US20030230194A1 - Activated carbon fibers and related methods for the use and production thereof and of making protective clothing and a filter module - Google Patents
Activated carbon fibers and related methods for the use and production thereof and of making protective clothing and a filter module Download PDFInfo
- Publication number
- US20030230194A1 US20030230194A1 US10/463,018 US46301803A US2003230194A1 US 20030230194 A1 US20030230194 A1 US 20030230194A1 US 46301803 A US46301803 A US 46301803A US 2003230194 A1 US2003230194 A1 US 2003230194A1
- Authority
- US
- United States
- Prior art keywords
- polymer
- carbon fibers
- metal
- activated carbon
- organic
- 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.)
- Abandoned
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 230000001681 protective effect Effects 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 239000000835 fiber Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000004917 carbon fiber Substances 0.000 claims abstract description 28
- 229920000620 organic polymer Polymers 0.000 claims abstract description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000000578 dry spinning Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 229920001169 thermoplastic Polymers 0.000 claims 2
- 239000004416 thermosoftening plastic Substances 0.000 claims 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000005087 graphitization Methods 0.000 abstract description 6
- 230000006641 stabilisation Effects 0.000 abstract description 6
- 238000011105 stabilization Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 229920000592 inorganic polymer Polymers 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 copolyaramides Polymers 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
Definitions
- the invention relates to activated porous carbon fibers, in particular for the adsorption or separation of gaseous substances, and also to methods for the use and production thereof and of making protective clothing and a filter module.
- the production of activated carbon fibers by surface treatment of carbon fibers has been known for a relatively long time.
- precursor materials of polyacrylonitrile (PAN) or pitch are preferably used because of the good mechanical and adsorption properties of the carbon fibers that can be obtained therefrom.
- PAN polyacrylonitrile
- the production of activated carbon fibers based on polyacrylonitrile precursors begins with the stabilization in air at approximately 230-300° C. that is standard for carbon fibers. Chemical transformation of the polyacrylonitrile forms an infusible fiber.
- the resultant oxidized fiber can be activated directly or, more frequently, first processed further to form a textile structure. Heating the fibers to temperatures above approximately 1200° C. activates them. However, in contrast with the process for conventional carbon fibers, the activation is not carried out in an inert atmosphere, but in an oxidizing one. Typical oxidizing agents of this process step are H 2 O or CO 2 . The reaction of the oxidizing agents results in a strong attack on the surface of the fiber, whereby a porous surface is formed. The size of the specific surface area and the configuration of the carbon atoms within the surface pores substantially determine the selectivity and strength of adsorption of chemical substances by the activated carbon fiber. The activation of the carbon fibers that are produced based on pitch precursors is effected in a similar manner by surface oxidation of the carbonized fiber.
- the production of membranes with a particularly high specific surface area using porous fibers is described in European Patent Application EP 0 394 449 A1, which corresponds to U.S. Pat. No. 5,089,135.
- the membranes are formed by porous hollow carbon fibers.
- the production method provides for spinning polymer mixtures of PAN-based polymer A and (pyrolyzable) polymer B (i.e. a polymer that can be decomposed by heat), if applicable with a solvent and solubilizer, to form hollow polymer fibers.
- the hollow form is achieved, for example, by the use of slotted nozzles, with the inside diameter of the fibers being a few 100 ⁇ m.
- the porosity of the hollow fibers is established by the decomposition of the polymer B.
- the polymer B is decomposed at temperatures below 600° C.
- vinyl and methacrylate polymers are listed as the polymers.
- Their specific viscosity is specified as being preferably in the range of 0.1 to 0.4.
- U.S. Pat. No. 6,364,936 B1 to Rood, et al. describes the set-up of an adsorption/desorption module of activated carbon fibers.
- One or more hollow elements of activated carbon fiber fabric is/are configured lengthwise. The fiber elements are heated directly by electric current in order to be able to carry out selective adsorption of constituents from the gas stream and the subsequent desorption thereof.
- activated carbon fibers including pores of carbon fibers filled at least in part, that is, to at least 30% by volume, by active substances.
- the active substances are formed by carbon, metals and/or metal carbides originating from the carbonization of organic or metallo-organic polymers that are already present in a finely distributed manner in the precursor fiber for the production of carbon fibers.
- the carbon fibers are activated by producing pores that are partly filled with carbon, metal, and/or metal carbide.
- These active centers are formed by the carbonization of particles of an organic or metallo-organic polymer that are distributed in the carbon precursor fiber formed by polyacrylonitrile polymer.
- the production method for carbon fibers described at the beginning does not need to be changed substantially for this.
- the carbon fibers in accordance with the invention are suitable in particular for the adsorption or separation of gases.
- a method that provides for mixed polymers from a polyacrylonitrile-based (PAN-based) precursor for carbon fibers (polymer A) and a carbonizable polymer (polymer B) to be spun to form mixed fibers.
- PAN-based polyacrylonitrile-based
- polymer B carbonizable polymer
- the mixed fibers are stabilized.
- the fibers are carbonized to form the finished activated carbon fibers.
- the polymer B is selected with regard to its solubility and particle size so that it is present in the PAN-based fiber in a finely distributed or microdispersed manner.
- the framework of the carbon fiber is established from the PAN-based portion, while the decomposition product of the polymer B remains (behind) as a highly porous and active material and forms pores that are filled at least in part in and on the carbon fiber.
- the initial composition of the polymer B different carbon residues, metals or metal carbides that have differing selectivities with respect to different adsorbates can also be obtained in this way.
- the polymer B is only partly decomposed so that its solid and non-volatile residue remains as an active substance in the fiber.
- the active centers of the activated carbon fibers are thus substantially formed by the solid decomposition products of the polymer B.
- the method in accordance with the invention provides the following steps:
- PAN-based polymers that are usual in the market for the production of carbon fibers, also called precursors, are used as the polymer A. Typically, they are synthesized as copolymers from over 90 mol % acrylonitrile units and further comonomer units.
- a carbonizable organic or metallo-organic polymer whose carbonization residue is at least 22 wt % and preferably over 30 wt %, is used as the polymer B.
- the carbonization residue is that residue of the polymer B in wt % that results under the conditions of carbonization treatment of the corresponding mixed fiber. These are temperatures above 500° C. under non-oxidizing conditions.
- the carbonization residue of the polymer B preferably is below that of the PAN-based polymer. If the more intensive pyrolysis in the case of polymer B results in a greater volume shrinkage than in the case of the precursor material of polymer A, then opened pores are formed as a result. Particularly preferably, however, polymers B are used that show a comparatively small shrinkage in volume in the case of carbonization. As a result, the regions of carbonized polymer B remain microporous and increase the specific surface area of the fiber in an advantageous manner.
- the pores in the carrier fiber are at least in part filled by the generally microporous decomposition products of the polymer B. The pores are preferably filled to at least 30% by volume and particularly preferably to at least 50% by volume with the decomposition products that are, if applicable, microporous.
- the polymer B content typically lies below 50 wt % of the polymer mixture of A and B and preferably in the range of 3 to 40 wt %.
- the precondition for the formation of discrete regions of residues of the carbonization of polymer B is that the polymer B is already present in the mixed fiber in a finely dispersed or microdispersed manner.
- the particle size of the polymer B should not exceed 50% of the fiber diameter of the resulting mixed fiber.
- the average diameter of the individual particles of the polymer B preferably lies below 1500 nm and particularly preferably below 800 nm.
- the partly filled pores formed after the carbonization of the fibers should not have less than an average minimum diameter. This minimum diameter is approximately 30 nm.
- a microdispersed distribution is guaranteed in particular if the polymer B has a low level of solubility or no solubility at all in the PAN spinning solution.
- Usual PAN spinning solutions for the wet or dry spinning process contain solvents. In accordance with the invention, polymers B that are insoluble in the solvent used are therefore preferred.
- the polymers B are to have a melting point above the process temperature of the oxidization of the mixed fiber. Resins or polymers that cross-link to form infusible compounds are preferred. Examples of suitable organic polymers B are inter alia polyesters, phenolic resins, polyamides, polyaramides, copolyaramides, para-aramides, or cellulose.
- metallo-organic polymers such compounds in which metallic atoms are incorporated directly into the polymer chain and also those in which the metallic atoms are bound in a complex manner, in particular to heteroatoms, such as O or N.
- heteroatoms such as O or N.
- carboxyl, carbonyl, and imine groups crop up in the latter case.
- complex organic metal salts that are present in an aggregated and high-molecular form also can number among the metallo-organic polymers.
- Polyacetates, polymeric cyclopentadienyls or polymeric alcoholates, or acetylacetonates inter alia number among the metallo-organic polymers in accordance with the invention.
- Preferred metal constituents of the metallo-organic polymers are the transition metals, in particular of the first series, and the platinum metals. These are distinguished by high chemical activity in atomic form or as a carbide compound and establish a high and in part very selective adsorption capacity.
- Metallo-organic compounds or complex organic compounds of the elements Ti, Cr, W, Fe, Co, Ni, Pd, and Pt are particularly preferred.
- the metallo-organic polymer B also can contain further metal in elementary form, whereby the active region content of the fiber can be further increased.
- Resin-bonded metal micropowders of the elements Ti, Cr, Fe, or Pt are preferably used in this connection.
- the carbonization residue of the metallo-organic compounds typically includes a mixture of carbon, metal, and metal carbide in a varying composition.
- the carbonization residue of the compound used is preferably over 25 wt %, particularly preferably above 35 wt %.
- the fiber diameter of the mixed fibers in accordance with the invention after the spinning process is below 200 ⁇ m, with the range between 10 to 30 ⁇ m, which is usual for PAN fibers as precursor material for conventional carbon fibers, being preferred. Thick fibers above approximately 60 ⁇ m are, if applicable, also to be constructed as profiled fibers, since in this way their surface area is further enlarged.
- the mixed fibers are rendered infusible. This occurs by oxidation at temperatures of preferably 230 to 300° C. In a known way, as a result of dehydration and cyclization at a molecular level, stabilization of the polyacrylonitrile takes place that renders the polymer infusible and carbonizable.
- the polymers B are also present in an infusible form. If applicable, the cross-linkage of the polymer B that leads to the stabilization likewise first takes place in this method step. Subsequent cross-linkage is observed, for example, in the case of polyesters or phenolic resins.
- a preferred form of heat treatment for the stabilization provides for heating in air to 230° C. with a holding time of approximately 140 minutes at a heating rate of approximately 5° C./minute. Shorter process times can be rendered possible by higher temperature levels, for example approximately 60 minutes at approximately 270° C.
- metallo-organic compounds are used as the polymer B, an isothermal temperature profile at the lowest possible temperature is to be preferred, because overheating of the fiber under oxidizing conditions is to be avoided, since there is a risk of oxidation of the metallo-organic compounds to form metal oxides that are generally undesired.
- Partly carbonized fibers have inter alia reduced thermal conductivity, as a result of which, they have an advantage in applications that demand good thermal insulation compared with the carbon fibers.
- Such partly carbonized fibers are also referred to collectively as carbon fibers in the following.
- a further aspect of the invention is the use of the activated fibers to separate gas mixtures and to adsorb gaseous substances.
- the separation of CO 2 is considered in this connection.
- a typical configuration for separating gaseous substances, and in particular CO 2 as well, is set up out of two modules that alternately perform the function of adsorption, followed by desorption. The modules can then be heated in an advantageous manner by utilizing the electrical conductivity of the carbon fibers.
- the set-up of filter modules for example in the chemical industry, is designated as a further application.
- the fiber material can also be used as a component part of activated and, if applicable, thermally insulating protective clothing.
- the protective clothing can perform the additional function of adsorption of harmful substances.
- the partly carbonized fibers have the advantage over the carbon fibers, since the textile processibility and the wear comfort of the clothing are clearly better.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/656,259 US7708805B2 (en) | 2002-06-17 | 2007-01-22 | Method of producing carbon fibers, and methods of making protective clothing and a filter module |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10226969A DE10226969B4 (de) | 2002-06-17 | 2002-06-17 | Aktivierte Kohlenstofffasern und Verfahren zu ihrer Herstellung |
DE10226969.6 | 2002-06-17 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/656,259 Division US7708805B2 (en) | 2002-06-17 | 2007-01-22 | Method of producing carbon fibers, and methods of making protective clothing and a filter module |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030230194A1 true US20030230194A1 (en) | 2003-12-18 |
Family
ID=29716514
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/463,018 Abandoned US20030230194A1 (en) | 2002-06-17 | 2003-06-17 | Activated carbon fibers and related methods for the use and production thereof and of making protective clothing and a filter module |
US11/656,259 Expired - Fee Related US7708805B2 (en) | 2002-06-17 | 2007-01-22 | Method of producing carbon fibers, and methods of making protective clothing and a filter module |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/656,259 Expired - Fee Related US7708805B2 (en) | 2002-06-17 | 2007-01-22 | Method of producing carbon fibers, and methods of making protective clothing and a filter module |
Country Status (7)
Country | Link |
---|---|
US (2) | US20030230194A1 (de) |
EP (1) | EP1375707B1 (de) |
JP (1) | JP4460232B2 (de) |
AT (1) | ATE441747T1 (de) |
DE (2) | DE10226969B4 (de) |
ES (1) | ES2333113T3 (de) |
PT (1) | PT1375707E (de) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100181212A1 (en) * | 2006-08-09 | 2010-07-22 | Matthias Koch | Monolithic materials for gas stores |
CN102167319A (zh) * | 2011-05-13 | 2011-08-31 | 江苏大学 | 一种醋糟制备活性炭的方法 |
US8961661B1 (en) * | 2012-10-24 | 2015-02-24 | Hrl Laboratories, Llc | Polymer/scaffold nanocomposites for hydrogen storage |
CN104445193A (zh) * | 2014-12-03 | 2015-03-25 | 盐城工学院 | 具有去除难降解有机污染废水2,4,6三氯酚作用的枝叶多孔炭及其制备方法与应用 |
US10131770B2 (en) | 2014-02-26 | 2018-11-20 | Toray Industries, Inc. | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
CN110656403A (zh) * | 2019-11-07 | 2020-01-07 | 武汉纺织大学 | 一种易导电掺金属聚丙烯腈碳纤维及其制备方法 |
CN113694691A (zh) * | 2021-07-16 | 2021-11-26 | 西安交通大学 | 一种含金属的单原子流体制备方法 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE602004028492D1 (de) * | 2003-09-19 | 2010-09-16 | Teijin Ltd | Verfahren zur herstellung von faserförmiger aktivkohle und daraus hergestellter vliesstoff |
DE102006010862B4 (de) * | 2005-12-20 | 2010-01-14 | BLüCHER GMBH | Aktivkohle mit katalytischer Aktivität |
KR100953147B1 (ko) | 2008-02-28 | 2010-04-16 | 충남대학교산학협력단 | 금속 촉매가 균일하게 증착된 수소저장매체용 탄소나노섬유및 그 제조방법 |
US9181134B1 (en) | 2011-04-27 | 2015-11-10 | Israzion Ltd. | Process of converting textile solid waste into graphite simple or complex shaped manufacture |
DE102011080548A1 (de) * | 2011-08-05 | 2013-02-07 | Sgl Carbon Se | Precursorfasern auf Basis von nachwachsenden Rohstoffen |
FR2980191B1 (fr) * | 2011-09-20 | 2014-10-24 | Commissariat Energie Atomique | Procede de fabrication d'un materiau composite silicium/carbone et utilisation d'un tel materiau |
US9409337B2 (en) | 2013-11-08 | 2016-08-09 | Georgia Tech Research Corporation | Polyacrylonitrile/cellulose nano-structure fibers |
CN104018249B (zh) * | 2014-06-10 | 2016-05-18 | 中国科学院理化技术研究所 | 一种高比表面积微孔活性炭纳米纤维的制备方法 |
CN104307470B (zh) * | 2014-09-30 | 2016-06-29 | 天津理工大学 | 一种高吸附量的纤维素纤维基活性炭纤维的制备方法及其产品和应用 |
WO2016057696A1 (en) | 2014-10-08 | 2016-04-14 | Georgia Tech Research Corporation | High strength and high modulus carbon fibers |
CN104556029B (zh) * | 2014-12-21 | 2017-03-08 | 沈阳工程学院 | 石油渣油与焦油渣联合制备活性炭和燃料油 |
KR102206860B1 (ko) * | 2016-01-05 | 2021-01-22 | 코오롱인더스트리 주식회사 | 하이브리드 활성탄소섬유 및 그의 제조방법 |
EP3246436A1 (de) | 2016-05-19 | 2017-11-22 | DWI - Leibniz-Institut für Interaktive Materialien e.V. | Verfahren zur herstellung hochporöser kohlenstofffasern durch schnelle karbonisierung von kohlenstoffvorläuferfasern |
US10874547B2 (en) | 2017-07-10 | 2020-12-29 | David L. Burge | Therapeutic textile articles and methods of use |
CN110078106B (zh) * | 2019-05-07 | 2021-11-16 | 李平 | 电石渣的回收利用方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111396A (en) * | 1960-12-14 | 1963-11-19 | Gen Electric | Method of making a porous material |
US3628984A (en) * | 1968-05-27 | 1971-12-21 | Nippon Carbon Co Ltd | Method for the manufacture of heat-resistant carbonaceous products having low permeability |
US3666526A (en) * | 1966-01-06 | 1972-05-30 | Gen Electric | Refractory porous bodies |
US3922334A (en) * | 1973-01-31 | 1975-11-25 | Airco Inc | Foam carbonization and resulting foam structures |
US4067956A (en) * | 1976-10-08 | 1978-01-10 | Chemotronics International, Inc. | Reticulated anisotropic porous vitreous carbon |
US4100314A (en) * | 1977-03-29 | 1978-07-11 | Airco, Inc. | Method for increasing the strength and density of carbonaceous products |
US4220846A (en) * | 1978-07-26 | 1980-09-02 | The Fluorocarbon Company | Method and apparatus utilizing a porous vitreous carbon body particularly for fluid heating |
US4362646A (en) * | 1979-09-28 | 1982-12-07 | Toho Beslon Co., Ltd. | Process for the production of fibrous activated carbon |
US5089135A (en) * | 1988-01-20 | 1992-02-18 | Mitsubishi Rayon Co., Ltd. | Carbon based porous hollow fiber membrane and method for producing same |
US5895716A (en) * | 1995-07-18 | 1999-04-20 | The B.F. Goodrich Company | Wet friction materials, methods of making them, and apparatus containing the same |
US6364936B1 (en) * | 2000-05-15 | 2002-04-02 | The Board Of Trustees Of The University Of Illinois | Selective sorption and desorption of gases with electrically heated activated carbon fiber cloth element |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925524A (en) * | 1972-06-22 | 1975-12-09 | Celanese Corp | Process for the production of carbon filaments |
JPS58146446A (ja) | 1982-02-25 | 1983-09-01 | Asahi Chem Ind Co Ltd | 固定層触媒 |
GB2168966B (en) * | 1984-11-14 | 1988-09-01 | Toho Beslon Co | High-strength carbonaceous fiber |
EP0394449A4 (en) * | 1988-03-15 | 1990-12-12 | Mitsubishi Rayon Co., Ltd. | Porous hollow carbon fiber film and method of manufacturing the same |
JPH02160924A (ja) * | 1988-12-08 | 1990-06-20 | Mitsubishi Rayon Co Ltd | 多孔質炭素繊維及びその製造法 |
CA2007067A1 (en) * | 1989-01-11 | 1990-07-11 | Martin E. Ketterer | Composite metal-loaded carbon fibers |
US5700573A (en) * | 1995-04-25 | 1997-12-23 | Mccullough; Francis Patrick | Flexible biregional carbonaceous fiber, articles made from biregional carbonaceous fibers, and method of manufacture |
-
2002
- 2002-06-17 DE DE10226969A patent/DE10226969B4/de not_active Expired - Fee Related
-
2003
- 2003-06-13 JP JP2003168936A patent/JP4460232B2/ja not_active Expired - Fee Related
- 2003-06-16 AT AT03013625T patent/ATE441747T1/de active
- 2003-06-16 ES ES03013625T patent/ES2333113T3/es not_active Expired - Lifetime
- 2003-06-16 DE DE50311860T patent/DE50311860D1/de not_active Expired - Fee Related
- 2003-06-16 EP EP03013625A patent/EP1375707B1/de not_active Expired - Lifetime
- 2003-06-16 PT PT03013625T patent/PT1375707E/pt unknown
- 2003-06-17 US US10/463,018 patent/US20030230194A1/en not_active Abandoned
-
2007
- 2007-01-22 US US11/656,259 patent/US7708805B2/en not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111396A (en) * | 1960-12-14 | 1963-11-19 | Gen Electric | Method of making a porous material |
US3666526A (en) * | 1966-01-06 | 1972-05-30 | Gen Electric | Refractory porous bodies |
US3628984A (en) * | 1968-05-27 | 1971-12-21 | Nippon Carbon Co Ltd | Method for the manufacture of heat-resistant carbonaceous products having low permeability |
US3922334A (en) * | 1973-01-31 | 1975-11-25 | Airco Inc | Foam carbonization and resulting foam structures |
US4067956A (en) * | 1976-10-08 | 1978-01-10 | Chemotronics International, Inc. | Reticulated anisotropic porous vitreous carbon |
US4100314A (en) * | 1977-03-29 | 1978-07-11 | Airco, Inc. | Method for increasing the strength and density of carbonaceous products |
US4220846A (en) * | 1978-07-26 | 1980-09-02 | The Fluorocarbon Company | Method and apparatus utilizing a porous vitreous carbon body particularly for fluid heating |
US4362646A (en) * | 1979-09-28 | 1982-12-07 | Toho Beslon Co., Ltd. | Process for the production of fibrous activated carbon |
US5089135A (en) * | 1988-01-20 | 1992-02-18 | Mitsubishi Rayon Co., Ltd. | Carbon based porous hollow fiber membrane and method for producing same |
US5895716A (en) * | 1995-07-18 | 1999-04-20 | The B.F. Goodrich Company | Wet friction materials, methods of making them, and apparatus containing the same |
US6364936B1 (en) * | 2000-05-15 | 2002-04-02 | The Board Of Trustees Of The University Of Illinois | Selective sorption and desorption of gases with electrically heated activated carbon fiber cloth element |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100181212A1 (en) * | 2006-08-09 | 2010-07-22 | Matthias Koch | Monolithic materials for gas stores |
CN102167319A (zh) * | 2011-05-13 | 2011-08-31 | 江苏大学 | 一种醋糟制备活性炭的方法 |
US8961661B1 (en) * | 2012-10-24 | 2015-02-24 | Hrl Laboratories, Llc | Polymer/scaffold nanocomposites for hydrogen storage |
US10131770B2 (en) | 2014-02-26 | 2018-11-20 | Toray Industries, Inc. | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
CN104445193A (zh) * | 2014-12-03 | 2015-03-25 | 盐城工学院 | 具有去除难降解有机污染废水2,4,6三氯酚作用的枝叶多孔炭及其制备方法与应用 |
CN110656403A (zh) * | 2019-11-07 | 2020-01-07 | 武汉纺织大学 | 一种易导电掺金属聚丙烯腈碳纤维及其制备方法 |
CN113694691A (zh) * | 2021-07-16 | 2021-11-26 | 西安交通大学 | 一种含金属的单原子流体制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1375707A1 (de) | 2004-01-02 |
ES2333113T3 (es) | 2010-02-17 |
JP2004044074A (ja) | 2004-02-12 |
US20070132128A1 (en) | 2007-06-14 |
EP1375707B1 (de) | 2009-09-02 |
US7708805B2 (en) | 2010-05-04 |
DE10226969A1 (de) | 2004-01-15 |
DE10226969B4 (de) | 2006-05-18 |
ATE441747T1 (de) | 2009-09-15 |
PT1375707E (pt) | 2009-12-09 |
DE50311860D1 (de) | 2009-10-15 |
JP4460232B2 (ja) | 2010-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7708805B2 (en) | Method of producing carbon fibers, and methods of making protective clothing and a filter module | |
US8993199B2 (en) | Flexible carbon fiber nonwoven fabric | |
KR100605006B1 (ko) | 전기방사법으로 제조한 나노섬유의 탄소화에 의한 나노세공 분포를 갖는 활성탄소섬유의 제조방법 | |
JP4456600B2 (ja) | 樟脳を用いた多孔性炭素ナノ繊維の製造方法及びこの方法により製造された炭素ナノ繊維 | |
JP4223042B2 (ja) | 炭素繊維不織布の製造方法 | |
US3529044A (en) | Production of inorganic fibrous materials | |
Ko | Influence of continuous stabilization on the physical properties and microstructure of PAN‐based carbon fibers | |
US4904424A (en) | Ceramic alloys from colloidal metal alloy suspensions | |
JP4612287B2 (ja) | 実質的にウイスカのない炭化ケイ素繊維およびその製造方法 | |
KR100623881B1 (ko) | 전기방사에 의한 폴리아크릴로 나이트릴-폴리이미드 나노복합섬유 제조와 이를 이용한 나노 탄소섬유 및 활성탄소섬유 제조 방법 | |
CN105696114A (zh) | 可调控碳纤维材料孔径及孔隙率的制备方法及碳纤维材料 | |
KR20090041135A (ko) | 백금족 금속 입자가 분산된 탄소 또는 흑연화 나노섬유 및그의 제조방법 | |
TWI798660B (zh) | 不融化聚苯醚纖維、不融化聚苯醚成形體、碳纖維、活性碳纖維、碳纖維成形體、活性碳纖維成形體、及其製造方法 | |
EP3443152A1 (de) | Auf polyacrylonitril basierende graphitfaser | |
EP3558867A1 (de) | Graphitmaterial | |
JP2007080742A (ja) | 固体高分子電解質型燃料電池用炭素繊維シート及びその製造方法 | |
KR101221615B1 (ko) | 전기방사에 의한 탄소나노섬유의 제조방법 | |
JPH02242920A (ja) | 複合金属入り炭素繊維 | |
CN113388959B (zh) | 一种低软化点沥青基柔性纳米碳纤维薄膜及其制备方法 | |
KR20240086183A (ko) | 폐의류를 이용한 활성 탄소섬유 및 그 제조 방법 | |
JP2514253B2 (ja) | シリコンカ―バイド系成形物及びその製造法 | |
JPH03167315A (ja) | ピッチ系中空炭素繊維の製造方法 | |
JP2002001071A (ja) | 組紐状炭素中空糸膜 | |
JP2003292317A (ja) | 炭素質物質の製造方法及び該製造方法により得られた炭素質物質、並びに活性炭 | |
JP2002326808A (ja) | 炭素質物質の製造方法及び該製造方法により得られた炭素質物質 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: SGL CARBON AG,GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HEINE, MICHAEL;NEUERT, RICHARD;ZIMMERMANN-CHOPIN, RAINER;SIGNING DATES FROM 20030623 TO 20030626;REEL/FRAME:023960/0136 |