WO1996000271A1 - Use of carbonyl compounds for marking hydrocarbons - Google Patents

Abstract

The invention concerns the use of beta -dicarbonyl or aromatic ortho-hydroxycarbonyl compounds to mark hydrocarbons, as well as hydrocarbons containing beta -dicarbonyl or aromatic ortho-hydroxycarbonyl compounds as markers and a method of assaying beta -dicarbonyl or aromatic ortho-hydroxycarbonyl compounds in hydrocarbons.

Description

Use of carbonyl compounds for marking hydrocarbons

description

The present invention relates to the use of carbonyl compounds for labeling hydrocarbons, hydrocarbons containing carbonyl compounds as labeling agents, and to a method for detecting carbonyl compounds in hydrocarbons.

The labeling of hydrocarbons, e.g. Products from the refining of petroleum, is usually made for tax reasons, since the same product, depending on

Application purpose, can be taxed differently. For example, heating oil is usually marked, since it is taxed much less than that which is identical in composition to diesel oil.

Suitable marking agents for hydrocarbons should in particular

- have sufficient resistance under the usual conditions of use,

- do not change the physico-chemical properties of the fuel or the solvent,

have sufficient stability which enables their use even in the form of highly concentrated solutions,

- Can be separated from the marked medium by simple chemical or physical methods.

can be used even in small quantities,

be detectable by simple, fast and sensitive detection methods and

be toxicologically safe.

The object of the present invention was to provide new marking agents for liquid or liquefiable by compression hydrocarbons. Such markers should be readily available and have the property profile mentioned above. 2

It has now been found that carbonyl compounds of the formula

R! -CO-CH ₂ -CO-R ² ₍ D _or

R ^{1 is} hydrogen, -C ₄ alkyl, -C ₄ alkoxy or a radical of the formula

in der X für eine direkte Bindung, Sauerstoff oder Imino und Z¹ und Z² unabhängig voneinander jeweils für Wasserstoff, Cχ-C₄-Alkyl, Cι-C₄-Alkoxy oder Halogen stehen,

in which X is a direct bond, oxygen or imino and Z ¹ and Z ² are each independently hydrogen, Cχ-C ₄ -alkyl, Cι-C ₄ -alkoxy or halogen,

R ^{2 is} hydrogen, -CC ₄ alkyl or a radical of the formula

worin X, Z¹ und Z² jeweils die obengenannte Bedeutung besitzen,

where X, Z ¹ and Z ² each have the meaning given above,

R ^{3 is} hydrogen, hydroxy, -CC ₄ alkyl or -CC ₄ alkoxy and

L ¹ and L ² each independently represent hydrogen, hydroxy, C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy or halogen and

the ring A can be benzo-fused, advantageously for labeling hydrocarbons.

All alkyl groups occurring in the above formulas can be both straight-chain and branched.

R ¹ , R ² , R ³ , L ¹ , L ² , Z ¹ and Z ² are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. R ¹ , R ³ , L ¹ , L ² , Z ¹ and Z ² are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy.

L ¹ , L ² , Z ¹ and Z ² are, for example, fluorine, chlorine or bromine.

Labeling in the sense of the invention means an addition of the carbonyl compounds of the formula I and / or II to hydrocarbons, the hydrocarbons thereby not being visible to the human eye, but the carbonyl compounds of the formula I and / or II being changed by the here Detection methods described in more detail are easily and clearly visible.

Hydrocarbons in the sense of the invention are generally understood to mean products such as are obtained in the refining of petroleum. These are e.g. Propane, butane, pentane, hexane, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin or dimethylnaphthalene. In particular, these are mineral oils, for example fuels, such as gasoline, kerosene or diesel oil, or oils, such as heating oil or motor oil.

Furthermore, this also includes products such as those used for processing certain types of plants, e.g. Rape or sunflowers. Such products are also known under the term "bio-diesel".

The hydrocarbons are generally in the liquid state under normal conditions or are in the gaseous state and are e.g. by compression, liquefiable, e.g. Liquefied petroleum gas, such as propane or butane.

It goes without saying that the carbonyl compounds of the formulas I and II cannot be used exclusively for the labeling of hydrocarbons. With similar success, they can also be used to label other organic solvents.

Carbonyl compounds of the formula I are preferably used, in which R ^{1 is} C ¹ -C ₄ -alkyl, C ¹ -C ₄ -alkoxy or a radical of the formula

worin Z¹ und Z² jeweils die obengenannte Bedeutung besitzen, und R² Cχ-C -Alkyl bedeuten, als Markierungsmittel.

where Z ¹ and Z ² each have the meaning given above, and R ^{2 is} Cχ-C-alkyl, as a marking agent.

Furthermore, preference is given to using carbonyl compounds of the formula II in which R ^{3 is} hydrogen, hydroxy or C 1 -C 8 -alkoxy, in particular hydrogen or hydroxy, and L ¹ and L ^{2 are} each hydrogen and ring A is not benzo-fused as a marking agent .

It is particularly preferred to use carbonyl compounds of the formula I in which R ^{1 is} C ¹ -C ₄ -alkyl or C] _. -C ₄ alkoxy and R ² Cι-C ₄ alkyl, as a marking means.

Of particular importance is the use of carbonyl compounds of the formula I in which R ¹ and R ² independently of one another are each C ¹ -C ₄ -alkyl, in particular methyl, as the marking agent.

To mark the hydrocarbons, the carbonyl compounds of the formula I and / or II are used either in bulk or in the form of solutions. Organic solvents are suitable as solvents. Aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics, which is commercially available under the name Shellsol AB (Shell), are preferably used. In general, a concentration of carbonyl compound of 20 to 80% by weight, based on the solution, is chosen.

It is also possible to use other cosolvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol or cyclohexanol, glycols, such as butylethylene glycol or methylpropylene glycol, amines, such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine or xylidine, alkanolamines, such as 3- (2-methoxyethoxy) propylamine, o-cresol, m-cresol, p-cresol, ketones , such as diethyl ketone or cyclohexanone, lactones such as γ-butyrolactone, carbonates such as ethylene carbonate or propylene carbonate, phenols such as t-butylphenol or nonylphenol, esters such as methyl phthalate, ethyl phthalate, phthalate (2-ethylhexyl) ester, ethyl acetate , Butyl acetate or cyclohexyl acetate, amides such as N, N-dimethylformamide, N, N-diethylacetamide or N-methylpyrrolidinone, or mixtures thereof. Another object of the present invention are hydrocarbons containing one or more carbonyl compounds of the formula I and / or II as labeling agents.

The hydrocarbons preferably have a content of 5 to 1000 ppm, in particular 10 to 1000 ppm, of marking agent. Particularly noteworthy is a content of 10 to 500 ppm, in particular 50 to 100 ppm.

In practice, it is expedient to use rather large amounts of marking agent, so that the examination of the marked hydrocarbon in any case still gives a positive reaction, in particular with regard to a possible dilution of the hydrocarbon in the event of fraud.

In addition to the carbonyl compounds of the formula I and / or II, the hydrocarbons can also contain other labeling or denaturing agents known per se, such as furfural or C.I. Solvent Red 198 included.

It has also been found that the carbonyl compounds of the above formulas I and / or II can advantageously be detected in hydrocarbons if the hydrocarbons are treated with an aqueous-alcoholic or aqueous-acetone solution of an iron (III) salt.

Suitable iron (III) salts are e.g. Iron (IΙI) halides, such as iron (III) chloride or iron (III) bromide, iron (III) sulfate, iron (III) nitrate or iron (III) acetate. The use of ferric chloride is preferred.

The iron (III) salts are used in an aqueous-alcoholic or aqueous-acetone solution. The use of an aqueous-alcoholic solution is preferred.

Suitable alcohols for the preparation of the aqueous-alcoholic solution are e.g. Methanol, ethanol, propanol or isopropanol. The use of methanol or ethanol is preferred, the use of methanol being particularly noteworthy.

In each case, based on the weight of the reagent solution, suitable reagent solutions generally have a content of 0.05 to 0.5% by weight, preferably 0.1 to 0.3% by weight, iron (III) salts, 10 up to 90% by weight, preferably 40 to 70% by weight, of an alcohol or acetone and 10 to 90% by weight, preferably 30 to 60% by weight, Water, the total of the components of course giving 100 wt .-%.

When examining hydrocarbons which are in a liquid state under normal conditions, the detection is usually carried out by vigorously shaking about 20 ml of labeled hydrocarbon with about 2 ml of reagent solution for about 15 to 20 seconds.

Then the phase is allowed to separate. In the presence of the carbonyl compounds of the formula I and / or II, the lower aqueous phase has a red or violet-brown color. The color depends on the type of marking agent.

The content of the marking agent can be determined by methods known per se, e.g. by means of spectroscopic methods.

In the investigation of hydrocarbons which are in gaseous state under normal conditions but have been liquefied by compression, the detection is usually carried out in such a way that in a suitable container, e.g. a test tube, 1 to 2 ml of reagent solution and then drains the liquefied hydrocarbon from a gas bottle containing the liquefied hydrocarbon for about 15 to 30 seconds and collects it in the container. In this case, it is advantageous to let the hydrocarbon escape from the lying bottle, since in this case it will generally still emerge in the liquid state. Then the liquefied hydrocarbon is allowed to evaporate. In the presence of the carbonyl compounds of the formula I and / or II, the reagent solution then has a red or violet-brown color.

The carbonyl compounds of the formula I or II to be used according to the invention have the advantageous value mentioned at the outset

Property profile on. They are readily available and are well compatible with other additives which may be contained in the hydrocarbons to be labeled, e.g. Auxiliaries or other marking or denaturing agents.

The following examples are intended to explain the invention in more detail, example 1

Liquefied petroleum gas (butane), marked with acetylacetone in a concentration of 50 ppm

The butane was let out of the bottle tap for 20 seconds while the bottle was lying down, so that it emerges in liquid form. Then 20 ml of the hydrocarbon was mixed in a test tube with 2 ml of the following reagent:

0.1 g iron (III) chloride dissolved in

20 ml of water and

80 ml of methanol

After 20 seconds, the liquid gas had completely evaporated and the reagent was colored red.

Labeled propane behaves in an analogous manner.

Example 2 (comparison)

Example 1 was carried out with unmarked liquid gas. The reagent was yellow in color.

Example 3

Liquefied petroleum gas propane, labeled with salicylic acid in a concentration of 50 ppm

The test described in Example 1 was repeated. The reagent was clearly purple in color.

Labeled butane behaves in an analogous manner.

Example 4

20 ml of diesel oil marked with 50 ppm acetylacetone were placed in a separatory funnel. Then 2 ml of the reagent described in Example 1 were added and the mixture was shaken vigorously for 20 seconds. They were then allowed to sit down. The phases separated after 5 minutes. The lower aqueous phase was clearly red in color. Example 5

1 ml of the labeled diesel oil from Example 4 was diluted with 9 ml of unlabeled diesel oil. The procedure described in Example 4 was repeated with this mixture. The lower aqueous phase was slightly red in color.

Example 6 (comparison)

The procedure described in Example 4 was carried out with 20 ml of unlabeled diesel oil. The lower aqueous phase remained yellow.

Example 7

20 ml of diesel oil, labeled with 50 ppm salicylic acid, were placed in a separatory funnel. Then 2 ml of the reagent described in Example 1 were added and the mixture was shaken vigorously for 20 seconds. They were then allowed to sit down. The phases separated after 5 minutes. The lower aqueous phase was colored violet.

The examples listed in the following table were carried out in an analogous manner.

Example Markie Coal Concentration Reaction Agent hydrogen tration Color [ppm]

8 acetyl liquid gas 50 red acetone (butane)

9 acetyl liquid gas ^* 30 red acetone (butane)

10 acetyl-lead-free 50 red acetone gasoline

11 Acetyl Superben 50 Red Acetone Zin ^** >

12 Acetyl diesel 50 red acetone

13 Acetyl diesel 5 pink acetone

14 Acetoacetic liquid gas 50 Red acid methyl ester

15 Acetoacetic acid diesel oil 500 red acid methyl ester

16 Acetoacetic lead-free 500 red acid petrol methyl ester Example Markie Coal Concentration Reaction Agent hydrogen tration Color [ppm]

17 Acetoacetic- lead-free 500 red acid ethyl gasoline ester

18 Acetoacetic acid diesel oil 500 red acid ethyl ester

19 Acetoacetic lead-free 500 red acid butyl gasoline ester

20 Acetoacetic acid diesel oil 500 red acid butyl ester

21 Acetoacetic- lead-free 100 brown acid-N-gasoline (3-methylphenyl) amide

22 Acetoacetic-Diesel Oil 100 Brown Acid-N- (3-methylphenyl) amide

23 Salicylic liquid gas 50 Violet acid (butane)

24 Salicyl¬ Superben- 50 violet acid tin **>

25 salicylic diesel 50 violet acid

26 Salicylic lead-free 500 violet acid gasoline

27 Salicylic Diesel 100 Violet aldehyde

^* 'also contained 10 ppm furfural

^** > additionally contained 20 ppm CI Solvent Red 198

Claims

Claims 1. Use of carbonyl compounds of the formula R ¹ -CO-CH ₂ -CO-R ² (I) or

wherein R ^{1 is} hydrogen, -C ₄ alkyl, -C ₄ alkoxy or a radical of the formula

in which X represents a direct bond, oxygen or imino and Z ¹ and Z ² independently of one another each represent hydrogen, C 1 -C ₄ -alkyl, C 1 -C ₄ alkoxy or halogen, R ^{2 is} hydrogen, -CC ₄ alkyl or a radical of the formula in which X, Z ¹ and DZ ² each have the meaning given above, R ^{3 is} hydrogen, hydroxy, -CC alkyl or -CC ₄ alkoxy and L ¹ and L ² are each independently hydrogen, Hydroxy, -CC ₄ alkyl, -C ₄ alkoxy or halogen mean and ring A may be fused to benzo for marking hydrocarbons. Use of carbonyl compounds of the formula I according to claim 1, characterized in that R ^{1 is} C ¹ -C ₄ alkyl, C ¹ -C ₄ alkoxy or a radical of the formula

wherein Z ¹ and Z ² each have the meaning given in claim 1, and R ^{2 is} C 1 -C 4 -alkyl. 3. Use of carbonyl compounds of the formula II according to claim 1, characterized in that R ^{3 is} hydrogen, hydroxy or -CC ₄ alkoxy, and L ¹ and L ^{2 are} each hydrogen and the ring A is not benzo-fused. 4. Use of carbonyl compounds of the formula I according to claim 1, characterized in that R ^{1 is} C ¹ -C ₄ -alkyl or C ¹ -C ₄ -alkoxy and R ^{2 is} C ¹ -C ₄ -alkyl. 5. Use of carbonyl compounds of the formula I according to claim 1, characterized in that R ¹ and R ² each independently represent C 1 -C 4 -alkyl. 6. hydrocarbons containing one or more carbonyl compounds according to claim 1 as a marking agent. 7. hydrocarbons containing 5 to 1000 ppm of one or more carbonyl compounds according to claim 1 as a marking agent. 8. A method for the detection of carbonyl compounds of the formulas I and / or II according to claim 1 in hydrocarbons, characterized in that the hydrocarbons are treated with an aqueous-alcoholic or aqueous-acetone solution of an iron (III) salt. Use of carbonyl compounds for marking hydrocarbons Summary Use of ß-dicarbonyl or aromatic ortho-hydroxycarbonyl compounds for labeling hydrocarbons, hydrocarbons containing ß-dicarbonyl or aromatic ortho-hydroxycarbonyl compounds as labeling agents, and a method for the detection of ß-dicarbonyl or aromatic ortho-hydroxycarbonyl compounds in hydrocarbons.