EP1204590A2 - Procede de fabrication controlee de billes de charbon actif - Google Patents

Procede de fabrication controlee de billes de charbon actif

Info

Publication number
EP1204590A2
EP1204590A2 EP00958108A EP00958108A EP1204590A2 EP 1204590 A2 EP1204590 A2 EP 1204590A2 EP 00958108 A EP00958108 A EP 00958108A EP 00958108 A EP00958108 A EP 00958108A EP 1204590 A2 EP1204590 A2 EP 1204590A2
Authority
EP
European Patent Office
Prior art keywords
sulfonation
temperature
polymer
sulfuric acid
activated carbon
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.)
Withdrawn
Application number
EP00958108A
Other languages
German (de)
English (en)
Inventor
Wolfgang Heschel
Dirk MÜLLER
Thorsten Keibel
Marlen Kolinke
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.)
Helsa Werke Helmut Sandler GmbH and Co KG
Original Assignee
Helsa Werke Helmut Sandler GmbH and Co KG
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 Helsa Werke Helmut Sandler GmbH and Co KG filed Critical Helsa Werke Helmut Sandler GmbH and Co KG
Publication of EP1204590A2 publication Critical patent/EP1204590A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents

Definitions

  • the present invention relates to the controlled production of spherical activated carbon, in particular the controlled production of spherical activated carbon from gel-like or macroporous polymers.
  • activated carbon Due to the comparatively large surface area of activated carbon and the resulting large adsorption capacity, activated carbon has long been used in various areas for cleaning tasks. Activated carbon is used in many different areas, such as the cleaning of flue gases or the cleaning of liquids, the activated carbon often being used as a filtration aid in the latter case.
  • ABC protective suits essentially consist of a textile outer fabric that is connected to an activated carbon filter material.
  • Spherical adsorbents that are fixed as a monolayer on a textile support are suitable as filters.
  • Powdered activated carbon on fine-pored polyurethane foam or pure activated carbon fabric are also used. These materials, which are at least partially composite materials, are assembled into appropriate suits that are pulled over the permanently worn clothing when used as protective clothing.
  • single-layer filter composites are also known, which can be worn as underwear in a suit.
  • combination filters consist of a combination of textile particle filter and activated carbon medium. Because, as already mentioned, the construction volume is often very limited, there are sometimes extreme requirements with regard to flow resistance, particle separation performance and adsorption capacity.
  • the activated carbon volume of the combination filter and the resulting adsorption capacity is relatively low.
  • the pore structure of the activated carbon is such that there is good adsorption kinetics even in the low partial pressure range ( ⁇ 100 ppm).
  • Combination filters can therefore be used excellently for reducing short-term concentration peaks, ie for smoothing.
  • a significant improvement in comfort is achieved by lowering odor-intensive components of the supply air flow below the odor threshold.
  • N-butane, toluene, sulfur dioxide and nitrogen oxide are used as key substances for determining such activated carbon or filter properties.
  • activated carbon matrix filters which have a significantly higher volume of activated carbon, are already used in various vehicle types in the upper middle and upper class. These so-called “extended bed” filters have an adsorption characteristic comparable to classic packed bed filters, but with a greatly reduced flow resistance. This effect is achieved by fixing activated carbon on the carrier walls of an open-pore polyurethane foam. If a spherical equilibrium fill in the sense of a random packing has an activated carbon volume of approx. 62.5% and a resulting gap volume of 37.5%, values of 35 to 40% result for matrix filters. It is therefore obvious that in order to achieve the bed bed adsorption characteristics (no immediate breakthrough and long breakthrough time followed by a steep increase in the breakthrough curve), a specific selection of the activated carbon must be made.
  • EP 0 326 271 B1 for example, is to be mentioned, from which the production of activated carbon, in particular from styrene-divinylbenzene copolymers, is known.
  • the copolymer is first used with a large excess of fuming sulfuric acid or oleum for a longer period Period treated. After sulfonation, the polysulfonated copolymer is washed extensively to remove excess acid and then dried. This process is extremely uneconomical due to the high use of sulfuric acid and the energy-intensive drying step, and with regard to the process wastewater that arises.
  • a method is known from WO 96/21616 in which a styrene-divinylbenzene copolymer with 5 to 50% by weight sulfuric acid is carbonized or pyrolyzed at a temperature of up to 750 ° C. Because the amount of sulfuric acid, which is already insufficient for monosulfonation of the aromatic nuclei, there is a comparatively high loss of mass during the pyrolysis. This method, too, cannot be carried out economically due to the loss of mass mentioned.
  • the process according to the invention advantageously enables the use of divinylbenzene polymers for the production of activated carbon, as a result of which the base is widened with respect to the starting material for the production of special activated carbon and activated carbon with modified properties is also obtained.
  • Another advantage of the method according to the invention lies in the streamlining of the overall method, in particular activation being provided only in the case of a special embodiment of the method according to the invention.
  • the sulfonation of the starting polymer is related to the properties of the final product, i.e. the number and distribution of the pores in the activated carbon according to their size and in relation to the total pore volume are of particular importance.
  • the present invention is based in part on the knowledge that a high sulfur content in the coke structure is particularly advantageous.
  • the sulfonation begins at relatively low temperatures, with the formation of sulfonic acid groups almost exclusively at temperatures up to about 200 ° C. electrophilic substitution takes place on the aromatic nuclei contained in the polymer.
  • the formation of sulfone groups then preferably takes place at temperatures above 200 ° C., which corresponds to a crosslinking of an aromatic nucleus already substituted by a sulfonic acid group with a further aromatic nucleus via the same sulfo group with the elimination of water.
  • a special process measure in the context of the present invention is to carry out the sulfonation of the polymer with sulfuric acid with agitation of the reaction mixture. It should be noted here that stationary sulfonation only leads to a sintered product which cannot be used for any of the intended areas of use. A free-flowing sulfonation product is only obtained when the reaction mixture has been thoroughly mixed.
  • the heating regime also plays a decisive role in sulfonation, although the product qualities can also be influenced by this factor. It is therefore necessary to choose a heating rate in the range from 5 to 20 Kelvin in order to bring the reaction material to the sulfonation temperature. With a heating rate below 5 K./Min. the heating and sulfonation process section is extended unnecessarily. With a heating rate of more than 20 K./Min. local overheating can occur, which has a negative impact on the end product, since this increases the tendency of the starting polymer to sinter.
  • Another way to influence the end product is to vary the ratio of H2SO4 to the polymer used. According to the invention, this ratio, calculated as the ratio of the pure substances, is 1.4: 1 to 3: 1.
  • the sulfuric acid used as the sulfonating agent is therefore in principle in excess, and it was possible to limit it to a maximum of three times the excess. This limits the excessive use of sulfuric acid, which further increases the economics of the process.
  • the reaction mixture After completion of the sulfonation with sulfuric acid, the reaction mixture is allowed to cool to a temperature of ⁇ 50 ° C. Subsequently, the sulfonated polymer by heating the product to a temperature of 250 ° C with a heating rate of 5 to 15 K./Min. and 30 min. hold at 250 ° C, further heating up to 330 ° C with a heating rate of 2 to 10 K / min. and then further heating up to a temperature of 750 to 900 ° C with a heating rate of 30 to 50 K / min. and pyrolyzed at the maximum temperature reached for 5 to 10 minutes.
  • the sulfonation is usually carried out in such a way that sulfuric acid and polymer are initially introduced into a reaction vessel and then opened
  • Sulfonation temperature to be heated.
  • the sulfuric acid is initially introduced and heated to the sulfonation temperature.
  • the polymer to be sulfonated is then added. Since the temperature in the reaction vessel drops as a result of the polymer input, the
  • the sulfonation is preferably carried out for 20 to 40 minutes, the sulfonation being carried out under reduced pressure in a special process variant.
  • the vacuum in the reaction vessel is dimensioned so that the pressure difference to the environment is about 50 to 550 mbar.
  • reaction time can advantageously be limited to 20 to 40 minutes, since in the sulfonation Reaction product formed water is removed from the equilibrium and thus the further sulfonation is favored.
  • dilute sulfuric acid as a sulfonating agent is also possible in the sulfonation of gel-like or macroporous polymers.
  • sulfuric acid with a concentration of about 54 to 96% by weight of H 2 SO4 as the sulfonating agent.
  • dilute sulfuric acid it is particularly preferred to carry out the process in combination with carrying out the sulfonation under reduced pressure.
  • reaction material is agitated and mixed sufficiently, because otherwise the tendency towards sintering of the starting polymer increases significantly, possibly due to local overheating. It is particularly preferred if the reaction material by rotating the
  • Reaction container is moved.
  • carrying out the sulfonation in a rotating reaction vessel is advantageous in that the flowability of the sulfonation product is better preserved.
  • the reason for this is assumed to be that the mechanical and possibly also thermal load on the starting polymer in a rotating reaction vessel is lower.
  • the pyrolysis in process step b) is generally carried out under a nitrogen atmosphere.
  • the pyrolysis takes place in an atmosphere composed of nitrogen and water vapor, which in a further development also contains carbon dioxide.
  • the water content of the pyrolysis atmosphere does not necessarily have to be metered in from the outside are brought in by the water content of the sulfonated polymer.
  • water vapor can also be metered into the pyrolysis atmosphere.
  • the pyrolysis atmosphere contains nitrogen and / or carbon dioxide in addition to nitrogen, there is advantageously no need for special activation. This enables a shortening of the process and, in particular, high energy savings. On the other hand, further activation makes it possible to adapt the adsorption properties of the spherical activated carbon produced to the anticipated requirements of the area of use.
  • composition of the activation atmosphere or special activation methods such as. B. impregnation with salt solutions are generally familiar to the expert and are selected depending on the requirement.
  • Macroporous and gel-like polymer as a starting material for sulfonation
  • a macroporous polymer was used for the sulfonation experiments, e.g. available under the name "LEWATIT” as pure dinvinylbenzene polymer, and a gel-like polymer, commercially available as styrene-divinylbenzene polymer under the name "LEWAPOL” with varying divinylbenzene (DVB) contents.
  • the water of reaction released during the sulfonation is removed from the reaction vessel by a pump (e.g. water jet pump).
  • a pump e.g. water jet pump
  • the heating is switched off and the reaction mixture is allowed to cool to room temperature, the reaction vessel continuing to rotate.
  • the bed is coked in an N 2 atmosphere in accordance with the specified values.
  • the coke which has cooled to room temperature, is then activated in a fluidized layer until the desired burn-up.
  • the sulfonated product can be activated during pyrolysis and without intermediate cooling.
  • mesopore-rich activates are obtained under conditions that are otherwise the same for sulfonation, coking and activation compared to a gel-like polymer (Examples 3 and 6).
  • the pore sizes were determined as follows:
  • Micropores ⁇ 7.6 nm
  • Mesopores 7.6 to 50 nm
  • Macropores > 50 nm.
  • the mass ratio of sulfuric acid to macroporous polymer can also have an influence on the proportion of macropores (absolutely non-percentage) (Examples 1 to 4).
  • Example 5 shows that a mass use ratio of 1: 1 results in a significant decrease in the coke and activate yield and in the volume-related BET surface area.
  • the sulfonation is also influenced by the type of reactor and the type of mechanical energy input. Therefore, sulfonation reactions in a fixed reaction vessel without mechanical stirrer and an inclined, rotating reaction vessel with and without lifting elements on the inner wall were used for corresponding experiments.
  • the polymer is poured into the fixed reaction flask and brought into contact with the corresponding amount of sulfuric acid.
  • the reaction mixture is homogenized with a mechanical stirrer.
  • this is only possible as long as the mixture is in suspension.
  • the mixing stops.
  • product movement no longer takes place.
  • a free-flowing reaction product cannot be obtained.
  • this is arranged at an angle of approximately 30 to 45 ° to the horizontal and rotates about its longitudinal axis at 1 to 30 revolutions / min.
  • Reaction vessels can be installed which promote mixing in the manner of lifting blades.
  • the temporary solidification of the reaction product which is also known as cake formation, which occurs at a certain reaction stage is avoided and the water vapor is evacuated uniformly from the reacting reaction mixture.
  • the advantages resulting from this design of the reactor are, on the one hand, a free-flowing sulfonation product and a considerable saving in sulfuric acid, since, compared to the fixed reactor, a significantly lower amount of sulfuric acid is sufficient for a corresponding sulfonation.
  • the utilization of the reaction space with the inclined recator is more than twice as good, as filling levels of up to 60% are possible. It has surprisingly been found that the mixing movements typical of the inclined reactor, in which the radial material movement is superimposed by rolling on the reactor wall by a material movement in the axial direction, thus promoting the homogenization of the reaction mixture, shortening the reaction time and thus contributing to energy savings ,
  • Example 11 a reaction vessel with a 2 liter capacity was used, into which 300 g of the respective polymer were introduced.
  • a dilute sulfuric acid can also be used.
  • sulfuric acid with a concentration in the range from 54 to 96% by weight of H2SO4 had no influence on the coke yield and the quality of the activates, provided the other conditions were kept the same. This can be seen from Examples 20 to 32 and Example 42, it also being found that an extension of the sulfonation time may be necessary when using a dilute heavy iron acid.
  • Tables 1 and 2 below show the results of the tests for the production of spherical activated carbon.
  • styrene-divinylbenzene copolymers with a divinylbenzene content of 2 and 4% by weight and a so-called monodispersed styrene-divinylbenzene polymer with a divinylbenzene content of about 8%, which was mixed with a swelling agent, were investigated, the Sulfonation hold time, d. H. the reaction time and the mass ratio of sulfuric acid to polymer were varied.
  • the result is that the divinylbenzene content in the range between 2 and 8% by weight has no significant influence on the
  • Activat quality and yield possesses.
  • the pore structure can be changed in a targeted manner both via the sulfonation time and via the acid content. With short sulfonation times and comparatively low acid-polymer ratios, when using gel-like styrene-divinylbenzene polymer, microporous activates with an increased macropore volume are obtained. By changing these two control variables of the process, activated carbons can be produced with a deliberately different macro-pore structure, but approximate agreement of the BET surface area and consequently corresponding adsorption capacity. The adsorption rate can be controlled via the macro-pore structure. In the sulfonation of macroporous polymer, i. H.
  • the mesopore volume of the spherical activated carbon to be produced can be adjusted.
  • a short hold time of about 20 minutes during sulfonation provides extremely mesopore-rich coke and activates with the same BET surface area, while a long hold time of about 90 minutes reduces the mesopore content to 1/3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Procédé de fabrication contrôlée de charbon actif en billes à partir de polymères sous forme de gel ou macroporeux, sur la base de polymères divinylbenzol ou styrol-divinylbenzol, par sulfonation du polymère avec de l'acide sulfurique. Ledit procédé consiste à agiter le mélange de réaction à une température de sulfonation de 200 à 250 °C pendant une durée de 20 à 90 minutes, le rapport calculé sur la base des substances pures H2SO4/polymère au début de la sulfonation se trouvant dans la plage de 1,4/1 à 3/1 et le rythme de chauffe jusqu'à obtention de la température de sulfonation étant de l'ordre de 5 à 20 K/min. Ledit procédé consiste ensuite à refroidir le polymère sulfoné à une température < 50 °C, à pyroliser le polymère sulfoné par chauffe du produit à une température de 250 °C avec un rythme de chauffe de 5 à 15K/min. et à maintenir ledit produit pendant 30 min. à 250 °C, à continuer la chauffe jusqu'à 330 °C avec un rythme de chauffe de 2 à 10 K/min., puis à chauffer finalement le produit jusqu'à une température de 750 à 900 °C avec un rythme de chauffe de 50 K/min. et à maintenir le produit à la température maximale atteinte pendant 5 à 10 minutes.
EP00958108A 1999-07-05 2000-07-01 Procede de fabrication controlee de billes de charbon actif Withdrawn EP1204590A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19930732A DE19930732A1 (de) 1999-07-05 1999-07-05 Verfahren zur gesteuerten Herstellung von Kugelaktivkohle
DE19930732 1999-07-05
PCT/DE2000/002209 WO2001002295A2 (fr) 1999-07-05 2000-07-01 Procede de fabrication controlee de billes de charbon actif

Publications (1)

Publication Number Publication Date
EP1204590A2 true EP1204590A2 (fr) 2002-05-15

Family

ID=7913553

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00958108A Withdrawn EP1204590A2 (fr) 1999-07-05 2000-07-01 Procede de fabrication controlee de billes de charbon actif

Country Status (4)

Country Link
EP (1) EP1204590A2 (fr)
AU (1) AU6979200A (fr)
DE (1) DE19930732A1 (fr)
WO (1) WO2001002295A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE283238T1 (de) 2000-04-28 2004-12-15 Bluecher Gmbh Verfahren zur herstellung kugelförmiger aktivkohle
DE10148286A1 (de) * 2001-09-29 2003-04-17 Sandler Helmut Helsa Werke Verfahren zur Herstellung von Aktivkohle mit einer definierten Porenstruktur
DE10254241A1 (de) * 2002-11-20 2004-06-09 RVG Berlin-Brandenburg Gesellschaft für Verfahrensentwicklung und Recyclingtechnologien mbH Kugelaktivkohle
RU2257343C2 (ru) * 2003-03-14 2005-07-27 Закрытое акционерное общество "Межотраслевое юридическое агентство "Юрпромконсалтинг" Способ получения сферического углеродного адсорбента
US7662747B2 (en) 2003-08-11 2010-02-16 De Ruiter Ernest Activated charcoal production
DE102005038554A1 (de) * 2005-08-12 2007-02-15 Cernius Holding Gmbh Verfahren zur Herstellung von Kugelaktivkohle
DE202005021822U1 (de) 2005-08-12 2010-05-27 BLüCHER GMBH Kugelaktivkohle
DE102005062160A1 (de) 2005-12-19 2007-06-21 BLüCHER GMBH Aktivkohle für die medizinische Verwendung
DE102006022178A1 (de) * 2006-04-18 2007-10-25 BLüCHER GMBH Mit Adsorbentien beaufschlagte Plattenmaterialien für den Trockenbau
DE202006016898U1 (de) 2006-10-12 2007-11-22 BLüCHER GMBH Hochleistungsadsorbentien auf der Basis von Aktivkohle mit hoher Mikroporosität

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5230799A (en) * 1975-09-04 1977-03-08 Sumitomo Chem Co Ltd Method for production of porous carbon
JPS5350088A (en) * 1976-10-19 1978-05-08 Sumitomo Chem Co Ltd Production of spherical activated carbon
JPS62197308A (ja) * 1986-01-31 1987-09-01 Japan Organo Co Ltd 合成樹脂の炭化方法
US4839331A (en) * 1988-01-29 1989-06-13 Rohm And Haas Company Carbonaceous adsorbents from pyrolyzed polysulfonated polymers
DE4304026B4 (de) * 1992-02-28 2005-02-17 Mhb Filtration Gmbh & Co. Kg Verfahren zur Entsorgung von verbrauchten Ionenaustauschern
RU2077479C1 (ru) * 1992-11-30 1997-04-20 Акционерное общество закрытого типа "Экофор" Способ получения активированного угля
IT1273678B (it) * 1993-08-12 1997-07-09 Bluecher Hasso Von Processo per la produzione di carbone attivo
JPH11501606A (ja) * 1995-01-11 1999-02-09 ブリュッヒャー，ハッソ フォン 粒状活性炭の製造方法
EP0814056B1 (fr) * 1996-06-22 2002-03-27 MHB Filtration GmbH & CO. KG Procédé de préparation de charbon actif granulaire
DE19752593C5 (de) * 1997-11-27 2005-02-17 Helsa-Werke Helmut Sandler Gmbh & Co. Kg Verfahren zur Herstellung von Aktivkohle aus Polymeren mit aromatischen Kernen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0102295A2 *

Also Published As

Publication number Publication date
WO2001002295A3 (fr) 2001-03-29
AU6979200A (en) 2001-01-22
DE19930732A1 (de) 2001-01-18
WO2001002295A2 (fr) 2001-01-11

Similar Documents

Publication Publication Date Title
DE2317455C3 (de) Chromatographisches Füllmaterial
DE10191656B4 (de) Verfahren zur Herstellung kugelförmiger Aktivkohle
DE3220671C2 (fr)
DE60035545T2 (de) Ein auf einem metalloxid der Gruppe IVB basierende Katalysatorträger, seine Herstellung und seine Verwendungen
DE60103505T2 (de) Aktivkohle und expandierten graphit enthaltendes kompositmaterial
DE60104901T2 (de) Hydroverfahrenskatalysator und dessen anwendung
DE2419827C3 (de) Verfahren zur Herstellung von kugelförmiger Aktivkohle
EP2720794B1 (fr) Matériaux poreux à base d&#39;oxydes métalliques mixtes ainsi que leur production et leur utilisation
EP2720789B1 (fr) Production des matériaux poreux à base d&#39;oxydes de titane et/ou vanadium
CH644277A5 (de) Verfahren zur herstellung von filtermaterial und dessen verwendung.
DE69102244T2 (de) Packungsmaterial für Flüssigkeitschromatographie und Verfahren zu dessen Herstellung.
WO2015086109A1 (fr) Système catalytique basé sur du charbon activé en granulés comme support et son utilisation
DE2917234C3 (de) Katalysator zur Konzentrierung von Wasserstoffisotopen
EP1204590A2 (fr) Procede de fabrication controlee de billes de charbon actif
DE3881562T2 (de) Verfahren zur Herstellung von nicht gesinterte Cristobalitsilica.
EP0002251B1 (fr) Procédé de préparation d&#39;un catalyseur ou support de catalyseur de charbon actif résistant à l&#39;attrition
WO2015040186A1 (fr) Procédé de fabrication d&#39;un produit poreux à base de carbone
EP0952960B1 (fr) Charbon actif granule issu de residus de distillation
DE102011013314A1 (de) Mikroporöses Kohlenstoffmaterial und Verfahren zum Bilden desselben
DE3428421A1 (de) Verfahren zur herstellung von als katalysatortraeger verwendbarem aluminiumoxid
EP1036034B1 (fr) Production de charbon actif a partir de polymeres a noyaux aromatiques
EP0814056B1 (fr) Procédé de préparation de charbon actif granulaire
DE2153658A1 (de) Verfahren zur Herstellung von Form körpern aus Aluminiumoxid
DE2326937A1 (de) Kohlenstoffhaltiger poroeser koerper und verfahren zu seiner herstellung
DE10024312B4 (de) Verfahren zur Modifizierung der Oberflächen von feinporösen Adsorbentien sowie Verfahren zur Herstellung eines Molekularsiebes unter Anwendung dieses Verfahrens

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: 20011130

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030516