DE19653238A1 - High-grade granular activated charcoal production without sulphur di:oxide emission - Google Patents

High-grade granular activated charcoal production without sulphur di:oxide emission

Info

Publication number
DE19653238A1
DE19653238A1 DE19653238A DE19653238A DE19653238A1 DE 19653238 A1 DE19653238 A1 DE 19653238A1 DE 19653238 A DE19653238 A DE 19653238A DE 19653238 A DE19653238 A DE 19653238A DE 19653238 A1 DE19653238 A1 DE 19653238A1
Authority
DE
Germany
Prior art keywords
activated charcoal
sulphur
granular activated
oxide emission
charcoal production
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Withdrawn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
DE19653238A
Other languages
German (de)
Inventor
Ernest De Dr Ruiter
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.)
MHB FILTRATION GMBH + CO. KG, 40699 ERKRATH, DE
Original Assignee
Bluecher GmbH
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
Priority claimed from DE19650414A external-priority patent/DE19650414A1/en
Application filed by Bluecher GmbH filed Critical Bluecher GmbH
Priority to DE19653238A priority Critical patent/DE19653238A1/en
Priority to US09/242,727 priority patent/US6300276B1/en
Priority to DE59710240T priority patent/DE59710240D1/en
Priority to EP97944759A priority patent/EP0952960B1/en
Priority to PCT/EP1997/004459 priority patent/WO1998007655A1/en
Priority to ES97944759T priority patent/ES2201327T3/en
Priority to AU46170/97A priority patent/AU4617097A/en
Publication of DE19653238A1 publication Critical patent/DE19653238A1/en
Withdrawn legal-status Critical Current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
    • 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
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor

Abstract

Production of granular, especially spherical activated charcoal (I) comprises (a) forming free-running granules from a mixture of a distillation residue from diisocyanate manufacture, a carbonaceous processing aid and optionally other additives; (b) low temperature carbonisation; and (c) activation. Also claimed is (I) per se.

Description

Die Patentanmeldung 196 50 414.7 beschreibt Wege, um aus diversen Ionen­ austauschern, Vorstufen von diesen sowie Rückständen eine kugelförmige Aktivkohle herzustellen. Dabei ist es wichtig, vor dem eigentlichen Schwelen die Kügelchen unschmelzbar zu machen, um ein Zusammenbacken zu ver­ meiden. Das bedingt eine schon bei niedriger Temperatur einsetzende Vernet­ zung, die normalerweise über Radikale stattfindet. Es haben sich u. a. Sauer­ stoff und Isocyanate bewährt.The patent application 196 50 414.7 describes ways to get out of diverse ions exchangers, precursors of these and residues a spherical Manufacture activated carbon. It is important to do this before smoldering to make the beads infusible to prevent caking avoid. This requires Vernet to start at a low temperature tongue, which usually takes place via radicals. U. a. Sour Proven substance and isocyanates.

Es wurde jetzt gefunden, daß sich Diphenylmethan-Polyisocyanate besonders gut als Vernetzer bzw. auch als wesentlicher Bestandteil des zu schwelenden Materials eignen.It has now been found that diphenylmethane polyisocyanates in particular good as a crosslinker or as an essential part of the process to be smoldered Material.

Es wurde weiter gefunden, daß die so erhaltene Aktivkohle eine gegenüber normaler Aktivkohle erhöhte Affinität für saure Gase hat, was dem in Aromat­ systemen eingebauten Stickstoff zuzuschreiben ist.It was further found that the activated carbon thus obtained was compared to one normal activated carbon has increased affinity for acid gases, which is the same as in aromatics systems is due to built-in nitrogen.

Beim Schwelen, welches im Drehrohr oder in Wirbelschicht bzw. speziellen Öfen, wie Röhrenofen ("Tubular furnace", Etagenofen, Schneckengangofen usw.) durchgeführt wird, ist darauf zu achten, daß besonders unterhalb 250°C der Vernetzung (unschmelzbar machen) genügend Zeit geboten wird. Hier ist auch die Zugabe von etwas Luft der Vernetzung förderlich. Die Abspaltung von flüchtigen Bestandteilen ist ab 450°C weitgehend beendet. Ab 600°C ist es vorteilhaft, etwas Wasserdampf zuzugeben, um einer vorzeitigen Graphiti­ sierung entgegenzuwirken. Die Aktivierung wird in einer dem Fachmann be­ kannten Weise bei Temperaturen von 700-900°C durchgeführt, wobei Was­ serdampf, Luft oder CO2 eingeblasen wird.When smoldering, which is carried out in a rotary tube or in a fluidized bed or special furnaces such as tubular furnaces (multi-stage furnaces, multi-deck furnaces, screw-type furnaces, etc.), care must be taken to ensure that there is sufficient time, especially below 250 ° C, for the crosslinking (to make it infusible) is offered. The addition of some air is also conducive to networking here. The elimination of volatile constituents has largely ended at 450 ° C. From 600 ° C, it is advantageous to add some water vapor to counteract premature graphitization. The activation is carried out in a manner known to the person skilled in the art at temperatures of 700-900 ° C., water vapor, air or CO 2 being blown in.

Beispielexample

25 Teile Polystyrol-Abfälle wurden in 25 Teilen Steinkohlenteerpech aufge­ schmolzen und mit 50 Teilen Diphenylmethan-Poly-(meist tri-)isocyanat ver­ setzt. Die Masse wurde warm extrudiert und mittels eines Marumerizers zu Kügelchen mit Durchmesser 0,3-2,0 mm geformt. Die Schwelung geschah in einem 20 l Drehrohr der Fa. Plecq. Es wurde in 60 min. auf 150°C unter N2 unter Zugabe von ca. 10% Luft angeheizt und bei dieser Temperatur 60 min. verweilt. Danach wurde mit 3°C/min. auf 450°C und mit 5°C/min. auf 700°C aufgeheizt. Ab 600°C wurden ca. 5% Wasserdampf zugegeben. Der Pyroly­ se-Rückstand betrug 56%, das Schüttgewicht ca. 910 g/l. Die Aktivierung wur­ de im gleichen Drehrohr bei 850°C mit 25% Wasserdampf in N2während 120 min. durchgeführt. Es wurde in einer Ausbeute von 41% eine hochwertige, abriebfeste Kugelkohle mit einer inneren Oberfläche von 1.250 m2/g erhalten. Je nach Bedarf kann die innere Oberfläche von 600-1.500 m2/g variieren.25 parts of polystyrene waste were melted in 25 parts of coal tar pitch and mixed with 50 parts of diphenylmethane poly (mostly tri) isocyanate. The mass was extruded warm and formed into beads with a diameter of 0.3-2.0 mm using a Marumerizer. The smoldering took place in a 20 l rotary tube from Plecq. It was in 60 min. heated to 150 ° C under N 2 with the addition of about 10% air and at this temperature for 60 min. lingers. Then at 3 ° C / min. to 450 ° C and at 5 ° C / min. heated to 700 ° C. From 600 ° C about 5% water vapor was added. The pyrolysis residue was 56%, the bulk density was about 910 g / l. The activation was carried out in the same rotary tube at 850 ° C with 25% water vapor in N 2 for 120 min. carried out. A high-quality, abrasion-resistant spherical carbon with an inner surface area of 1,250 m 2 / g was obtained in a yield of 41%. Depending on requirements, the inner surface can vary from 600-1,500 m 2 / g.

Claims (5)

1. Verfahren zur Herstellung hochwertiger kugelförmiger Adsorbentien, da­ durch gekennzeichnet, daß eine Aromatkerne enthaltende, hochviskose thermoplastische Masse mit 10-85% eines aromatischen Isocyanats, ins­ besondere ein Polyisocyanat auf Basis Diphenylmethan, versetzt wird, dann in 0,2 bis 2,0 mm große Kügelchen umgesetzt, geschwelt und akti­ viert wird.1. Process for the production of high-quality spherical adsorbents, characterized in that a highly viscous thermoplastic composition containing aromatic nuclei is mixed with 10-85% of an aromatic isocyanate, in particular a polyisocyanate based on diphenylmethane, then in 0.2 to 2.0 mm large balls are implemented, swollen and activated. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ausgangs­ material extrudiert und pelletiert wird.2. The method according to claim 1, characterized in that the output material is extruded and pelletized. 3. Verfahren nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, daß die Kügelchen bis 700°C geschwelt und zwischen 700-900°C aktiviert wer­ den.3. The method according to claim 1 and / or 2, characterized in that the Beaded up to 700 ° C and activated between 700-900 ° C the. 4. Verfahren nach einem oder mehreren der vorhergehenden Ansprüche, da­ durch gekennzeichnet, daß die Schwelung bis 250°C in leicht oxidierender Atmosphäre durchgeführt wird.4. The method according to one or more of the preceding claims, since characterized in that the smoldering up to 250 ° C in slightly oxidizing Atmosphere is performed. 5. Aktivkohlekügelchen nach einem oder mehreren der vorhergehenden An­ sprüche, dadurch gekennzeichnet, daß sie einen Durchmesser von 0,2 bis 2,0 mm aufweisen, sehr abriebfest sind, eine innere Oberfläche von 600-1.500 m2 und eine überdurchschnittliche Affinität für saure Gase besitzen.5. activated carbon beads according to one or more of the preceding claims, characterized in that they have a diameter of 0.2 to 2.0 mm, are very abrasion-resistant, an inner surface of 600-1,500 m 2 and an above-average affinity for acid gases have.
DE19653238A 1996-08-20 1996-12-20 High-grade granular activated charcoal production without sulphur di:oxide emission Withdrawn DE19653238A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE19653238A DE19653238A1 (en) 1996-12-05 1996-12-20 High-grade granular activated charcoal production without sulphur di:oxide emission
US09/242,727 US6300276B1 (en) 1996-08-20 1997-08-14 Granular activated carbon from distillation residues
DE59710240T DE59710240D1 (en) 1996-08-20 1997-08-14 GRANULAR ACTIVE CARBON FROM DISTILLATION RESIDUES
EP97944759A EP0952960B1 (en) 1996-08-20 1997-08-14 Granulated activated carbon from distillation residues
PCT/EP1997/004459 WO1998007655A1 (en) 1996-08-20 1997-08-14 Granulated activated carbon from distillation residues
ES97944759T ES2201327T3 (en) 1996-08-20 1997-08-14 GRANULATED ACTIVE CARBON FROM DISTILLATION RESIDUES.
AU46170/97A AU4617097A (en) 1996-08-20 1997-08-14 Granulated activated carbon from distillation residues

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19650414A DE19650414A1 (en) 1996-08-20 1996-12-05 High grade spherical adsorbents production from ion exchanger or precursor
DE19653238A DE19653238A1 (en) 1996-12-05 1996-12-20 High-grade granular activated charcoal production without sulphur di:oxide emission

Publications (1)

Publication Number Publication Date
DE19653238A1 true DE19653238A1 (en) 1998-06-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
DE19653238A Withdrawn DE19653238A1 (en) 1996-08-20 1996-12-20 High-grade granular activated charcoal production without sulphur di:oxide emission

Country Status (1)

Country Link
DE (1) DE19653238A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005038555A1 (en) * 2005-08-12 2007-02-15 Cernius Holding Gmbh Process for the preparation of spherical activated carbon
DE202016100320U1 (en) 2015-12-10 2016-12-28 BLüCHER GMBH Activated carbon, in particular particulate activated carbon, in particular with defined porosity properties
DE202021100461U1 (en) 2020-09-25 2022-01-07 Blücher Gesellschaft mit beschränkter Haftung supported catalysts
DE202020107404U1 (en) 2020-11-27 2022-03-01 Blücher Gesellschaft mit beschränkter Haftung Blasting media based on granular activated carbon

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2416198A1 (en) * 1978-02-06 1979-08-31 Kureha Chemical Ind Co Ltd SPHERICAL ACTIVE CARBON WITH HIGH PHYSICAL RESISTANCE AND LOW-DUST RELEASING AND ITS MANUFACTURING PROCESS
DE4304026A1 (en) * 1992-02-28 1993-09-02 Hasso Von Bluecher Exhausted granular organic ion exchange resins disposal for useful active carbon - by converting to carbon@ pellets by carbonising in mainly inert atmos. and activating in oxidising atmos. for cation exchange styrene] acrylic] acid resin
DE4328219A1 (en) * 1993-08-21 1995-02-23 Hasso Von Bluecher Spheres of activated carbon from ion exchangers
DE19600237A1 (en) * 1995-01-11 1996-07-18 Bluecher Hasso Von Prodn. of granulated active carbon

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2416198A1 (en) * 1978-02-06 1979-08-31 Kureha Chemical Ind Co Ltd SPHERICAL ACTIVE CARBON WITH HIGH PHYSICAL RESISTANCE AND LOW-DUST RELEASING AND ITS MANUFACTURING PROCESS
DE4304026A1 (en) * 1992-02-28 1993-09-02 Hasso Von Bluecher Exhausted granular organic ion exchange resins disposal for useful active carbon - by converting to carbon@ pellets by carbonising in mainly inert atmos. and activating in oxidising atmos. for cation exchange styrene] acrylic] acid resin
DE4328219A1 (en) * 1993-08-21 1995-02-23 Hasso Von Bluecher Spheres of activated carbon from ion exchangers
DE19600237A1 (en) * 1995-01-11 1996-07-18 Bluecher Hasso Von Prodn. of granulated active carbon

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE202016100320U1 (en) 2015-12-10 2016-12-28 BLüCHER GMBH Activated carbon, in particular particulate activated carbon, in particular with defined porosity properties
DE102016101215A1 (en) 2015-12-10 2017-06-14 BLüCHER GMBH Process for the production of activated carbon and activated carbon produced in this way and their use
DE202021100461U1 (en) 2020-09-25 2022-01-07 Blücher Gesellschaft mit beschränkter Haftung supported catalysts
WO2022063447A1 (en) 2020-09-25 2022-03-31 BLüCHER GMBH Method for producing supported metal catalysts with a granular activated carbon used as a catalyst support
DE102021102078A1 (en) 2020-09-25 2022-03-31 Blücher Gesellschaft mit beschränkter Haftung Process for preparing supported catalysts
DE202020107404U1 (en) 2020-11-27 2022-03-01 Blücher Gesellschaft mit beschränkter Haftung Blasting media based on granular activated carbon
DE102020134238A1 (en) 2020-11-27 2022-06-02 Blücher Gesellschaft mit beschränkter Haftung Blasting media based on granular activated carbon

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