IT8922522A1 - PROCESS FOR THE EXTRACTION OF ORGANIC MICROPOLLUTANTS FROM FLUIDS, USING REACTIVABLE SYNTHETIC MACROCYCLES - Google Patents
PROCESS FOR THE EXTRACTION OF ORGANIC MICROPOLLUTANTS FROM FLUIDS, USING REACTIVABLE SYNTHETIC MACROCYCLES Download PDFInfo
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- IT8922522A1 IT8922522A1 IT1989A22522A IT2252289A IT8922522A1 IT 8922522 A1 IT8922522 A1 IT 8922522A1 IT 1989A22522 A IT1989A22522 A IT 1989A22522A IT 2252289 A IT2252289 A IT 2252289A IT 8922522 A1 IT8922522 A1 IT 8922522A1
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- 238000000034 method Methods 0.000 title claims description 27
- 238000000605 extraction Methods 0.000 title claims description 25
- 150000002678 macrocyclic compounds Chemical class 0.000 title claims description 12
- 239000012530 fluid Substances 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- -1 halide halides Chemical class 0.000 claims description 5
- 230000007420 reactivation Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004458 analytical method Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001211 electron capture detection Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 238000003965 capillary gas chromatography Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Extraction Or Liquid Replacement (AREA)
Description
Descrizione dell?Invenzione industriale dal titolo: "PROCESSO PER L'ESTRAZIONE DA FLUIDI DI MICROINQUINANTI ORGA-NICI, UTILIZZANDO MACROCICLI SINTETICI RIATTIVABILI" Description of the industrial invention entitled: "PROCESS FOR THE EXTRACTION OF ORGANIC MICROPOLLUTANTS FROM FLUIDS, USING REACTIVABLE SYNTHETIC MACROCYCLES"
Riassunto Summary
Processo per l'estrazione da fluidi, e in particolare da soluzioni acquose, di microinquinanti organici, utilizzando particolari macrocicli sintetici riattivabi1i, insolubili in acqua, quali agenti di estrazione. Process for the extraction from fluids, and in particular from aqueous solutions, of organic micropollutants, using particular reactivable synthetic macrocycles, insoluble in water, as extraction agents.
* * * * * * * * * *
La necessit? di depurare le acque di scarico industriali e le acque per uso potabile ? ampiamente nota. La depurazione di acque contenenti alte concentrazioni di agenti inquinanti pu? essere efficacemente risolta, ad esemplo, mediante procedimenti di degradazione biologica. Tali procedimenti, per?, sono difficilmente applicabili nel caso di microinqu1nanti organici, cio? di sostanze organiche nocive allo stato di estrema diluizione. In questi casi i procedimenti pi? utilizzati sono basati sul-l'adsorbimento con carbone attivo o con resine scambiatrid di ioni (per esempio Amberlite XAD). L'adsorbente pi? utilizzato (B-730-05) The necessity? to purify industrial waste water and drinking water? widely known. The purification of water containing high concentrations of pollutants can? be effectively resolved, for example, by means of biological degradation processes. These procedures, however, are difficult to apply in the case of organic micro-pollutants, that is to say? of harmful organic substances in the state of extreme dilution. In these cases the most? used are based on adsorption with activated carbon or with ion exchange resins (for example Amberlite XAD). The adsorbent pi? used (B-730-05)
industrialmente ? il carbone attivo che, oltre al basso costo, presenta un'elevata attivit? decolorante accanto ad un'ottima capacit? adsorbente; il carbone, per?, presenta seri problemi a livello industriale, legati in particolare alle difficolt? tecnico-operative; la riattivazione, per esempio, viene scarsamente utilizzata a causa delle drastiche condizioni richieste e della grandezza degli impianti necessari alla sua attuazione. industrially? activated carbon which, in addition to the low cost, has a high activity? bleaching next to an excellent capacity? adsorbent; Coal, however, presents serious industrial problems, linked in particular to the difficulties? technical-operational; reactivation, for example, is rarely used due to the drastic conditions required and the size of the systems necessary for its implementation.
La Richiedente ha ora riscontrato risultati sorprendentemente migliori ricorrendo a composti macrociclici di formula particolare, che verranno dettagliati qui di seguito. In altre parole, la Richiedente ha messo a punto un nuovo e migliore processo per l'estrazione di microinquinanti organici, ad esempio idrocarburi aromatici^ alogenuri alifatici, animine aromatiche e triazine,da reflui acquosi, acquedotti, scarichi industriali eccetera, e per il loro successivo recupero quantitativo, in vista di una eventuale riutilizzazione o alienazione. Con il termine estrazione si intende la comp?essazione di detti composti microinquinanti, disciolti o dispersi nel sistema acquoso, da parte di un agente complessante solido, Insolubile nel mezzo acquoso. I composti macrod clici secondo l'invenzione possono estrarre quantit? microscopiche di sostanze organiche microinquinanti, sia da liquidi che da gas, operando in continuo oppure in discontinuo. The Applicant has now found surprisingly better results by resorting to macrocyclic compounds having a particular formula, which will be detailed below. In other words, the Applicant has developed a new and better process for the extraction of organic micropollutants, for example aromatic hydrocarbons ^ aliphatic halides, aromatic amines and triazines, from aqueous wastewater, aqueducts, industrial waste, etc., and for their subsequent quantitative recovery, in view of a possible reuse or disposal. The term extraction refers to the compaction of said micropolluting compounds, dissolved or dispersed in the aqueous system, by a solid complexing agent, Insoluble in the aqueous medium. The macrod-clic compounds according to the invention can extract quantities? microscopic micro-polluting organic substances, both from liquids and gases, operating continuously or discontinuously.
Nel suo aspetto pi? ampio l'Invenzione riguarda un processo per l'estrazione da un fluido, e in particolare da soluzioni acquose, di m1croinqu1nanti organici, utilizzando macrocicli sintetici e riattivabi1i, insolubili in acqua, quali agenti di estrazione, detti macrocicli essendo scelti fra 1 composti aventi formula (I): In its most? The invention relates to a process for the extraction from a fluid, and in particular from aqueous solutions, of organic micro-pollutants, using synthetic and reactivable macrocycles, insoluble in water, as extraction agents, said macrocycles being selected among the compounds having formula (THE):
dove R ? un gruppo alchilico, lineare o ramificato, avente da 1 a 30 atomi C. Detti composti di formula (I) sono noti comunemente come "CAVITANDS" e sono stati descritti, ad esempio, nel J. Chem. Soc., Chem. Commun. (1989), pagina 500. Detti CAVITANDS vengono ottenuti, come noto, mediante condensazione acido-catalizzata della resorcina con un'aldeide e successiva sostituzione nucleofila aromatica con 2,3-d1clorochinossalina, come descritto nel J. Am. Chem. Soc. (1982) 104, pagina 5826 e nel J. Chem. Soc. Chem. Commun. (1989), pagina 500. Detti CAVITANDS di formula (I) sono facilmente solubili nei comuni solventi organici clorurati, poco solubili in acetone, in ace where R? a linear or branched alkyl group having from 1 to 30 C atoms. Said compounds of formula (I) are commonly known as "CAVITANDS" and have been described, for example, in J. Chem. Soc., Chem. Commun. (1989), page 500. Said CAVITANDS are obtained, as known, by acid-catalyzed condensation of resorcinol with an aldehyde and subsequent nucleophilic aromatic substitution with 2,3-d1chloroquinoxaline, as described in J. Am. Chem. Soc. (1982) 104, page 5826 and in J. Chem. Soc. Chem. Commun. (1989), page 500. Said CAVITANDS of formula (I) are easily soluble in common chlorinated organic solvents, not very soluble in acetone, in ace
tato di etile e nei solventi aromatici (benzene, toluene eccetera) e completamente insolubili in acqua e alcool. Essi presentano una elevata stabilit? termica: la temperatura di decomposizione ? di circa 430 C. Detti CAVITANDS sono caratterizzati dalla presenza di una cavit? lipofila preorganizzata, larga 0,72 nm (nanometri) e profonda 0,83 nm (vedere figura 1). Tale cavit?, opportunamente vuotata dalle molecole di solvente con cui tende a riempirsi, ? in grado di ospitare {comp?essere) molecole organiche neutre, o parte di esse, di dimensioni non superiori al volume stesso della caviti. La stechiometria del complesso ? 1:1, cio? ogni cavitand pu? includere in cavit? una sola molecola di ospite. L'energia di associazione del complesso ? legata alle interazioni di tipo elettrostatico, che si instaurano tra il cavitand e la molecola complessata. La complessazione ? selettiva, cio? non vengono complessate tutte le molecole organiche di dimensioni tali da poter essere contenute totalmente o in parte nella cavit?. In acqua, essendo 1 cavitands completamente insolubili, il fattore determinante per la selettivit? della comp?essazione ? l idrofobicit? delle molecole ospite. Quanto pi? una sostanza organica ? idrofobica, tanto maggiore ? la tendenza dei cavitands a complessarla e la forza della loro interazione. L'idrofobicit? delle sostanze organiche pu? essere quantificata utilizzando, come parametro, il logaritmo (1n base 10) del coefficiente di ripartizione tra ottanolo e acqua della sostanza stessa (logPoct), come descritto in Chem. Rev. (1971) 7J_ pagina 525. I composti organici aventi logPoct uguale o superiore a 0,7 sono complessati in maniera significativa da una sospensione solida di cavitand in acqua. Nella Tabella I sono riportati alcuni esempi relativi all'estrazione, da parte di un cavitand di tipo (A) (R = CcH.0), di microinquinanti tipici, indicando il corrispondente logPoct. Il complesso che si forma tra cavitand e ospite ? ancora un solido completamente insolubile in acqua e quindi facilmente separabile dalla soluzione. Riscaldando il complesso a pressione ridotta, o in corrente di gas inerte, a una temperatura uguale o superiore a 200 C (preferibilmente fra 200 e 400 C) si opera la contemporanea rigenerazione (riattivazione) del cavitand e l'Isolamento dei micro-inquinanti estratti. tate of ethyl and in aromatic solvents (benzene, toluene, etc.) and completely insoluble in water and alcohol. They have a high stability? thermal: the decomposition temperature? of about 430 C. Said CAVITANDS are characterized by the presence of a cavity? preorganized lipophilic, 0.72 nm wide (nanometers) and 0.83 nm deep (see figure 1). This cavity, suitably emptied by the solvent molecules with which it tends to fill,? capable of hosting (comp? being) neutral organic molecules, or part of them, of dimensions not greater than the volume of the cavity itself. The stoichiometry of the complex? 1: 1, that is? each cavitand can? include in the cavity? a single host molecule. The association energy of the complex? linked to electrostatic interactions, which are established between the cavitand and the complexed molecule. The complexation? selective, that is? not all the organic molecules of such size as to be contained totally or partially in the cavity are complexed. In water, since the cavitands are completely insoluble, the determining factor for the selectivity? of the comp? essation? l hydrophobicity? of host molecules. How much more? an organic substance? hydrophobic, all the greater? the tendency of the cavitands to complex it and the strength of their interaction. The hydrophobicity? of organic substances can? be quantified using, as a parameter, the logarithm (1n base 10) of the partition coefficient between octanol and water of the substance itself (logPoct), as described in Chem. Rev. (1971) 7J_ page 525. Organic compounds having logPoct equal to or greater than 0.7 are significantly complexed by a solid suspension of cavitand in water. Table I shows some examples relating to the extraction, by a type (A) cavitand (R = CcH.0), of typical micropollutants, indicating the corresponding logPoct. The complex that forms between cavitand and host? again a solid completely insoluble in water and therefore easily separable from the solution. By heating the complex at reduced pressure, or in a stream of inert gas, to a temperature equal to or higher than 200 C (preferably between 200 and 400 C), the simultaneous regeneration (reactivation) of the cavitand and the isolation of the extracted micro-pollutants are carried out. .
Come si vede dagli esempi, sono stati ottenuti risultati soddisfacenti con un gran numero di microinquinanti aventi logPoct superiore a 0,7; citiamo in particolare le seguenti classi di microinquinanti: As can be seen from the examples, satisfactory results have been obtained with a large number of micropollutants having logPoct higher than 0.7; we mention in particular the following classes of micropollutants:
A) gli idrocarburi aromatici, opzionalmente alogenatl e/o sostituiti con nitrogruppi (NO^) e/o con gruppi CN; A) aromatic hydrocarbons, optionally halogenated and / or substituted with nitrogroups (NO ^) and / or with CN groups;
B) le animine aromatiche, opzionalmente alogenate e/o sostituite con nitrogruppi; B) aromatic amines, optionally halogenated and / or substituted with nitrogroups;
C) le triazine e in particolare l'atrazina; C) triazines and in particular atrazine;
D) gli alogenuri alitatici aventi da 1 a 18 atomi C. D) halide halides having from 1 to 18 C atoms.
I fattori determinanti nell'efficienza di estrazione dei microinquinanti da soluzioni acquose sono la concentrazione del cavitand, 1 tempi del trattamento e la tecnica di agitazione della soluzione. La quantit? di cavitand ? di massima fra 0,1 e 2 g per litro di fluido micro-inquinato. Dai dati riportati per qualcuno dei microinquinanti in Tabella II si pu? notare che passando da una concentrazione di cavitand di 0,2 g/litro a 1 g/litro si ha un aumemento medio della percentuale di mlcrolnquinanti estratti del 25%; soltanto in pochi casi, in cui l'efficienza ? particolarmente elevata o particolarmente scarsa, non si notano variazioni apprezzabili al1'aumentare della concentrazione. Al contrario appare nulla l'Influenza della variazione di concentrazione dei microinquinanti. In tabella III sono riportati i valori di estrazione relativi ad una concentrazione media di 100 e 10 microgrammi/Iitro (ppb) di microlnquinanti aromatici. La Tabella IV riporta 1 quantitativi di microinquinanti estratti, per concentrazioni medie di 10 e 1 microgrammi/litro (ppb) di alogenurl alifatici. Difficilmente i reflui industriali e i pozzi di acque sorgive presentano una composizione di sostanze nocive costante nel tempo, e ci? crea naturalmente gravi problemi nella scelta della metodologia d1 depurazione e nella progettazione e dimensionamento dell'impianto opportuno. Il mantenimento completo dell'efficienza di estrazione da parte del cavitands, al variare della concentrazione di microinquinanti, ? quindi d1 grande importanza tecnica. The determining factors in the extraction efficiency of micropollutants from aqueous solutions are the concentration of the cavitand, the treatment times and the stirring technique of the solution. The quantity of cavitand? generally between 0.1 and 2 g per liter of micro-polluted fluid. From the data reported for some of the micropollutants in Table II you can? to note that passing from a concentration of cavitand of 0.2 g / liter to 1 g / liter there is an average increase in the percentage of extracted mlcrol pollutants of 25%; only in a few cases, in which efficiency? particularly high or particularly low, there are no appreciable variations as the concentration increases. On the contrary, the influence of the concentration variation of micropollutants appears to be null. Table III shows the extraction values relating to an average concentration of 100 and 10 micrograms / Iiter (ppb) of aromatic micro-pollutants. Table IV reports 1 quantities of extracted micropollutants, for average concentrations of 10 and 1 micrograms / liter (ppb) of aliphatic halogenurl. Industrial wastewater and spring water wells hardly have a composition of harmful substances that is constant over time, and what? naturally creates serious problems in the choice of the purification methodology and in the design and sizing of the appropriate plant. The complete maintenance of the extraction efficiency by the cavitands, as the concentration of micropollutants varies,? therefore it is of great technical importance.
I cavitands, come gi? detto, riescono ad estrarre anche quantit? estremamente piccole di microinquinanti da un fluido; essi possono essere impiegati, per esempio, per depurare soluzioni acquose in cui il tenore di microinquinanti ? fra 0,001 ppb e 100 ppm, in particolare fra 1 ppb e 100 ppm. The cavitands, as already? said, they manage to extract even quantities? extremely small micro-pollutants from a fluid; they can be used, for example, to purify aqueous solutions in which the content of micropollutants? between 0.001 ppb and 100 ppm, in particular between 1 ppb and 100 ppm.
Particolarmente interessante ? l'analisi dell'effetto del tempo di trattamento sull'efficienza di estrazione. Tra i microinquinantl presi in esame nella Tabella V possiamo individuare i seguenti gruppi di molecole ospite: Particularly interesting? the analysis of the effect of the treatment time on the extraction efficiency. Among the micropollutants examined in Table V we can identify the following groups of host molecules:
(a) molecole con elevata affinit? per il cavitand che gi? dopo 30 minuti sono quasi completamente estratte (la maggior parte degli idrocarburi aromatici); (a) molecules with high affinity for the cavitand that already? after 30 minutes they are almost completely extracted (most of the aromatic hydrocarbons);
(b) molecole con media affinit? per il cavitand per le quali la percentuale di estrazione dipende direttamente dal tempo di contatto ; (b) molecules with medium affinity for the cavitand for which the percentage of extraction directly depends on the contact time;
(c) molecole con minore affinit? per il cavitand, le cui basse percentuali di estrazione, dopo 30 minuti non vengono significativamente incrementate da tempi di contatto superiori (una parte delle aniline). (c) molecules with lower affinity for cavitand, whose low extraction percentages, after 30 minutes are not significantly increased by longer contact times (a part of the anilines).
In Tabella VI sono riportati alcuni valori di confronto tra un cavitand di tipo ed un cavitand di tipo Table VI shows some comparison values between a type cavitand and a type cavitand
Si nota che non vi ? alcuna significativa diffe? Do you notice that there? any significant diffe?
renza nell'estrazione di idrocarburi aromatici, mentre nel caso delle ammlne aromatiche il cavitand di tipo (B) ha una efficienza migliore. Un consistente incremento di efficienza di estrazione ? riscontrato utilizzando gli ultrasuoni quale sistema di agitazione; nella Tabella VII il sistema di agitazione ad ultrasuoni viene confrontato con l?usuale sistema di agitazione meccanica. In alternativa la depurazione pu? essere realizzata facendo passare una corrente di acqua Inquinata su un letto fisso di cavitand, eventualmente supportato, per esempio, su carbone attivo, silice, allumina, zeoliti, siUcaliti, sabbia, farina di diatomee eccetera. Altri dettagli circa le tecnologie di adsorbimento e rigenerazione sono rintracciabili nella pubblicazione brevettuale internazionale WO 89/08092 il cui contenuto ? parte integrante della presente descrizione. Gli esempi che seguono hanno un fine puramente illustrativo e non limitano in alcun modo la portata dell'invenzione. in the extraction of aromatic hydrocarbons, while in the case of aromatic amines the cavitand of type (B) has a better efficiency. A significant increase in extraction efficiency? found using ultrasound as a stirring system; in Table VII the ultrasonic stirring system is compared with the usual mechanical stirring system. Alternatively, the purification can? be carried out by passing a current of polluted water on a fixed bed of cavitand, possibly supported, for example, on activated carbon, silica, alumina, zeolites, silica, sand, diatomaceous earth and so on. Other details about the adsorption and regeneration technologies can be found in the international patent publication WO 89/08092 whose content? integral part of this description. The following examples are purely illustrative and do not in any way limit the scope of the invention.
ESEMPIO 1 EXAMPLE 1
(A) Preparazione di soluzioni acquose contaminate contenenti diverse concentrazioni di composti microinquinanti L?ottenimento di queste soluzioni comport? la preparazione di una soluzione madre concentrata dei composti microinquinanti in alcool ?-propilico, solvente in cui essi sono solubili e che non viene complessato dal cavitand; per diluizione della soluzione madre con acqua si ottennero le necessarie soluzioni acquose contaminate. (A) Preparation of contaminated aqueous solutions containing different concentrations of micropolluting compounds. the preparation of a concentrated stock solution of the micropolluting compounds in? -propyl alcohol, a solvent in which they are soluble and which is not complexed by cavitand; by diluting the mother solution with water, the necessary contaminated aqueous solutions were obtained.
(B) Prove di adsorbimento (in discontinuo) (B) Adsorption tests (discontinuous)
Le prove vennero effettuate mettendo in contatto la quantit? prescelta di cavitand con un volume noto di soluzione acquosa contaminata (in una beuta di vetro); l'agitazione necessaria venne realizzata mediante agitatore magnetico (200 giri/minuto). L'agitazione tramite ultrasuoni venne effettuata lasciando la beuta per un tempo prestabilito in una vaschetta ad ultrasuoni con frequenza di 48 KHz. La valutazione della capacit? complessante dei cavitands, nei confronti dei microinquinantl, ha comportato la messa a punto delle seguenti metodiche analitiche: The tests were carried out by putting in contact the quantity? pre-selected cavitand with a known volume of contaminated aqueous solution (in a glass flask); the necessary stirring was carried out by means of a magnetic stirrer (200 rpm). The ultrasonic agitation was carried out by leaving the flask for a predetermined time in an ultrasonic tank with a frequency of 48 KHz. The assessment of the capacity? complexing of the cavitands, towards the micropollutants, led to the development of the following analytical methods:
Bl) Determinazione delle ammine aromatiche e dei solventi aromatici azotati; il metodo si basava su un'estrazione in fase solida, con colonnine di silice di tipo C18 (silice trattata con alchilclorosi1ani), e sulla successiva analisi per gascromatografia capillare e rivelazione alla fiamma alcalina (NPD). Bl) Determination of aromatic amines and nitrogenous aromatic solvents; the method was based on a solid phase extraction, with C18 type silica columns (silica treated with alkylchlorosis1anes), and on the subsequent analysis by capillary gas chromatography and alkaline flame detection (NPD).
B2) Determinazione dei solventi aromatici clorurati; il metodo si basava su un'estrazione in fase solida con colonnine di silice di tipo C18 e sulla successiva analisi per gascromatografia capillare e sulla rivelazione alla cattura d1 elettroni (ECD). B2) Determination of chlorinated aromatic solvents; the method was based on a solid phase extraction with C18 type silica columns and on the subsequent analysis by capillary gas chromatography and on electron capture detection (ECD).
B3) Determinazione della naftalina; il metodo si basava su un'estrazione in fase solida, con colonnine d1 silice di tipo C18, e sulla successiva analisi per gascromatografia capillare e rivelazione a ionizzazione di fiamma (FID). B3) Determination of naphthalene; the method was based on a solid phase extraction, with silica columns of type C18, and on the subsequent analysis by capillary gas chromatography and flame ionization detection (FID).
B4) Determinazione del clorobenzene; B4) Determination of chlorobenzene;
il metodo si basava su un'analisi gascromatografica e rivelazione a ionizzazione di fiamma (FID) impiegando ia tecnica dello spazio di testa. the method was based on gas chromatography and flame ionization detection (FID) analysis using the headspace technique.
B5) Determinazione del solventi alifatici alogenati; il metodo si basava su un'analisi gascromatografica e rivelazione a cattura d1 elettroni (ECD) impiegando la tecnica dello spazio di testa. B5) Determination of halogenated aliphatic solvents; the method was based on gas chromatography analysis and electron capture detection (ECD) using the headspace technique.
(C) Riattivazione del cavitand (C) Reactivation of the cavitand
Il complesso cavitand-microinquinante che si form? dopo l'effettuazione di ogni prova venne separato dalla soluzione acquosa mediante filtrazione su setto poroso. Tale solido venne quindi riscaldata ad una temperatura tra 200 e 260 C per 4 ore, in un fornetto sotto vuoto (0,01 mm Hg). I microinquinanti complessati vennero bloccati da una opportuna trappola per essere poi alienati o recuperati. Il cavitand rigenerato era invece disponibile per nuovi cicli. Dati e risultati sono riportati nelle tabelle da I a VII. The cavitand-micropollutant complex that is formed? after carrying out each test it was separated from the aqueous solution by filtration on a porous septum. This solid was then heated to a temperature between 200 and 260 C for 4 hours, in a vacuum oven (0.01 mm Hg). The complexed micropollutants were blocked by a suitable trap to be then alienated or recovered. The regenerated cavitand was instead available for new cycles. Data and results are reported in Tables I to VII.
* ESEMPIO 2 (prova in continuo su letto fisso) * EXAMPLE 2 (continuous test on a fixed bed)
3 3
200 cm di acqua contaminata con 191 ppb di vennero eluiti su una colonna contenente 1,6 g di Cavitand di tipo (A). Vennero raccolte ed analizzate (con la metodica analitica B5), 3 200 cm of water contaminated with 191 ppb di was eluted on a column containing 1.6 g of Cavitand type (A). They were collected and analyzed (with the analytical method B5), 3
due frazioni di 4 cm ciascuna. Dati e risultati sono riportati in tabella Vili two fractions of 4 cm each. Data and results are reported in Table VIII
TABELLA Vili TABLE VIII
Quantit? di cloroformio rimosso da acqua passata su letto di Cavitand di tipo (A). Concentrazione iniziale di Quantity of chloroform removed from water passed on a Cavitand bed of type (A). Initial concentration of
191 ppb. 191 ppb.
Come si pu? notare, si ottengono comp?essazioni significative di cloroformio, anche con una percolazione di acqua inquinanta su letto fisso di Cavitand di tipo (A). How can you? to note, significant compen- sations of chloroform are obtained, even with a percolation of polluting water on a fixed bed of Cavitand type (A).
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| IT02252289A IT1237521B (en) | 1989-11-28 | 1989-11-28 | Extraction process for organic micro pollutant containing fluids, using synthetic macro cycles that can be reactivated. |
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| IT02252289A IT1237521B (en) | 1989-11-28 | 1989-11-28 | Extraction process for organic micro pollutant containing fluids, using synthetic macro cycles that can be reactivated. |
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| IT8922522A0 IT8922522A0 (en) | 1989-11-28 |
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| IT1237521B IT1237521B (en) | 1993-06-08 |
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