ITMI941320A1 - Composizione marcante-denaturante particolarmente adatta per marcare e denaturare combustibili - Google Patents

Composizione marcante-denaturante particolarmente adatta per marcare e denaturare combustibili Download PDF

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Publication number
ITMI941320A1
ITMI941320A1 IT001320A ITMI941320A ITMI941320A1 IT MI941320 A1 ITMI941320 A1 IT MI941320A1 IT 001320 A IT001320 A IT 001320A IT MI941320 A ITMI941320 A IT MI941320A IT MI941320 A1 ITMI941320 A1 IT MI941320A1
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IT
Italy
Prior art keywords
denaturing
marking
fuels
composition according
liquefiable
Prior art date
Application number
IT001320A
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English (en)
Inventor
Francesco Piscitelli
Silvana Rabacchi
Virginio Sarto
Original Assignee
Basf Italia
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.)
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Publication date
Application filed by Basf Italia filed Critical Basf Italia
Publication of ITMI941320A0 publication Critical patent/ITMI941320A0/it
Priority to ITMI941320A priority Critical patent/IT1269947B/it
Priority to CA002193886A priority patent/CA2193886A1/en
Priority to EP95923333A priority patent/EP0766724A1/de
Priority to BR9508104A priority patent/BR9508104A/pt
Priority to JP8502759A priority patent/JPH10502111A/ja
Priority to HU9603550A priority patent/HUT76753A/hu
Priority to PCT/EP1995/002330 priority patent/WO1996000271A1/de
Priority to MX9700119A priority patent/MX9700119A/es
Priority to AU27928/95A priority patent/AU2792895A/en
Priority to PL95317941A priority patent/PL317941A1/xx
Priority to CZ963792A priority patent/CZ379296A3/cs
Priority to IL11419595A priority patent/IL114195A0/xx
Priority to CO95027629A priority patent/CO4410389A1/es
Publication of ITMI941320A1 publication Critical patent/ITMI941320A1/it
Priority to NO965554A priority patent/NO965554L/no
Application granted granted Critical
Publication of IT1269947B publication Critical patent/IT1269947B/it

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Description

Descrizione del brevetto per invenzione industriale avente per titolo:
"Composizione marcante-denaturante particolarmente adatta per marcare e denaturare prodotti combustibili".
DESCRIZIONE
L'invenzione si riferisce ad una composizione marcante e denaturante particolarmente adatta, alla marcatura e denaturazione di combustibili liquidi o liquefacibili per compressione.
E' noto ai tecnici del ramo che la denaturazione di combustibili liquidi o liquefacibili per compressione consiste nell'aggiungere degli appositi additivi, chiamati denaturanti, la cui presenza in detti combustibili è rivelabile mediante trattamento con opportuni reagenti; inoltre, la loro quantità può essere determinata per mezzo di una semplice reazione colorimetrica.
E' correntemente necessario marcare i prodotti petroliferi (per esempio i combustibili o i solventi industriali) a causa della differenza di prezzo con la quale lo stesso prodotto può essere commercializzato .
Infatti, come conseguenza di diversi rapporti di tassazione, gasoli per scopi agricoli o per industria della pesca, hanno aliquote di tassazione più basse del gasolio per autotrazione, pertanto, questa situazione è soggetta a subire frodi fiscali quando il prodotto viene utilizzato per scopi differenti da quelli previsti dai regolamenti tributari.
Un marcante o una composizione marcante ideali dovrebbero possedere le seguenti caratteristiche;
soddisfacente stabilità nelle normali condizioni d'uso
non alterare le caratteristiche chimico-fisiche del combustibile o del solvente
- sufficiente stabilità per permetterne l'uso in forme di soluzione concentrata
ridottissime possibilità di eliminazione per mezzo di metodi chimici o fisici
- possibilità di uso in piccole quantità - possibilità di identificazione per mezzo di metodi semplici, veloci e sensibili
- assenza di caratteristiche tossicologiche. La richiedente ha ora trovato una nuova famiglia di sostanze marcanti che presenta le caratteristiche chimico-fisiche adatte alla marcatura di una larga serie di prodotti combustibili derivante sia dalla distillazione del petrolio che da altri tipi di produzione (per es. biodiesel) .
Nella sua forma più ampia, l'invenzione consiste in una composizione marcante e denaturante particolarmente adatta per combustibili liquidi o liquefacibili derivanti dalla distillazione del petrolio e altri prodotti equivalenti (ad esempio a combustibili ottenuti da trattamento di vegetali) a base uno o più prodotti organici corrispondenti alle seguenti formule (I) o (II):
O O II II
R1 C CH 2CR2 ( I )
dove
R1 e R2 sono uguali o diversi e rappresentano :
H, (C1-C4) alchile oppure
dove
X = H, N H oppure O, e
Z , Y = CH3, oppure alogeno
M = H, OH oppure (C1-C4) alchile e
L, T = H, OH, (C1-C4) alchile, alogeno, oppure un anello aromatico.
Secondo la presente invenzione, la quantità di prodotto da impiegare come marcante può variare entro ampi limiti e il valore minimo dipende sia dal particolare prodotto impiegato che dal test di identificazione .
Impiegando come marcante il composto con R1=R2=-CH3 (2,4-pentandione) e usando il semplice e rapido test per il riconoscimento qualitativo descritto in seguito possono essere usate concentrazioni fino a 5 ppm.
Con lo stesso metodo, il marcante può successivamente essere dosato in modo quantitativo. In pratica, è opportuno aggiungere quantità maggiori di prodotto marcante, di modo che il test risulti positivo in ogni caso, anche in previsione di una possibile diluizione in caso di frode.
Da un punto di vista pratico, possono essere usate da 10 a 500 ppm (preferibilmente 50-100 ppm) di marcante.
I vantaggi connessi con questo derivato organico sono i seguenti:
- nessuna modificazione delle caratteristiche chimico-fisiche dei carburanti;
nessuna modificazione di colore del carburante ;
- può essere maneggiato sia come composto puro che come soluzione in solventi organici compatibili con i carburanti, come ad esempio solventi aromatici come xilene, oppure paraffinici, oppure alcoli come l'isobutanolo e simili;
compatibilità con altre sostanze denaturanti, eventualmente già presenti nel carburante, quali, per esempio, furfurolo o coloranti organici quale Solvent Red 198.
Secondo la presente invenzione, per l'identificazione del prodotto si può usare un reattivo consistente in una soluzione diluita idro-alcolica o idro-acetonica di sali di Fe (III).
Nel caso di carburanti liquidi, a condizioni ambiente (ad esempio benzina o gasolio) si aggiungono 2 ml di reattivo a 20 ml di carburante marcato, in imbuto separatore. Si agita energeticamente per 15-20 secondi la miscela e poi si lascia stratificare. Si formano 2 fasi. In presenza di marcante la fase sottostante si colora di rosso o di viola-bruno a seconda del composto impiegato .
La quantità di marcante presente può essere dosata quantitativamente eseguendo una lettura spettrofotometrica, nel campo del visibile, operando sul contenuto della fase inferiore.
Nel caso di carburanti gassosi a condizioni ambiente, ma usualmente liquefatti per compressione (ad esempio GPL) il saggio viene eseguito nel seguente modo:
si pongono in una provetta 1-2 ml di reattivo e poi si lascia fuoriuscire dal contenitore del GPL, raccogliendo, nella provetta stessa, una certa quantità di carburante liquefatto.
Si lascia evaporare il GPL e in circa 15-20 secondi, in presenza di marcante, il reattivo si colora analogamente a quanto avviene con i carburanti liquidi.
Gli esempi che seguono servono a meglio illustrare la presente invenzione, senza, tuttavia, limitarla.
Esempio 1
GPL, in bombola, marcato con 2,4-pentandione, ad una concentrazione di 50 ppm. Dal rubinetto della bombola si fa uscire, per 15-20 secondi, del carburante, tenendo la bombola capovolta, (in modo che il carburante esca ancora allo stato liquido) e lo si raccoglie in una provetta contenente 1-2 mi del seguente reattivo:
0,1 g di FeC13 disciolto in
20 ml di acqua e
80 ml di metanolo.
In 15-20 secondi, il GPL evapora completamente e il reattivo si colora di rosso.
Esempio 2 (Confronto)
Questo esempio, è un esempio di confronto per dimostrare l'efficacia e la funzionalità del marcante secondo la presente invenzione. La stessa prova dell'esempio 1 viene eseguita con del GPL non marcato: il reattivo rimane di colore giallo.
Esempio 3
GPL in bombola marcato con acido salicilico (acido 2-idrossibenzoico) ad una concentrazione di 50 ppm. Si ripete il saggio descritto all'esempio 1: il reattivo si colora nettamente di viola.
Esempio 4
20 ml di gasolio marcato ad una concentrazione di 50 ppm con 2,4-pentandione vengono messi in imbuto separatore. Quindi si aggiungono 2 mi del reattivo descritto nell'Esempio 1 e si agita vigorosamente la miscela per 15-20 secondi. Si lascia decantare. Dopo circa 5 minuti si separano due fasi, l'inferiore delle quali risulta nettamente colorata di rosso.
Esempio 5
1 ml di gasolio, marcato come nell'esempio 4, è diluito con 9 ml di gasolio non marcato. Si ripete il saggio descritto all'esempio 4. La fase inferiore risulta ancora debolmente colorata di rosso.
Esemplo 6 (Confronto)
Si esegue il saggio descritto all'esempio 4, su 20 ml di gasolio non marcato: la fase inferiore rimane gialla.
Esempio 7
20 ml di gasolio, marcato ad una concentrazione di 50 ppm con acido salicilico (acido 2-idrossibenzoico), vengono messi in imbuto separatore. Quindi si aggiungono 2 ml di reattivo e si agita vigorosamente la miscela per 15-20
secondi. Si lascia decantare. Dopo circa 5 minuti si separano due fasi, l'inferiore delle quali è nettamente colorata di viola.
Esempi 8-27
Si è sostanzialmente ripetuta la procedura descritta nell'esempio 1, nel caso di combustibili GPL e quella descritta nell'esempio 4 per i gasoli o per le benzine, apportando di volta in volta le modifiche indicate nella Tabella che segue:
(1)contenenteanche 10ppm difurfurolo
(2)coloratacon 20 ppa diSolventRed 198

Claims (1)

  1. RIVENDICAZIONI 1. Composizione marcante e denaturante, particolarmente adatta per marcare e denaturare prodotti combustibili liquidi, o liquefacibili per compressione, a base di un derivato β-dicarbonilico di formula (I), oppure da un derivato orto-idrossicarbonilico di formula (II): dove R1 e sono uguali o diversi e rappresentano: H, (C1 -C4) alchile oppure dove X - H, N H oppure 0, e Z, Y = CH3, oppure alogeno in cui M = H, OH oppure alchile e L, T = H, OH, (C1-C4) alchile, alogeno, oppure un anello aromatico 2. Composizione marcante e denaturante secondo la rivendicazione 1, contenente anche un solvente organico aromatico oppure un alcool. 3. Composizione marcante e denaturante secondo le rivendicazioni 1 e 2, contenente eventualmente anche furfurolo. 4. Composizione marcante e denaturante secondo le rivendicazioni 1, 2 0 3 contenente eventualmente anche coloranti del tipo comunemente usato nell'industria dei carburanti. 5. Carburanti liquidi o liquefacibili per compressione caratterizzati dal fatto di contenere da 10 a 1000 ppm di una composizione secondo la rivendicazione 1. 6. Carburanti liquidi o liquefacibili caratterizzati dal fatto di contenere da 30 a 500 ppm di una composizione secondo la rivendicazione 1. 7. Carburanti liquidi o liquefacibili per compressione secondo la rivendicazione 4, caratterizzati dal fatto che la composizione secondo la rivendicazione 1 è costituita sostanzialmente dal composto 2,4-pentandione. 8. Gas di petrolio liquefatto (GPL) secondo la rivendicazione 5, caratterizzato dal fatto che la composizione secondo la rivendicazione 1 è costituita sostanzialmente dal composto 2,4-pentandione. 9. Gas di petrolio liquefatto (GPL) secondo la rivendicazione 7, contenente anche furfurolo.
ITMI941320A 1994-06-24 1994-06-24 Composizione marcante-denaturante particolarmente adatta per marcare e denaturare combustibili IT1269947B (it)

Priority Applications (14)

Application Number Priority Date Filing Date Title
ITMI941320A IT1269947B (it) 1994-06-24 1994-06-24 Composizione marcante-denaturante particolarmente adatta per marcare e denaturare combustibili
PCT/EP1995/002330 WO1996000271A1 (de) 1994-06-24 1995-06-16 Verwendung von carbonylverbindungen zum markieren von kohlenwasserstoffen
AU27928/95A AU2792895A (en) 1994-06-24 1995-06-16 Use of carbonyl compounds for marking hydrocarbons
BR9508104A BR9508104A (pt) 1994-06-24 1995-06-16 Uso de composto de carbonila hidrocarboneto e processo para detectar composto de carbonila
JP8502759A JPH10502111A (ja) 1994-06-24 1995-06-16 炭化水素の標識のためのカルボニル化合物の使用
HU9603550A HUT76753A (en) 1994-06-24 1995-06-16 Use of carbonil compounds for marking hydrocarbons
CA002193886A CA2193886A1 (en) 1994-06-24 1995-06-16 Use of carbonyl compounds for marking hydrocarbons
MX9700119A MX9700119A (es) 1994-06-24 1995-06-16 Uso de compuestos de carbonilo como marcadores para hidrocarburos.
EP95923333A EP0766724A1 (de) 1994-06-24 1995-06-16 Verwendung von carbonylverbindungen zum markieren von kohlenwasserstoffen
PL95317941A PL317941A1 (en) 1994-06-24 1995-06-16 Application od carbonyl compounds for labelling hydrocarbons
CZ963792A CZ379296A3 (en) 1994-06-24 1995-06-16 Use of carbonyl compounds for labelling hydrocarbons, method of their detection in hydrocarbons and hydrocarbons containing thereof
IL11419595A IL114195A0 (en) 1994-06-24 1995-06-16 Use of carbonyl compounds as markers for hydrocarbons
CO95027629A CO4410389A1 (es) 1994-06-24 1995-06-22 Hidrocarburos que comprenden uno o mas compuestos de carbo- nilo
NO965554A NO965554L (no) 1994-06-24 1996-12-23 Anvendelse av karbonylforbindelser for markering av hydrokarboner

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FR2787577B1 (fr) * 1998-12-16 2001-03-02 Total Raffinage Distrib Indicateur colore pour la mesure de la repartition des familles d'hydrocarbures contenues dans un melange, son procede d'obtention et ses utilisations
FR2971254B1 (fr) * 2011-02-08 2014-05-30 Total Raffinage Marketing Compositions liquides pour marquer les carburants et combustibles hydrocarbones liquides, carburants et combustibles les contenant et procede de detection des marqueurs
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GB287192A (en) * 1926-10-25 1928-03-22 British Dyestuffs Corp Ltd Improvements in and relating to fuels for internal combustion engines
GB473653A (en) * 1936-04-15 1937-10-15 Ig Farbenindustrie Ag Improvements in the manufacture and production of carbon compounds of high molecularweight
US2205408A (en) * 1938-08-09 1940-06-25 Gen Aniline & Film Corp Fluorescent hydrocarbon oil
US3508875A (en) * 1967-10-03 1970-04-28 Union Oil Co Method for tracing the flow of water in subterranean formations
NL7103060A (it) * 1970-03-11 1971-09-14
IT1222752B (it) * 1987-09-28 1990-09-12 Acna Chimica Organica Metodo di marcatura di prodotti petroliferi e di solventi organici
GB8802237D0 (en) * 1988-02-02 1988-03-02 Shell Int Research Detection of chemicals by immunoassay
FR2650606B1 (fr) * 1989-08-07 1992-04-30 Aussedat Rey Papier de securite infalsifiable et composition aqueuse ou organique utile, notamment pour rendre un papier infalsifiable
JPH048798A (ja) * 1990-04-26 1992-01-13 Yoshibi:Kk 高輝度有色炎発生用液化ガス燃料
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CO4410389A1 (es) 1997-01-09
ITMI941320A0 (it) 1994-06-24
IT1269947B (it) 1997-04-16
CA2193886A1 (en) 1996-01-04
EP0766724A1 (de) 1997-04-09
JPH10502111A (ja) 1998-02-24
HU9603550D0 (en) 1997-02-28
NO965554L (no) 1997-02-18
AU2792895A (en) 1996-01-19
NO965554D0 (no) 1996-12-23
MX9700119A (es) 1997-04-30
CZ379296A3 (en) 1997-06-11
WO1996000271A1 (de) 1996-01-04
BR9508104A (pt) 1997-08-12
HUT76753A (en) 1997-11-28
IL114195A0 (en) 1995-10-31
PL317941A1 (en) 1997-05-12

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