliability of the template and the characteristics of the various voids 28. For example, some of the voids had different dimensions in different directions.
  • Fig. 11 illustrates areas 34 that were not contained within the ID of the quadrilobal surface, but that do contribute to the OD achieved.
  • the templated carbon fibers can be activated to form high surface area adsorptive materials for filtration applications.
  • Many activation processes are known in the literature such as heating with CO 2 or water steam. Activation can be achieved by maintaining a temperature within the range of approximately 800°C to approximately 950°C for approximately 30 minutes.
  • templated carbon fiber from Example 5 in Table 1 can be activated with CO 2 at a temperature of approximately 950°C for approximately 30 minutes.
  • a BET surface area of 1557m 2 /g and a micro-pore volume ( ⁇ 20 ⁇ ) of 0.6415cm 3 /g may be obtained. These values are comparable to those of coconut based activated carbon granules, which are often used as adsorbents in cigarette filters.
  • Modified 1R4F cigarette models containing 66mg and 150mg of activated templated carbon fibers were prepared under the configurations shown in Figs. 1 and 2 , respectively.
  • plug 12 had a length of 12mm
  • carbon article 22 had a length of 8mm
  • second plug 16 had a length of 7mm
  • plug 12 had a length of 10mmm
  • carbon article 22 had a length of 17mm.
  • the cigarettes were smoked under FTC conditions while the smoke chemistry was analyzed by FTIR and GC/MS methods.
  • Tables 2-3 and Figs. 12 and 13 the filters formed in accordance with the present invention are effective at reducing a wide range of smoke gas phase components when used in cigarette smoke filtration.
  • Table 2 compares a standard 1R4F cigarette to a cigarette containing a carbon article according to the present invention with the processing specifications described in Example 5 from Table 1.
  • the 1R4F cigarette is a Kentucky Reference filtered cigarette provided by the Tobacco and Health Research Institute, University of Kentucky for research purposes.
  • the first row of Table 2 lists the characteristics of control sample 1R4F, which are relatively exemplary characteristics of a control cigarette.
  • the second and third rows of Table 2 list the characteristics of modified samples TF-66-1 and TF-66-2, respectively, which were made according to the present invention and which were provided as a percentage difference in characteristics from the control sample 1R4F.
  • Modified samples TF-66-1 and TF-66-2 were cigarettes with the structure shown in Fig. 1 in which plug 12 was 12mm, plug 16 was 7mm and the carbon article 24 was 5mm in axial length. The carbon article weighed 66mg. However, these values are exemplary only and any lengths and/or weights could be selected.
  • Table 2 provides the TPM values of an 1R4F sample.
  • the standard deviation is given with the 1R4F data.
  • the values reported for modified samples TF-66-1 and TF-66-2 are given as a change from the 1R4F standard.
  • a change of greater than three times the standard deviation of the 1R4F control sample is considered significant.
  • the acetaldehyde (AA), methanol (MeOH) and isoprene (ISOP) in the total particulate matter (TPM) all decreased as a result of employing the present invention.
  • Hydrogen cyanide (HCN) increased slightly, but not significantly.
  • Table 2 Modified Sample Cigarettes Compared to the Control Sample cigarette.
  • Figs. 12 and 13 further illustrate how samples modified according to the present invention reduce the puff-by-puff delivery of acrolein and 1,3-butadiene.
  • Fig. 12 illustrates puff-by-puff acrolein delivery of modified 1R4F cigarettes compared to TF-66 and TF-150 samples.
  • Fig. 13 illustrates the puff-by-puff 1,3-butadiene Delivery of Modified 1 R4F cigarettes compared to TF-66 and TF-150 samples.
  • FIG. 12 shows the amount of acrolein in mainstream smoke for different puffs from Kentucky reference IR4F cigarettes and the modified samples.
  • Acrolein in cigarette smoke is measured on a per puff basis.
  • Cigarettes are smoked with a 35cm 3 puff volume of two second duration, once every 60 seconds.
  • the puff-by-puff acrolein deliveries are reported for eight determinations of 1R4F as well as the modified samples.
  • the first puff accounts for between 15% and 20% of the total delivery of the 1R4F, but generally near 0 for the modified samples.
  • the puff process is repeated seven more times according to well known and reported methods to obtain the graph shown in Fig. 12 .
  • a similar method is used to determine the delivery of 1,3-butadiene.
  • acrolein and 1,3-butadiene As shown in Figs. 12 and 13 the content of the constituent gases increases each puff due to saturation of the filter. However, delivery of acrolein and 1,3-butadiene is lower for the sample created using the method of the present invention. In fact, acrolein and 1,3-butadiene delivery in the samples was nearly zero for the first several puffs.
  • Table 3 further illustrates the benefits of the present invention.
  • the first column lists characteristics and components common to cigarettes and cigarette smoke.
  • the second column labeled “1R4F Standard Deviation,” lists the standard deviation of certain gas phase components present in a control 1R4F cigarette.
  • Columns labeled TF-66 and TF-150 list the changes in component gas levels as a result of using filters made in accordance with the present invention, and more particularly Example 5 from Table 1.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Ceramic Products (AREA)
EP06820934.5A 2005-06-29 2006-06-28 Method for producing carbon fibres Not-in-force EP1910592B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/170,225 US20070000507A1 (en) 2005-06-29 2005-06-29 Templated carbon fibers and their application
PCT/IB2006/003289 WO2007026253A2 (en) 2005-06-29 2006-06-28 Templated carbon fibers and their applications

Publications (2)

Publication Number Publication Date
EP1910592A2 EP1910592A2 (en) 2008-04-16
EP1910592B1 true EP1910592B1 (en) 2013-08-21

Family

ID=37588045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06820934.5A Not-in-force EP1910592B1 (en) 2005-06-29 2006-06-28 Method for producing carbon fibres

Country Status (7)

Country Link
US (1) US20070000507A1 (ru)
EP (1) EP1910592B1 (ru)
JP (1) JP5281889B2 (ru)
KR (1) KR101342808B1 (ru)
EA (1) EA013577B1 (ru)
UA (1) UA94584C2 (ru)
WO (1) WO2007026253A2 (ru)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0019417D0 (en) * 2000-08-09 2000-09-27 Mat & Separations Tech Int Ltd Mesoporous carbons
US8591855B2 (en) * 2000-08-09 2013-11-26 British American Tobacco (Investments) Limited Porous carbons
GB0506278D0 (en) 2005-03-29 2005-05-04 British American Tobacco Co Porous carbon materials and smoking articles and smoke filters therefor incorporating such materials
CA2584947C (en) * 2007-03-12 2012-06-26 C-Tech Industries, Inc. Wastewater treatment and recycling system
US9370353B2 (en) * 2010-09-01 2016-06-21 Abbott Cardiovascular Systems, Inc. Suturing devices and methods
US8790556B2 (en) * 2012-07-25 2014-07-29 Celanese Acetate Llc Process of making tri-arc filaments
KR101628461B1 (ko) * 2014-06-23 2016-06-09 오씨아이 주식회사 탄소섬유 단열재 및 이의 제조방법
EP3450596B1 (en) * 2016-04-27 2024-08-21 Toray Industries, Inc. Porous fiber, adsorbent material, and purifying column
CN106866341B (zh) * 2017-01-20 2019-08-06 中国科学院青岛生物能源与过程研究所 一种分离回收发酵尾气中低浓度异戊二烯的方法
CN116332670B (zh) * 2023-03-14 2024-07-09 松山湖材料实验室 多孔碳发热体及其制备方法、多孔碳雾化芯与电子烟

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8617831D0 (en) * 1986-07-22 1986-08-28 British Petroleum Co Plc Production of porous shaped articles
US5057368A (en) 1989-12-21 1991-10-15 Allied-Signal Filaments having trilobal or quadrilobal cross-sections
US5509430A (en) * 1993-12-14 1996-04-23 American Filtrona Corporation Bicomponent fibers and tobacco smoke filters formed therefrom
US5510063A (en) * 1994-04-15 1996-04-23 Corning Incorporated Method of making activated carbon honeycombs having varying adsorption capacities
JP3073403B2 (ja) 1994-09-05 2000-08-07 松下電器産業株式会社 クリーム半田印刷装置
US6143412A (en) * 1997-02-10 2000-11-07 President And Fellows Of Harvard College Fabrication of carbon microstructures
JP2001073226A (ja) * 1999-08-30 2001-03-21 Gun Ei Chem Ind Co Ltd 複合繊維、フェノール系極細炭素繊維およびそれらの製造方法
US6583075B1 (en) * 1999-12-08 2003-06-24 Fiber Innovation Technology, Inc. Dissociable multicomponent fibers containing a polyacrylonitrile polymer component
MY128157A (en) * 2000-04-20 2007-01-31 Philip Morris Prod High efficiency cigarette filters having shaped micro cavity fibers impregnated with adsorbent or absorbent materials
JP2001316945A (ja) * 2000-05-11 2001-11-16 Sumitomo Durez Co Ltd 炭素繊維及び繊維状活性炭
JP3590606B2 (ja) * 2001-11-16 2004-11-17 日本原子力研究所 テンプレートを利用したカーボンナノチューブの作製法
CA2481381C (en) * 2002-04-12 2012-11-13 Philip Morris Products S.A. Activated carbon fiber cigarette filter
JP2004036038A (ja) * 2002-07-03 2004-02-05 Mitsubishi Rayon Co Ltd 炭素繊維前駆体繊維、それを用いる炭素繊維の製造方法及びその炭素繊維から得られるフィラメント状カーボンナノファイバー
JP2004176236A (ja) * 2002-09-30 2004-06-24 Teijin Ltd 炭素繊維の製造方法

Also Published As

Publication number Publication date
JP5281889B2 (ja) 2013-09-04
UA94584C2 (ru) 2011-05-25
KR101342808B1 (ko) 2013-12-17
KR20080019027A (ko) 2008-02-29
EA013577B1 (ru) 2010-06-30
EA200800167A1 (ru) 2008-04-28
US20070000507A1 (en) 2007-01-04
EP1910592A2 (en) 2008-04-16
WO2007026253A2 (en) 2007-03-08
WO2007026253A3 (en) 2007-07-19
JP2009500528A (ja) 2009-01-08

Similar Documents

Publication Publication Date Title
EP1910592B1 (en) Method for producing carbon fibres
KR101334430B1 (ko) 형상화된 미세-채널을 가지는 주형을 이용한 탄소 일체형튜브 및 그것의 제조방법
US7370657B2 (en) Activated carbon-containing sorbent
DE60311769T3 (de) Zigarettenfilter mit geperlter Aktivkohle
EP1494552B1 (en) Activated carbon fiber cigarette filter
US8227376B2 (en) Carbon beads with multimodal pore size distribution
JP4916453B2 (ja) 喫煙物品における表面改質活性炭
US9259031B2 (en) Filter for a smoking article
KR100588056B1 (ko) 담배 필터
JPH0458876A (ja) たばこフィルター用繊維束

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080129

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20110210

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 628175

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006038028

Country of ref document: DE

Effective date: 20131017

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 628175

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130821

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130821

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130703

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131221

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131223

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131122

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20140522

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006038028

Country of ref document: DE

Effective date: 20140522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140628

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130821

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20060628

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20220628

Year of fee payment: 17

Ref country code: GB

Payment date: 20220622

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220628

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220620

Year of fee payment: 17

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230529

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006038028

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240103

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230628