WO2001002295A2 - Method for the controlled production of spherical activated carbon - Google Patents
Method for the controlled production of spherical activated carbon Download PDFInfo
- Publication number
- WO2001002295A2 WO2001002295A2 PCT/DE2000/002209 DE0002209W WO0102295A2 WO 2001002295 A2 WO2001002295 A2 WO 2001002295A2 DE 0002209 W DE0002209 W DE 0002209W WO 0102295 A2 WO0102295 A2 WO 0102295A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfonation
- temperature
- polymer
- sulfuric acid
- activated carbon
- Prior art date
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
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00958108A EP1204590A2 (en) | 1999-07-05 | 2000-07-01 | Method for the controlled production of spherical activated carbon |
AU69792/00A AU6979200A (en) | 1999-07-05 | 2000-07-01 | Method for the controlled production of spherical activated carbon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19930732.6 | 1999-07-05 | ||
DE19930732A DE19930732A1 (en) | 1999-07-05 | 1999-07-05 | Process for the controlled production of spherical activated carbon |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001002295A2 true WO2001002295A2 (en) | 2001-01-11 |
WO2001002295A3 WO2001002295A3 (en) | 2001-03-29 |
Family
ID=7913553
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2000/002209 WO2001002295A2 (en) | 1999-07-05 | 2000-07-01 | Method for the controlled production of spherical activated carbon |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1204590A2 (en) |
AU (1) | AU6979200A (en) |
DE (1) | DE19930732A1 (en) |
WO (1) | WO2001002295A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001083368A1 (en) * | 2000-04-28 | 2001-11-08 | Bluecher Hasso Von | Method for producing spherical activated carbon |
DE10148286A1 (en) * | 2001-09-29 | 2003-04-17 | Sandler Helmut Helsa Werke | Activated charcoal production by sulfonating copolymer, pyrolysis and activation, uses catalytic additive regulating pore structure in educt mixture of copolymer and sulfuric acid |
WO2005016819A1 (en) * | 2003-08-11 | 2005-02-24 | BLüCHER GMBH | Activated charcoal production |
DE102005038554A1 (en) * | 2005-08-12 | 2007-02-15 | Cernius Holding Gmbh | Process for the preparation of spherical activated carbon |
DE102005038555A1 (en) * | 2005-08-12 | 2007-02-15 | Cernius Holding Gmbh | Process for the preparation of spherical activated carbon |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE20221998U1 (en) * | 2002-11-20 | 2010-05-12 | BLüCHER GMBH | Spherical active carbon |
DE102005062160A1 (en) | 2005-12-19 | 2007-06-21 | BLüCHER GMBH | Activated charcoal for medical use |
DE102006022178A1 (en) * | 2006-04-18 | 2007-10-25 | BLüCHER GMBH | Adsorbent coated sheet materials for drywall construction |
DE202006016898U1 (en) | 2006-10-12 | 2007-11-22 | BLüCHER GMBH | High performance adsorbents based on activated carbon with high microporosity |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2322876A1 (en) * | 1975-09-04 | 1977-04-01 | Sumitomo Chemical Co | PROCESS FOR THE PRODUCTION OF POROUS CARBON PRODUCTS AND NEW PRODUCTS THUS OBTAINED |
EP0326271A1 (en) * | 1988-01-29 | 1989-08-02 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
FR2687941A1 (en) * | 1992-02-28 | 1993-09-03 | Bluecher Hasso Von | PROCESS FOR THE RECOVERY OF USED ION EXCHANGERS. |
GB2280898A (en) * | 1993-08-12 | 1995-02-15 | Bluecher Hasso Von | Activated carbon |
WO1996021616A1 (en) * | 1995-01-11 | 1996-07-18 | Bluecher Hasso Von | Process for producing granulated active carbon |
EP0814056A1 (en) * | 1996-06-22 | 1997-12-29 | Blücher GmbH | Process for manufacturing activated carbon |
WO1999028234A1 (en) * | 1997-11-27 | 1999-06-10 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Production of active carbon from polymers with aromatic nuclei |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5350088A (en) * | 1976-10-19 | 1978-05-08 | Sumitomo Chem Co Ltd | Production of spherical activated carbon |
JPS62197308A (en) * | 1986-01-31 | 1987-09-01 | Japan Organo Co Ltd | Method for carbonizing synthetic resin |
RU2077479C1 (en) * | 1992-11-30 | 1997-04-20 | Акционерное общество закрытого типа "Экофор" | Method of preparing activated carbon |
-
1999
- 1999-07-05 DE DE19930732A patent/DE19930732A1/en not_active Withdrawn
-
2000
- 2000-07-01 AU AU69792/00A patent/AU6979200A/en not_active Abandoned
- 2000-07-01 EP EP00958108A patent/EP1204590A2/en not_active Withdrawn
- 2000-07-01 WO PCT/DE2000/002209 patent/WO2001002295A2/en not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2322876A1 (en) * | 1975-09-04 | 1977-04-01 | Sumitomo Chemical Co | PROCESS FOR THE PRODUCTION OF POROUS CARBON PRODUCTS AND NEW PRODUCTS THUS OBTAINED |
EP0326271A1 (en) * | 1988-01-29 | 1989-08-02 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
FR2687941A1 (en) * | 1992-02-28 | 1993-09-03 | Bluecher Hasso Von | PROCESS FOR THE RECOVERY OF USED ION EXCHANGERS. |
GB2280898A (en) * | 1993-08-12 | 1995-02-15 | Bluecher Hasso Von | Activated carbon |
WO1996021616A1 (en) * | 1995-01-11 | 1996-07-18 | Bluecher Hasso Von | Process for producing granulated active carbon |
EP0814056A1 (en) * | 1996-06-22 | 1997-12-29 | Blücher GmbH | Process for manufacturing activated carbon |
WO1999028234A1 (en) * | 1997-11-27 | 1999-06-10 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Production of active carbon from polymers with aromatic nuclei |
Non-Patent Citations (4)
Title |
---|
DATABASE CHEMABS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ARTYUSHENKO, V. V. ET AL: "Activation of a styrene-divinylbenzene copolymer in a fluidized bed" retrieved from STN Database accession no. 110:76950 CA XP002040969 & KHIM. TEKHNOL. (KIEV) (1988), (6), 45-51 , 1988, * |
DATABASE CHEMABS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MURAKAMI, YOSHIAKI ET AL: "Granular activated carbon" retrieved from STN Database accession no. 89:181873 CA XP002040874 & JP 53 050088 A (SUMITOMO CHEMICAL CO., LTD., JAPAN) 8. Mai 1978 (1978-05-08) * |
DATABASE CHEMABS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; OKIDO, SADAO ET AL: "Carbonization of synthetic resin" retrieved from STN Database accession no. 107:239318 CA XP002040873 & JP 62 197308 A (JAPAN ORGANO CO., LTD., JAPAN;KURARAY CHEMICAL CO., LTD.) 1. September 1987 (1987-09-01) * |
DATABASE WPI Section Ch, Week 199745 Derwent Publications Ltd., London, GB; Class A13, AN 1997-488132 XP002099118 & RU 2 077 479 C (EKOFOR STOCK CO), 20. April 1997 (1997-04-20) * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001083368A1 (en) * | 2000-04-28 | 2001-11-08 | Bluecher Hasso Von | Method for producing spherical activated carbon |
US7288504B2 (en) | 2000-04-28 | 2007-10-30 | BLüCHER GMBH | Method for producing spherical activation carbon |
US8927457B2 (en) | 2000-04-28 | 2015-01-06 | BLüCHER GMBH | Process for producing spherical activated carbon |
DE10148286A1 (en) * | 2001-09-29 | 2003-04-17 | Sandler Helmut Helsa Werke | Activated charcoal production by sulfonating copolymer, pyrolysis and activation, uses catalytic additive regulating pore structure in educt mixture of copolymer and sulfuric acid |
WO2005016819A1 (en) * | 2003-08-11 | 2005-02-24 | BLüCHER GMBH | Activated charcoal production |
US7662747B2 (en) | 2003-08-11 | 2010-02-16 | De Ruiter Ernest | Activated charcoal production |
DE102005038554A1 (en) * | 2005-08-12 | 2007-02-15 | Cernius Holding Gmbh | Process for the preparation of spherical activated carbon |
DE102005038555A1 (en) * | 2005-08-12 | 2007-02-15 | Cernius Holding Gmbh | Process for the preparation of spherical activated carbon |
US8021463B2 (en) | 2005-08-12 | 2011-09-20 | Blucher Gmbh | Method for producing spherical activated carbon |
US8147589B2 (en) | 2005-08-12 | 2012-04-03 | Blucher Gmbh | Method for producing spherical activated carbon |
Also Published As
Publication number | Publication date |
---|---|
DE19930732A1 (en) | 2001-01-18 |
EP1204590A2 (en) | 2002-05-15 |
WO2001002295A3 (en) | 2001-03-29 |
AU6979200A (en) | 2001-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2317455C3 (en) | Chromatographic packing material | |
DE60035545T2 (en) | A catalyst support based on a Group IVB metal oxide, its preparation and uses | |
EP1276694B1 (en) | Method for producing spherical activated carbon | |
DE2419827C3 (en) | Process for the production of spherical activated carbon | |
DE60103505T2 (en) | ACTIVATED CARBON AND EXPANDED GRAPHITE CONTAINING COMPOSITE MATERIAL | |
DE60104901T2 (en) | HYDRODEX CATALYST AND ITS USE | |
EP2720789B1 (en) | Production of titanium oxide- and/or vanadium oxide-based porous materials | |
EP3046891B1 (en) | Method for producing a porous carbon product | |
CH644277A5 (en) | METHOD FOR PRODUCING FILTER MATERIAL AND THE USE THEREOF. | |
EP3079818A1 (en) | Catalyst system based on spherical activated carbon as a carrier and use thereof | |
DE202012005818U1 (en) | Porous materials based on metallic mixed oxides | |
DE102011013314A1 (en) | Microporous carbon material and method of forming the same | |
EP0002251B1 (en) | Process for the preparation of an attrition-resistant active carbon catalyst or catalyst support | |
DE2917234C3 (en) | Catalyst for the concentration of hydrogen isotopes | |
EP1204590A2 (en) | Method for the controlled production of spherical activated carbon | |
DE3428421A1 (en) | METHOD FOR PRODUCING ALUMINUM OXIDE USED AS CATALYST SUPPORT | |
EP1036034B1 (en) | Production of active carbon from polymers with aromatic nuclei | |
EP0814056B1 (en) | Process for manufacturing activated carbon | |
DE2153658A1 (en) | Process for the production of molded bodies from aluminum oxide | |
DE2326937C2 (en) | ||
DE1471375B2 (en) | POROESE ALUMINUM OXIDE SINTER BODY AND PROCESS FOR THEIR PRODUCTION | |
DE102015122923A1 (en) | Process for the preparation of a supercapacitor | |
DE10024312B4 (en) | A method of modifying the surfaces of microporous adsorbents and methods of making a molecular sieve using this method | |
DE102006053155B4 (en) | Open-cell ceramic foam and its use | |
DE1471375C (en) | Porous alumina sintered bodies and process for their manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000958108 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2000958108 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000958108 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |