CH550121A - Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation process - Google Patents
Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation processInfo
- Publication number
- CH550121A CH550121A CH841571A CH841571A CH550121A CH 550121 A CH550121 A CH 550121A CH 841571 A CH841571 A CH 841571A CH 841571 A CH841571 A CH 841571A CH 550121 A CH550121 A CH 550121A
- Authority
- CH
- Switzerland
- Prior art keywords
- fibers
- fiber
- centrifugal
- dissolved
- temperatures
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 10
- 238000003763 carbonization Methods 0.000 title claims abstract description 6
- 239000011368 organic material Substances 0.000 title abstract 2
- 238000009987 spinning Methods 0.000 title 1
- 238000007664 blowing Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000001419 dependent effect Effects 0.000 claims description 4
- 239000002657 fibrous material Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000009950 felting Methods 0.000 claims description 2
- 238000007380 fibre production Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 101100456896 Drosophila melanogaster metl gene Proteins 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C01B32/354—After-treatment
- C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The organic material in the form of a metl or soln. is converted into fibres by a centrifugal or blowing process and heated to cause carbonisation while still suspended in a gas stream. PreF. the fibres are subjected to preoxidation before carbonisation e.g. by being conveyed in an air stream through an oven with an initial section at a lower temp. They may be activated after carbonisation, by usual means, and converted into felts. Carbon fibres are produced in a single, simple and economic procesS. They are suitable for insulation, filtration, as catalyst carriers or active carbon fibre.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Kohlefasern und AktivkohlefasenL
Es ist bekannt. dass das Erhitzen von karbonisierbaren, faserigen Produkten aus Cellulose, Polyacrylnitril u. dgl. bei höheren Temperaturen zu kohlenstoffhaltigen, faserigen Produkten führt. Die bisher bekannten Verfahren waren alle auf teure Ausgangsmaterialien angewiesen und brauchten aufwendige Ofenanlagen. Dadurch erhöhte sich der Gestehungspreis für Kohlefaserprodukte so, dass diese für industrielle Zwecke nur in Spezialfällen angewendet wurden.
Zweck der Erfindung ist, Kohlefasern oder aktivierte Kohlefasern direkt aus den kohlenstoffhaltigen, organischen Verbindungen zu niedrigeren Gestehungskosten herzustellen.
Erfindungsgemäss wird dies dadurch erreicht, dass man organische Stoffe in einen gelösten oder geschmolzenen Zustand bringt und einem Schleuder- und/oder Zerblaseverfahren unterwirft und die organischen Stoffe nach Ausbildung der Faserform noch im Schwebezustand auf Temperaturen erhitzt, bei welchen das Fasermaterial karbonisiert.
Vor der Karbonisierung kann gegebenenfalls eine Voroxydation durchgeführt werden. Die Voroxydation kann auch so geführt werden, dass sie gleichzeitig mit der Faserbildung stattfindet.
Die Fasern können wie folgt hergestellt werden:
Das karbonisierbare fasrige Ausgangsmaterial wird in einem gelösten oder geschmolzenen Zustand nach dem Schleuderverfahren, z.B. Trommelschleuderverfahren, bzw.
Zerblaseverfahren, z.B. Düsenblasverfahren zu Fasern verarbeitet. Das Ausgangsmaterial wird in einem gelösten oder geschmolzenen Zustand einem Vorratsbehälter, einer Schmelzwanne, einem Schmelzaggregat oder dgl. entnommen und in die entsprechende Apparatur zur Faserbildung eingespiesen.
Die zur Faserbildung verwendeten Apparaturen sind in ähnlicher Form aus der Mineralfaserherstellung bekannt. Der Unterschied besteht darin, dass wesentlich niedrigere Temperaturen benötigt werden. Die Faserstärken können in grosser Breite variiert werden, und es kann ein sehr niedriger Titer, der sich beim erfindungsgemässen Verfahren vorteilhaft auswirkt, erreicht werden.
An die zur Faserbildung verwendete Schleuder- oder Zerblasevorrichtung schliesst sich zweckmässig ein beheizter Schacht an. Bei Verwendung eines Lösungsmittels wird dieses freigesetzt und entfernt. Die in Schwebe befindlichen Fasern können direkt bei Temperaturen von 1 500C bis 300"C und unter Zuführung von Sauerstoff voroxydiert werden. Anschliessend werden die voroxydierten Fasern in der Verkokungszone im Schacht bei Temperaturen von 3000C bis 1 2000C karbonisiert.
Die beiliegende Zeichnung stellt eine beispielsweise Aus führungsform dar.
Das Ausgangsmaterial gelangt von einem Vorratsbehälter 5 in die Schleudervorrichtung 1 und fällt in den beheizten Schacht 2. Die freigesetzten Lösungsmitteldämpfe werden durch den Auslass 3 entfernt. Der Schacht gliedert sich in die Aushärtezone 6, Voroxydationszone 7 und Verkokungszone 8.
Nötigenfalls wird der Prozess mit einem Steuergas, das am oberen Schachtende 9 eingeblasen wird, gesteuert. Die Fasern werden mit Sauerstoff 4 voroxydiert. Die verkokten Fasern werden nun auf einem endlosen Transportband 10 aufgefangen und gegebenenfalls der Aktivierung 11 nach gebräuchlichen Methoden und/oder der Verfilzung 12 zugeführt.
Als Ausgangsmaterialien können Kunstharze, Polymere oder allgemein kohlenstoffhaltige Verbindungen, die entweder thermisch oder durch Zusatz von Lösungsmitteln zunächst in einen gelösten oder geschmolzenen Zustand gebracht werden, Anwendung finden. Beispielsweise können Polyacrylnitr;I Phenolharze, usw. in gelöster Form, organische Polymere, wie Phenolharze, in geschmolzener Form, aber auch Teer, Pech, Bitumen, usw. in geschmolzener oder gelöster Form zur Anwendung gelangen.
Die nach dem erfindungsgemässen Verfahren hergestellten Kohlefasern und die daraus hergestellten Filze eignen sich hervorragend für Isolationszwecke, zur Filtration korrosiver Medien, als Katalysatorträger oder Faseraktivkohle.
Beispiel
200 g Phenolharz vom Resoltyp wurden auf 90"C erwärmt und zu Fasern verschleudert. Hierbei wurden 10 g/ Min. verflüssigtes Harz auf eine Schleuderscheibe aufgegeben, die mit 1400 U/Min. lief.
Die Schleuderscheibe hatte einen Durchmesser von 15 cm.
Das verflüssigte Harz wurde etwa 6 cm vom Scheibenmittelpunkt entfernt aufgegeben (Schleudergeschwindigkeit - 9 m/ sek.).
Die Flugbahn der so entstandenen Fasern wurde durch einen Steuerstrahl (Gas) nach unten in einen Ofenraum abgelenkt. Der Ofen hatte einen lichten Durchmesser von 0,8 m und eine lichte Höhe von insgesamt 2,5 m. Er wurde elektrisch beheizt und zwar so, dass bei konstanter Gasströmung ein Temperaturgefälle von - 3,80/com vorlag. In der Höhe von - 250 wurde mittels Düsen Luft eingeblasen, um eine Vernetzung des Phenolharzes zu bewirken.
In der Temperaturzone oberhalb 300"C trat eine Verkokung der Fasern ein. Die entstandenen flüchtigen Komponenten wurden nach oben abgeführt, wobei die zugeführte Luft eine teilweise Verbrennung bewirkte und somit das Abscheiden von Teerprodukten verhinderte.
Steuergas, Luftzufuhr und flüchtige Bestandteile wurden an den, an der Ofenhaube = = 1,5 m angeordneten Saug- stutzen abgeführt.
Die erhaltenen Fasern wurden auf einem perforierten Boden aufgefangen und gewogen.
Die Ausbeute betrug 68 g = 34%, bezogen auf eingesetzes Phenolharz.
PATENTANSPRUCH
Verfahren zur Herstellung von Kohlefasern und Aktivkohlefasern unter Hitzebehandlung von karbonisierbarem faserigem Ausgangsmaterial, dadurch gekennzeichnet, dass man organische Stoffe in einen gelösten oder geschmolzenen Zustand bringt und einem Schleuder- und/oder Zerblaseverfahren unterwirft und diese nach Ausbildung der Faserform noch im Schwebezustand auf Temperaturen erhitzt, bei welchen das Fasermaterial karbonisiert.
UNTERANSPRÜCHE
1. Verfahren nach Patntanspruch, dadurch gekennzeichnet, dass man vor der Karbonisierung eine Voroxydation durchführt.
2. Verfahren nach Patentanspruch und Unteranspruch 1, dadurch gekennzeichnet, dass man die Voroxydation während der Faserbildung durchführt.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
The invention relates to a method for producing carbon fibers and activated carbon fibers
It is known. that the heating of carbonizable, fibrous products made of cellulose, polyacrylonitrile u. Like. At higher temperatures leads to carbon-containing, fibrous products. The processes known up to now were all dependent on expensive raw materials and required complex furnace systems. This increased the cost price for carbon fiber products so that they were only used for industrial purposes in special cases.
The purpose of the invention is to produce carbon fibers or activated carbon fibers directly from the carbon-containing organic compounds at lower production costs.
According to the invention, this is achieved by bringing organic substances into a dissolved or molten state and subjecting them to a centrifugal and / or blown process and, after the fiber shape has been formed, heating the organic substances to temperatures at which the fiber material carbonizes.
If necessary, a pre-oxidation can be carried out before carbonation. The pre-oxidation can also be carried out in such a way that it takes place simultaneously with the fiber formation.
The fibers can be made as follows:
The carbonizable fibrous starting material is in a dissolved or molten state after the centrifugal process, e.g. Drum spin process or
Blowing process, e.g. Jet blowing process processed into fibers. The starting material is removed in a dissolved or molten state from a storage container, a melting tank, a melting unit or the like and fed into the corresponding apparatus for fiber formation.
The apparatus used for fiber formation are known in a similar form from mineral fiber production. The difference is that much lower temperatures are required. The fiber thicknesses can be varied over a wide range, and a very low titer, which has an advantageous effect in the method according to the invention, can be achieved.
A heated duct is expediently connected to the centrifugal or pulverizing device used for fiber formation. If a solvent is used, it will be released and removed. The suspended fibers can be pre-oxidized directly at temperatures of 1500C to 300C and with the addition of oxygen. The pre-oxidized fibers are then carbonized in the coking zone in the shaft at temperatures of 3000C to 1200C.
The accompanying drawing represents an example of implementation.
The starting material passes from a storage container 5 into the centrifugal device 1 and falls into the heated shaft 2. The released solvent vapors are removed through the outlet 3. The shaft is divided into the hardening zone 6, pre-oxidation zone 7 and coking zone 8.
If necessary, the process is controlled with a control gas that is blown in at the upper end of the shaft 9. The fibers are pre-oxidized with oxygen 4. The carbonized fibers are now caught on an endless conveyor belt 10 and, if necessary, fed to the activation 11 by conventional methods and / or to the felting 12.
Synthetic resins, polymers or generally carbon-containing compounds, which are first brought into a dissolved or molten state either thermally or by adding solvents, can be used as starting materials. For example, polyacrylonitrile, phenolic resins, etc. can be used in dissolved form, organic polymers such as phenolic resins, in molten form, but also tar, pitch, bitumen, etc., in molten or dissolved form.
The carbon fibers produced by the process according to the invention and the felts produced from them are outstandingly suitable for insulation purposes, for the filtration of corrosive media, as a catalyst carrier or fiber activated carbon.
example
200 g of phenolic resin of the resol type were heated to 90 ° C. and centrifuged to form fibers. In this process, 10 g / min. Of liquefied resin were applied to a centrifugal disc which ran at 1400 rpm.
The slinger had a diameter of 15 cm.
The liquefied resin was applied about 6 cm from the center of the disc (spin speed - 9 m / sec.).
The trajectory of the fibers produced in this way was deflected downwards into a furnace chamber by a control jet (gas). The furnace had a clear diameter of 0.8 m and a clear height of a total of 2.5 m. It was heated electrically in such a way that there was a temperature gradient of -3.80 / com with a constant gas flow. At a height of - 250 air was blown in by means of nozzles in order to bring about crosslinking of the phenolic resin.
In the temperature zone above 300 ° C., coking of the fibers occurred. The volatile components formed were discharged upwards, the air supplied causing partial combustion and thus preventing the separation of tar products.
Control gas, air supply and volatile components were discharged to the suction nozzle on the furnace hood = = 1.5 m.
The obtained fibers were collected on a perforated floor and weighed.
The yield was 68 g = 34%, based on the phenolic resin used.
PATENT CLAIM
Process for the production of carbon fibers and activated carbon fibers with heat treatment of carbonizable fibrous starting material, characterized in that organic substances are brought into a dissolved or molten state and subjected to a centrifugal and / or blown process and, after formation of the fiber shape, heated to temperatures while still in suspension, in which the fiber material is carbonized.
SUBCLAIMS
1. The method according to patent claim, characterized in that a pre-oxidation is carried out before carbonization.
2. The method according to claim and dependent claim 1, characterized in that the pre-oxidation is carried out during fiber formation.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH841571A CH550121A (en) | 1971-06-10 | 1971-06-10 | Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH841571A CH550121A (en) | 1971-06-10 | 1971-06-10 | Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH550121A true CH550121A (en) | 1974-06-14 |
Family
ID=4339977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH841571A CH550121A (en) | 1971-06-10 | 1971-06-10 | Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation process |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH550121A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2280430A1 (en) * | 1974-08-03 | 1976-02-27 | Shoei Chemical Ind Co | Catalyst homogeneously dispersed in carbonaceous fibre - obtd. by heating organo-metal cpd. contg. corresp. metal catalyst coated on fibre |
| EP0002251A2 (en) * | 1977-12-02 | 1979-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of an attrition-resistant active carbon catalyst or catalyst support |
-
1971
- 1971-06-10 CH CH841571A patent/CH550121A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2280430A1 (en) * | 1974-08-03 | 1976-02-27 | Shoei Chemical Ind Co | Catalyst homogeneously dispersed in carbonaceous fibre - obtd. by heating organo-metal cpd. contg. corresp. metal catalyst coated on fibre |
| EP0002251A2 (en) * | 1977-12-02 | 1979-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of an attrition-resistant active carbon catalyst or catalyst support |
| EP0002251A3 (en) * | 1977-12-02 | 1979-06-27 | Hoechst Aktiengesellschaft | Process for the preparation of an attrition-resistant active carbon catalyst or catalyst support |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |