ITMI930386A1 - PROCEDURE FOR DISPOSAL AND TREATMENT OF CONSUMED ION EXCHANGERS - Google Patents
PROCEDURE FOR DISPOSAL AND TREATMENT OF CONSUMED ION EXCHANGERS Download PDFInfo
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- ITMI930386A1 ITMI930386A1 IT000386A ITMI930386A ITMI930386A1 IT MI930386 A1 ITMI930386 A1 IT MI930386A1 IT 000386 A IT000386 A IT 000386A IT MI930386 A ITMI930386 A IT MI930386A IT MI930386 A1 ITMI930386 A1 IT MI930386A1
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- process according
- consumed
- carbonization
- exchange resins
- resins
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- 238000000034 method Methods 0.000 title claims description 18
- 238000011282 treatment Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000005539 carbonized material Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 101100127285 Drosophila melanogaster unc-104 gene Proteins 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
"Procedimento per lo smaltimento e il trattamento di scambiatori ionici consumati" "Procedure for the disposal and treatment of consumed ion exchangers"
DESCRIZIONE DESCRIPTION
La invenzione concerne un procedimento per lo smaltimento e il trattamento di scambiatori ionici di resine sintetiche che per lo pi? si presentano in forma granulare. The invention relates to a process for the disposal and treatment of ion exchangers of synthetic resins which for the most part? come in granular form.
Scambiatori ionici di resine sintetiche sono polimeri porosi che possiedono numerosi gruppi chimici con ioni scambiabili. Nella maggior parte dei casi ? presente una struttura copolimerizzata di stirene e divinilbenzene o stirene e acido acrilico la quale porta dei gruppi acidi, in particolare gruppi di acido solfonico, per gli scambiatori cationici o gruppi basici (ammini) per gli scambiatori anionici. Tali scambiatori ionici organici con una matrice polimerica a base di resine polistireniche, poliacriliche, polialchilamminiche o di fenolo-formaldeide, che possono esistere come resine scambiatrici di cationi o di anioni a seconda dei loro gruppi funzionali, ed anche resine di adsorbimento sono descritte in Ullmann's Encyclopedia of Industriai Chemistry, 5a edizione Volume A 14, VCH-Verlagsgesellschaf t mbH,, Weinheim, Germania 1989 nel capitolo "Ion Exchangers", in particolare alle pagine 394-398 e sono in commercio con i marchi Lewatit, Dowex, Kastel, Diaion, Relite, Purolite, Amberlite, Duolite, Imac, Ionac, Wofatit. Nel capitolo citato sono descritti alle pagine 399-448 anche numerosi usi delle resine,scambiatrici ioniche. Synthetic resin ion exchangers are porous polymers that possess numerous chemical groups with exchangeable ions. In most cases? there is a copolymerized structure of styrene and divinylbenzene or styrene and acrylic acid which carries acid groups, in particular sulphonic acid groups, for cation exchangers or basic (amino) groups for anion exchangers. Such organic ion exchangers with a polymeric matrix based on polystyrene, polyacrylic, polyalkylamine or phenol-formaldehyde resins, which can exist as cation or anion exchange resins depending on their functional groups, and also adsorption resins are described in Ullmann's Encyclopedia of Industriai Chemistry, 5th edition Volume A 14, VCH-Verlagsgesellschaf t mbH ,, Weinheim, Germany 1989 in the chapter "Ion Exchangers", in particular on pages 394-398 and are marketed under the brands Lewatit, Dowex, Kastel, Diaion , Relite, Purolite, Amberlite, Duolite, Imac, Ionac, Wofatit. Numerous uses of ion exchange resins are also described in the cited chapter on pages 399-448.
?e Con l'uso di rscambiatori ionici si tende in primo luogo allo scambio di ioni non desiderati presenti in acqua contro ioni meno dannosi o al completo allontanamento di ioni. Se i responsabili della durezza - principalmente Ca++ e Mg++ - vengono scambiati con Na+, allora l'acqua "dura" diventa "acqua dolce". Se i cationi e gli anioni vengono allontanati, si ottiene acqua demineralizzata. L'acqua dolce ? ad esempio necessaria per l'industria tessile, l'acqua demineralizzata per la produzione di vapore in particolare in reattori ad alta pressione . ? e With the use of ion exchangers there is a tendency in the first place to the exchange of unwanted ions present in the water against less harmful ions or to the complete removal of ions. If those responsible for hardness - mainly Ca ++ and Mg ++ - are exchanged for Na +, then "hard" water becomes "soft" water. If the cations and anions are removed, demineralized water is obtained. Fresh water? for example necessary for the textile industry, demineralised water for the production of steam in particular in high pressure reactors.
Gli scambiatori ionici perdono normalmente la loro efficacia mediante intasamento, vale a dire mediante aggiunta ai loro pori di particelle in sospensione o di residui inorganici come ad esempio composti del ferro. In effetti questi vengono di regola sciacquati tuttavia col tempo sempre pi? pori vengono ostruiti fino a che il letto deve essere rinnovato. Qui si pone il problema dello smaltimento e trattamento. Fintanto che nessuno degli ioni caricati dall'ambiente ? presente, gli scambiatori ionici consumati possono essere smaltiti e trattati in discariche. Ion exchangers normally lose their effectiveness by clogging, i.e. by adding suspended particles or inorganic residues such as iron compounds to their pores. In fact, these are usually rinsed, however, over time more and more? pores are clogged until the bed needs to be renewed. Here the problem of disposal and treatment arises. As long as none of the charged ions from the environment? present, the consumed ion exchangers can be disposed of and treated in landfills.
Resine scambiatrici di ioni organiche, granulari, diventate inattive sono contaminate con grandi quantit? di sostanze estranee organiche ed inorganiche come ad esempio particelle in sospensione di tutti i tipi, fango, microorganismi, alghe e diversi cationi ad-esempio sodio, potassio, ferro e calcio. La percentuale di questi contaminanti ? di regola fino al 20% in peso con riferimento alla sostanza secca. Le resine scambiatrici di ioni granulari da smaltire e trattare hanno per lo pi? anche una parte di acqua che pu? giungere fino al 50% in peso. Granular, organic ion exchange resins that have become inactive are contaminated with large quantities? of organic and inorganic foreign substances such as for example suspended particles of all types, mud, microorganisms, algae and various cations for example sodium, potassium, iron and calcium. The percentage of these contaminants? as a rule up to 20% by weight with reference to the dry matter. The granular ion exchange resins to be disposed of and treated have mostly? also a part of water that can? reach up to 50% by weight.
Oggetto dell'invenzione ? un procedimento per lo smaltimento e il trattamento di tali scambiatori ionici organici, granulari, consumati, con il quale essi sono trasformati in sferette di carbone attivo mediante carbonizzazione in atmosfera prevalentemente inerte a temperature comprese fra 300 e 900?C e successiva attivazione in una atmosfera ossidante. Object of the invention? a process for the disposal and treatment of such organic, granular, consumed ion exchangers, with which they are transformed into spheres of activated carbon by carbonization in a predominantly inert atmosphere at temperatures between 300 and 900 ° C and subsequent activation in an atmosphere oxidant.
E' noto il fatto di trasformare dei polimeri vinilaromatici , reticolati, macroporosi, polisolfonati, precisamente definiti in particelle adsorbenti contenenti carbonio mediante riscaldamento a temperature fino a 1200?C (US-PS 4.957.897). I gruppi di acido solfonico vengono scissi con la pirolisi, si formano dei siti radicalici che portano a strutture reticolate troppo forti che non sono fondibili e contengono carbonio poco volatile. It is known to transform vinylaromatic, cross-linked, macroporous, polysulphonated polymers, precisely defined, into adsorbent particles containing carbon by heating at temperatures up to 1200 ° C (US-PS 4.957.897). The sulphonic acid groups are broken down with pyrolysis, radical sites are formed which lead to too strong cross-linked structures that are not meltable and contain low volatile carbon.
Non era tuttavia da aspettarsi che anche da scambiatori ionici di resine sintetiche consumati, fortemente contaminati potessero essere ottenute delle sferette di carbone attivo resistenti alla abrasione di alta qualit? mediante pirolisi, e che le diverse sostanze estranee non nuocessero alla qualit? e alla resistenza degli adsorbenti. Sorprendentemente, la struttura dei macropori e dei mesopori del materiale di partenza si conserva con la distruzione degli inquinanti e con la carbonizzazione. I prodotti organici e biologici accumulati vengono distrutti o si volatilizzano senza formare residui carboniosi rilevanti, in particolare quando la carbonizzazione viene effettuata in atmosfera debolmente ossidante. However, was it not to be expected that even from consumed, heavily contaminated synthetic resin ion exchangers, high quality abrasion resistant activated carbon beads could be obtained? by pyrolysis, and that the various foreign substances did not harm the quality? and to the resistance of the adsorbents. Surprisingly, the structure of the macropores and mesopores of the starting material is preserved with the destruction of pollutants and with carbonization. The accumulated organic and biological products are destroyed or volatilize without forming relevant carbon residues, in particular when the carbonization is carried out in a weakly oxidizing atmosphere.
Nelle resine scambiatrici di cationi consumate, i cationi sono di regola fissati ai gruppi di acido solfonico e vengono per la maggior parte trasformati in solfati a temperature comprese fino a 400?C. A temperature pi? alte questi sono ridotti con carbonio, il che porta a considerevoli quote di solfuri. E' quindi vantaggioso trasformare in primo luogo prima della carbonizzazione le resine scambiatrici di cationi nella forma H+ . Questo n.albo 38 avviene opportunamente mediante un lavaggio acido del materiale ancora umido e perci? prima dell'essiccamento . In consumed cation exchange resins, the cations are usually attached to the sulfonic acid groups and are for the most part transformed into sulphates at temperatures up to 400 ° C. At higher temperatures? high these are reduced with carbon, which leads to considerable amounts of sulphides. It is therefore advantageous to transform the cation exchange resins into the H + form first before carbonization. This issue number 38 is suitably carried out by an acid washing of the still wet material and therefore? before drying.
Per allontanare la parte acquosa, che come menzionato pu? giungere sino al 50% della resina scambiatrice di ioni organica granulare, si consiglia di essiccare le resine granulari, consumate, da smaltire, il che avviene preferibilmente in un forno rotativo o in un letto fluido. Prima del raggiungimento della temperatura di intenerimento e di regola dopo l'essiccamento, gli scambiatori ionici di resine sintetiche vengono opportunamente spolverati con una polvere inorganica inerte, preferibilmente polvere di carbone, al fine di impedire un incollamento e di mantenere la struttura granulare durante l'intero trattamento. To remove the watery part, which as mentioned can? reach up to 50% of the granular organic ion exchange resin, it is advisable to dry the granular resins, consumed, to be disposed of, which takes place preferably in a rotary oven or in a fluid bed. Before reaching the softening temperature and usually after drying, the ion exchangers of synthetic resins are suitably dusted with an inert inorganic powder, preferably coal dust, in order to prevent sticking and to maintain the granular structure during the whole treatment.
Fino ad una temperatura di 400?C, preferibilmente fino a circa 300-350?C, la atmosfera inerte della carbonizzazione pu? contenere 0,2-4 volumi % di ossigeno. La percentuale di ossigeno viene opportunamente regolata mediante aggiunta di aria. Questa pre-ossidazione si consiglia non solo con riferimento alle impurit? biologiche e alle altre impurit? organiche, ma anche in connessione con Up to a temperature of 400? C, preferably up to about 300-350? C, the inert atmosphere of the carbonization can? contain 0.2-4% volumes of oxygen. The percentage of oxygen is suitably regulated by adding air. This pre-oxidation is recommended not only with reference to impurities? biological and other impurities organic, but also in connection with
lo spolveramento ed un incremento lento della temperatura anche con riferimento alla carbonizzazione di resine scambiatrici di ioni del tipo a gel. Per. quanto riguarda gli scambiatori ionici che non contengono gruppi di acido solfonico, ad esempio scambiatori anionici o resine adsorbenti, questa pre-ossidazione favorisce inoltre la trasformazione dei granuli in una forma non volatile. Per quanto riguarda questi tipi di resina pu? essere anche opportuno di lavorarli insieme con resine scambiatrici <? >di cationi che contengono gruppi di acido solfonico. dusting and a slow increase in temperature also with reference to the carbonization of ion exchange resins of the gel type. For. as regards ion exchangers that do not contain sulphonic acid groups, for example anion exchangers or adsorbent resins, this pre-oxidation also favors the transformation of the granules into a non-volatile form. As for these types of resin pu? it is also advisable to work them together with exchange resins <? > of cations that contain sulphonic acid groups.
Minori quantit? di cationi, come ioni alcalini e alcalino-terrosi, ad esempio quelli di sodio, potassio etc. o calcio, che vengono trasformati in solfati gi? all'inizio della pirolisi, non disturbano la carbonizzazione e la attivazione, essi sorprendentemente favor oono persino l'attivit? delle sferette di carbone attivo ottenute. Lesser quantities of cations, such as alkaline and alkaline-earth ions, for example those of sodium, potassium etc. or calcium, which are transformed into sulphates already? at the beginning of the pyrolysis, they do not disturb the carbonization and the activation, they surprisingly favor or even the activity? of the activated carbon spheres obtained.
Alla carbonizzazione si associa la attivazione del materiale carbonizzato a circa 700?C. Essa, come la carbonizzazione, pu? essere realizzata in un forno rotativo o, ancora meglio in un letto fluido. Per la attivazione, alla atmosfera in prevalenza inerte viene aggiunto vapore acqueo e/o diossido di carbonio in una quantit? compresa fra 3 e 50, preferibilmente fra 3 e 15% in volume. La temperatura dell'attivazione pu? giungere fino ai 900?. Per motivi di risparmio energetico, la attivazione pu? essere effettuata nello stesso dispositivo dopo la carbonizzazione. Pu? essere tuttavia sensato dal punto di vista del processo tecnico e dell'apparato, di effettuare l'attivazione in uno stadio separato, a parte, tanto pi? che la carbonizzazione fino a temperature di circa 50O?C porta gi? con se un rilevante restringimento ed una perdita di peso del materiale di partenza del 60-90%. La percentuale di carbonio delle sferette di carbone attivo dopo l'attivazione ? al di sopra del 90% in peso. Carbonization is associated with the activation of the carbonized material at about 700? C. It, like carbonization, can? be made in a rotary kiln or, even better, in a fluidized bed. For activation, a quantity of water vapor and / or carbon dioxide is added to the mainly inert atmosphere. between 3 and 50, preferably between 3 and 15% by volume. The temperature of the activation can? reach up to 900 ?. For reasons of energy saving, the activation can? be carried out in the same device after carbonization. Pu? however, it is sensible from the point of view of the technical process and of the apparatus, to carry out the activation in a separate stage, apart, all the more? that the carbonization up to temperatures of about 50O? C brings down? with it a significant shrinkage and a weight loss of the starting material of 60-90%. The percentage of carbon of the activated carbon beads after activation? above 90% by weight.
Esempio 1 Example 1
1 kg di uno scambiatore ionico macr?poroso a base di stirene e divinilbenzene, che era presente in forma H+ e veniva utilizzato come catalizzatore nella sintesi di additivi per carburante (MTBE) ed era diventato inattivo, venne essiccato in forno rotativo a 110?C. La perdita di peso, cagionata dalla evaporazione di idrocarburi e da un po' di umidit?, era di circa il 13%. La temperatura venne poi portata a 300?C, in un'atmosfera di gas inerte all'85% e di aria al 15%, e ivi mantenuta per 1 ora. Con ci? l'aumento di peso ammontava a circa l'8%. In seguito la temperatura venne aumentata a 700?C nel corso di 3 ore in atmosfera inerte. Nell'intervallo di 700-900?C venne aggiunto il 5% di vapore acqueo. L'incremento della temperatura da 700 a 820?C durava 30 minuti, in ulteriori 10 minuti furono raggiunti i 900?C. 1 kg of a macr? Porous ion exchanger based on styrene and divinylbenzene, which was present in the H + form and was used as a catalyst in the synthesis of fuel additives (MTBE) and had become inactive, was dried in a rotary kiln at 110 ° C . The weight loss, caused by the evaporation of hydrocarbons and some humidity, was about 13%. The temperature was then raised to 300 ° C, in an atmosphere of 85% inert gas and 15% air, and maintained there for 1 hour. With us? weight gain amounted to about 8%. Thereafter the temperature was raised to 700 ° C over the course of 3 hours in an inert atmosphere. In the range of 700-900 ° C, 5% water vapor was added. The temperature increase from 700 to 820 ° C lasted 30 minutes, in a further 10 minutes 900 ° C was reached.
La resa, con riferimento al materiale di partenza, ammontava al 28%. In nessun momento le sferette si incollavano insieme. Durante la pirolisi venne osservato un restringimento di circa 0,8 mm del diametro a 0,6-0,7 mm. La densit? apparente delle sferette era di 1,08 g/cm^ per un volume dei pori maggiore di 0,9 ml/g, di cui 0,55 ml/g erano micropori. Con il metodo BET venne determinata una superficie specifica di 1080 m^/g. Una grossa sferetta di 0,5 mm pot? essere caricata in modo puntiforme con 300 g senza venire a rottura. The yield, with reference to the starting material, amounted to 28%. At no time did the spheres stick together. During pyrolysis, a shrinkage of about 0.8 mm in diameter to 0.6-0.7 mm was observed. The density apparent of the spheres was 1.08 g / cm2 for a pore volume greater than 0.9 ml / g, of which 0.55 ml / g were micropores. With the BET method a specific surface of 1080 m ^ / g was determined. A large ball of 0.5 mm pot? be point loaded with 300 g without breaking.
Esempio 2 Example 2
1 kg di uno scambiatore cationico del tipo a gel che era stato .utilizzato per l?addolcimento delle acque e non possedeva pi? alcuna sufficiente attivit?, venne trasformato nella forma H+ con una soluzione di acido cloridrico. Dopo essiccazione superficiale all'aria, l'umidit? ammontava a circa il 50%. Dopo essiccazione a 110?C, venne ossidato a 300?C per 6 ore in aria. In seguito si procedette come nell'esempio 1. La resa, con riferimento al materiale di partenza, ammontava al 31%. Le sferette erano in parte incollate. 1 kg of a gel-type cation exchanger that had been used for water softening and no longer possessed no sufficient activity, it was transformed into the H + form with a hydrochloric acid solution. After surface drying in the air, the humidity? amounted to about 50%. After drying at 110 ° C, it was oxidized at 300 ° C for 6 hours in air. Then one proceeded as in example 1. The yield, with reference to the starting material, amounted to 31%. The spheres were partially glued.
Esempio 3 Example 3
Con lo stesso materiale dell'esempio 2 si procedette dapprima nello stesso modo, tuttavia dopo la ossidazione a 300?C venne spolverato con il 5% di polvere di carbone e l'incremento della temperatura venne effettuato a 700?C in 6 ore. With the same material as in Example 2, the same procedure was carried out at first, however after the oxidation at 300 ° C it was dusted with 5% coal dust and the temperature was increased to 700 ° C in 6 hours.
L'incollamento delle sferette e la formazione di una struttura a bolle poteva cosi essere evitato. La superficie interna delle particelle di carbone attivo ottenute ammontava a circa 1000 m2/g (BET), la resa, con riferimento al materiale di partenza, ammontava al 40%. Con un diametro di 0,5 mm, il carico di rottura medio era di 250 g? The sticking of the spheres and the formation of a bubble structure could thus be avoided. The internal surface of the activated carbon particles obtained amounted to about 1000 m2 / g (BET), the yield, with reference to the starting material, was 40%. With a diameter of 0.5mm, the average breaking load was 250g?
Nello stesso modo furono trasformate a carbone attivo anche resine adsorbenti macroporose a base di un copolimero di divinilbenzene, che erano consumate e contenevano ancora sostanze organiche adsorbite. Poich? in questi prodotti mancano gruppi di acido solfonico, una pre-ossidazione ? particolarmente importante per la formazione, di ponti di carbonio. In the same way, macroporous adsorbent resins based on a copolymer of divinylbenzene were converted to activated carbon, which were consumed and still contained adsorbed organic substances. Since? these products lack sulphonic acid groups, a pre-oxidation? particularly important for the formation of carbon bridges.
Claims (13)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4206132 | 1992-02-28 |
Publications (3)
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| ITMI930386A1 true ITMI930386A1 (en) | 1994-08-26 |
| IT1264353B1 IT1264353B1 (en) | 1996-09-23 |
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| IT93MI000386A IT1264353B1 (en) | 1992-02-28 | 1993-02-26 | PROCEDURE FOR THE DISPOSAL AND TREATMENT OF CONSUMED ION EXCHANGERS |
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| JP (1) | JP2626956B2 (en) |
| KR (1) | KR0125587B1 (en) |
| CA (1) | CA2090649C (en) |
| DE (1) | DE4304026B4 (en) |
| FR (1) | FR2687941B1 (en) |
| GB (1) | GB2265143B (en) |
| IT (1) | IT1264353B1 (en) |
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| IT1273678B (en) * | 1993-08-12 | 1997-07-09 | Bluecher Hasso Von | ACTIVATED CARBON PRODUCTION PROCESS |
| NL1000078C2 (en) * | 1994-04-19 | 1996-04-22 | Bluecher Hasso Von | Odor filter for vacuum cleaners. |
| SE515506C2 (en) * | 1994-06-17 | 2001-08-20 | Mhb Filtration Gmbh & Co Kg | Odor filter for ventilation outlet hoods |
| SE509743C2 (en) * | 1994-06-17 | 1999-03-01 | Bluecher Hasso Von | Adsorptionsfilterskikt |
| DE4446253A1 (en) * | 1994-12-23 | 1996-06-27 | Hasso Von Bluecher | Textile material of active carbon for adsorption air filters |
| ATE224338T1 (en) * | 1995-01-11 | 2002-10-15 | Mhb Filtration Gmbh & Co Kg | METHOD FOR PRODUCING GRANULAR ACTIVATED CHARCOAL |
| DE59706726D1 (en) * | 1996-06-22 | 2002-05-02 | Mhb Filtration Gmbh & Co Kg | Process for the production of granular activated carbon |
| DE19653238A1 (en) * | 1996-12-05 | 1998-06-25 | Bluecher Gmbh | High-grade granular activated charcoal production without sulphur di:oxide emission |
| DE19650414A1 (en) * | 1996-08-20 | 1998-02-26 | Bluecher Gmbh | High grade spherical adsorbents production from ion exchanger or precursor |
| DE19752593C5 (en) | 1997-11-27 | 2005-02-17 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Process for the preparation of activated carbon from polymers with aromatic nuclei |
| US6143835A (en) * | 1998-04-03 | 2000-11-07 | Solutia Inc. | Polyacrylonitrile polymer treatment |
| US6277933B1 (en) | 1998-04-03 | 2001-08-21 | Solutia Inc. | Polyacrylonitrile particles by surfmer polymerization and sodium removal by chemical exchange |
| DE19912153B4 (en) * | 1999-03-18 | 2004-08-19 | Carbotex Produktions-Und Veredelungsbetriebe Gmbh | Process for the production of shaped high-performance adsorbents |
| DE19930732A1 (en) * | 1999-07-05 | 2001-01-18 | Sandler Helmut Helsa Werke | Process for the controlled production of spherical activated carbon |
| EP1276694B1 (en) | 2000-04-28 | 2004-11-24 | Blücher GmbH | Method for producing spherical activated carbon |
| DE50012022D1 (en) * | 2000-05-24 | 2006-03-30 | Carbotex Produktions Und Vered | METHOD FOR PRODUCING MOLDED ACTIVE CARBON |
| JP2006273772A (en) * | 2005-03-30 | 2006-10-12 | Japan Organo Co Ltd | Orally administered drug and method for producing the same |
| DE102005062160A1 (en) | 2005-12-19 | 2007-06-21 | BLüCHER GMBH | Activated charcoal for medical use |
| DE102006010862B4 (en) * | 2005-12-20 | 2010-01-14 | BLüCHER GMBH | Activated carbon with catalytic activity |
| BRPI0719764A8 (en) | 2006-10-09 | 2017-10-31 | British American Tobacco Investments Ltd | METHODS FOR CARBONIZING AND ACTIVATING CARBONACEOUS MATERIAL, AND FOR PREPARING ACTIVATED CARBON, ACTIVATED OVEN, PROCESSES FOR PREPARING AN ACTIVATED CARBON PRODUCT, FOR PREPARING A CARBONIZED PARTICULATE PRODUCT, AND FOR PRODUCING DISCRETE SOLID GLOBULES OF POLYMERIC MATERIAL, AND APPARATUS FOR FORMING SOLID GLOBULES POLYMERIC MATERIAL DISCRETS |
| DE202006016898U1 (en) | 2006-10-12 | 2007-11-22 | BLüCHER GMBH | High performance adsorbents based on activated carbon with high microporosity |
| DE102007050971B4 (en) | 2007-03-14 | 2014-12-31 | BLüCHER GMBH | Process for the preparation of high performance adsorbents based on activated carbon with high meso- and macroporosity, high performance adsorbents and their use |
| DE102009032810A1 (en) | 2009-07-10 | 2011-01-13 | BLüCHER GMBH | Plant and process for the production of activated carbon |
| WO2012171656A1 (en) | 2011-06-17 | 2012-12-20 | BLüCHER GMBH | Mixed metal oxide-based porous materials and the production and use thereof |
| WO2012171655A1 (en) | 2011-06-17 | 2012-12-20 | BLüCHER GMBH | Titanium oxide- and/or vanadium oxide-based porous materials and the production and use thereof |
| DE202011106025U1 (en) | 2011-08-14 | 2012-08-17 | BLüCHER GMBH | Activated carbon with metal-based component |
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| DE102012007392A1 (en) | 2011-11-07 | 2013-05-08 | BLüCHER GMBH | Nitrogen-modified or -functionalized activated carbon, preferably activated coal with nitrogen as catalytically active heteroatom obtained by surface oxidation of activated carbon using oxidizing reagent, useful to produce e.g. filter |
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| DE102016100159A1 (en) | 2015-11-30 | 2017-06-01 | BLüCHER GMBH | Functional footwear unit |
| 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 |
| DE102016101213A1 (en) | 2015-12-22 | 2017-06-22 | BLüCHER GMBH | Apparatus and method for modifying porous solids |
| WO2018059722A1 (en) | 2016-10-01 | 2018-04-05 | BLüCHER GMBH | Protective material having catalytic and/or reactive properties and the production and use of same |
| DE202017100965U1 (en) | 2016-12-23 | 2018-01-02 | BLüCHER GMBH | Protective clothing unit |
| DE102017126118A1 (en) | 2017-09-27 | 2019-03-28 | BLüCHER GMBH | Process and installation for the treatment and / or purification of water |
| DE202018100242U1 (en) | 2017-11-28 | 2018-12-07 | BLüCHER GMBH | Air-permeable surface filter material |
| KR102178391B1 (en) * | 2018-10-15 | 2020-11-12 | 이동희 | Recycling method of deodorant using waste cation exchange resin. |
| EP3994418B1 (en) | 2019-09-03 | 2023-04-12 | Blücher GmbH | Protective item in the form of protective clothing with splinter, puncture and/or cut protection properties, the protective item comprising or consisting of at least one textile planar material with splinter, puncture and/or cut protection properties. |
| WO2021047789A1 (en) | 2019-09-09 | 2021-03-18 | BLüCHER GMBH | Head covering, in particualr a hood or balaclava, for use as protective clothing |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5621724B2 (en) * | 1973-12-27 | 1981-05-21 | ||
| US4040990A (en) * | 1975-02-18 | 1977-08-09 | Rohm And Haas Company | Partially pyrolyzed macroporous polymer particles having multimodal pore distribution with macropores ranging from 50-100,000 angstroms |
| US4957897A (en) * | 1988-01-29 | 1990-09-18 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
| US4839331A (en) * | 1988-01-29 | 1989-06-13 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
-
1993
- 1993-02-11 DE DE4304026A patent/DE4304026B4/en not_active Expired - Fee Related
- 1993-02-26 GB GB9303956A patent/GB2265143B/en not_active Expired - Fee Related
- 1993-02-26 JP JP5062720A patent/JP2626956B2/en not_active Expired - Lifetime
- 1993-02-26 IT IT93MI000386A patent/IT1264353B1/en active IP Right Grant
- 1993-02-26 FR FR9302227A patent/FR2687941B1/en not_active Expired - Fee Related
- 1993-02-27 KR KR1019930002887A patent/KR0125587B1/en not_active Expired - Fee Related
- 1993-03-01 CA CA002090649A patent/CA2090649C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4304026A1 (en) | 1993-09-02 |
| JP2626956B2 (en) | 1997-07-02 |
| GB2265143B (en) | 1995-08-16 |
| ITMI930386A0 (en) | 1993-02-26 |
| FR2687941A1 (en) | 1993-09-03 |
| CA2090649A1 (en) | 1993-08-29 |
| JPH0692615A (en) | 1994-04-05 |
| IT1264353B1 (en) | 1996-09-23 |
| FR2687941B1 (en) | 1995-07-21 |
| KR0125587B1 (en) | 1998-04-11 |
| DE4304026B4 (en) | 2005-02-17 |
| CA2090649C (en) | 1999-02-02 |
| GB9303956D0 (en) | 1993-04-14 |
| KR930017632A (en) | 1993-09-20 |
| GB2265143A (en) | 1993-09-22 |
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