JPH02216457A - Identifying agent for petroleum product and method for adding this agent - Google Patents

Abstract

PURPOSE:To allow the easy addition of the identifying agent to petroleum products by using the compd. expressed by the prescribed formula. CONSTITUTION:The identifying agent of the petroleum products expressed by the formula I is dissolved in an org. solvent and the org. solvent is dissolved in the petroleum products. In the formula I, R1 and R2 denote a hydrogen atom or substd. or unsubstd. alkyl group; R3 and R4 denote a hydrogen atom or alkyl group, R1 and R2, both of which are the hydrogen atom, are excluded. In the formula I, R1 and R2 may be 1 to 12C straight chain or branched alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an identification agent added to petroleum products for the purpose of preventing tax evasion on petroleum products, and a method for adding the same.

In Japan, gasoline is taxed as a power fuel tax in the form of volatile speech and local road commentary, diesel oil is taxed as a diesel oil withdrawal tax, and aviation fuel is taxed as an aviation fuel tax. Mixing and selling different petroleum products is prohibited under tax laws and is also undesirable from a safety standpoint.

From this perspective, technology for identifying or quantifying the types of petroleum products is needed.

[Prior Art] As a method for identifying the type of petroleum product, there is a simple method for identifying gasoline mixed with kerosene (Japanese Patent Publication No. 53-37756 , Japanese Patent Publication No. 55-28020). However, this method is qualitative and cannot be quantitatively determined, and furthermore, it cannot be identified unless the amount of kerosene mixed in is within a certain range.

Additionally, consideration is being given to establishing a system in which an identification agent is added to petroleum products in advance and then distributed throughout the cloth, and the identification agent is analyzed and identified during inspections. One such method involves using a quinizarin derivative as an identification agent and observing the uniquely colored extract produced by extracting the quinizarin derivative at the time of inspection (Japanese Patent Publication No. 52-47).
718 Publication) and a method for identification and quantification using a bisazo colorant as an identification agent (Japanese Patent Publication No. 57-3694)
Publication No. 0). Furthermore, in the UK, kerosene is colored with coumarin, heating diesel oil is colored with an ab-based dye, and quinizarin is used as an identification agent.
In France, azo dyes and furfural are used as identification agents in heating oil.

However, none of these are fully satisfactory as identification agents for petroleum products. For example, quinizarins are extracted with aqueous caustic alkaline solution and identified by the resulting purple extract, but it is not easy to identify them. It has the disadvantage that it can be easily removed. Furfural produces a strong red complex salt with aniline acetate, but since furfural is originally contained in petroleum products, this method cannot be used to reliably identify it. It is said that it decomposes after about 6 months of storage, and there are problems with its stability.

Diphenylamine similarly requires a color reaction and cannot be easily identified, and is also unstable. Coumarin is extracted and hydrolyzed in a caustic aqueous solution and identified by observing the fluorescence of the resulting hydroxycinnamate aqueous solution, but this is not an easy identification method. Also, like quinizarin, it has the disadvantage that it can be easily removed with an alkaline aqueous solution.

[Problems to be solved by the invention] The following items are necessary for an identification agent for petroleum products.

(1)! It can simply be identified.

(2) It cannot be removed from petroleum products by simple operations.

(3) Can be identified with a small amount added.

(4) Not interfered with by impurities or other additives in petroleum products.

(5) Remains stable during storage.

(6) Can be easily added to petroleum products at a predetermined concentration.

(7) It is inexpensive.

(8) Knowledge 11.　　Quantitative determination can be performed with simple operations.

The present invention provides an identifying agent for petroleum products that satisfies the requirements (1) to (8) above, and also provides a simple method for adding the identifying agent to petroleum products.

[Means for solving the problems] The present invention is based on the general formula (1) (wherein R1 and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl group, N R3 and R4 represent a hydrogen atom or a methyl group) .

However, those in which RI and R2 are both hydrogen atoms are excluded. ) is an identification agent for petroleum products. Further, there is a method for adding the discriminating agent of the present invention to petroleum products, the gist of which is dissolving the discriminating agent of the present invention in an organic solvent and dissolving the organic solvent in the petroleum product.

Petroleum products as used in the present invention refer to liquid carbon-hydrogen compounds obtained from petroleum, such as gasoline, light oil, and thinners.

The identification agent of the present invention can be easily quantified in petroleum products using a fluorescence spectrophotometer without using conventional separation analysis means such as liquid chromatography. Also,
More conveniently, the type of petroleum product can be easily qualitatively identified by irradiating the petroleum product to which the identification agent of the present invention has been added in a dark place with excitation light and observing the generated fluorescence. The blended amount of the petroleum product can be determined informally by color comparison with a standard solution to which a predetermined amount of identification agent has been added. Specifically, during roadside checks, storage monitoring, etc., the extracted petroleum product is placed in a colorimetric tube, etc., and the fluorescence generated by the identification agent is observed by irradiating it with excitation light such as a black light in a dark box. This makes it possible to easily identify the oil type of a petroleum product on the spot. In addition, it is safer than quinizarin and coumarin, which are conventionally used as identification agents, because it does not require an alkaline aqueous solution. Moreover, the discriminating agent of the present invention has the advantage that it is not extracted by an alkaline aqueous solution and is stable in an alkaline aqueous solution, so that the added discriminating agent is not easily removed from petroleum products.

Furthermore, it has been found that the identification agent of the present invention has a high fluorescence quantum efficiency and can be detected even at a low concentration of about 0.2 ppm+ in petroleum products. That is, if 20 pp of the identification agent of the present invention is added to a petroleum product and shipped in cloth, it can be detected even if an illegal person mixes 1 part of this petroleum product with 99 parts of a different petroleum product.

Therefore, by using the identification agent of the present invention, it is possible to reduce the amount of identification agent added to petroleum products, and it is possible to reduce the amount of foreign matter in the original use of petroleum products, which is preferable.

As described above, the petroleum product identification agent of the present invention is a compound represented by the general formula (1).

The alkyl groups of R8 and R2 may be either straight chain or branched alkyl groups, and the alkyl groups are C, H.

It may have 0 substituents. Also, R1,
When one of Rz is a hydrogen atom, its tautomer is included in the present invention. Considering the use of the added petroleum product, it seems that alkylsilane groups are not desirable unless it is for a specific purpose such as preventing air pollution or preventing corrosion of engines, etc. Furthermore, if the alkyl group is too large, the solubility in petroleum products will decrease. Therefore,
In order to reduce the amount added to petroleum products, it is preferable to use a discriminating agent in which R1 and R2 are straight or branched alkyl groups having 1 to 12 carbon atoms.

When adding the discriminating agent of the present invention to petroleum products, if the discriminating agent is added directly to the petroleum product, it will be difficult to dissolve, and some parts may precipitate or the concentration may not be uniform. Therefore, in the method of adding an identification agent to a petroleum product according to the present invention, the identification agent is dissolved in an organic solvent, and the organic solvent is dissolved in the petroleum product. To give an example of a specific operation, it can be easily carried out by preparing a concentrated solution in which the identification agent is dissolved in these organic solvents at a high concentration, and then supplying a predetermined amount of this concentrated solution with a metering pump or the like. can. As an excellent feature of the discriminating agent of the present invention, compared to conventional quinizarine, azo-based, and anthraquinone-based discriminating agents, it is possible to use aromatic hydrocarbons such as benzene, toluene, and xylene, and organic solvents such as ethers, ketones, and esters. Therefore, the organic solvent used in the addition method of the present invention can be appropriately selected from a wide range of solvents.

The preferable addition amounts of the discriminating agent of the present invention are R1, R2, Rs-
Although it varies depending on the structure of the substituent for R4 and where the detection limit is set, 20 ppm or less is usually sufficient. The identification agent of the present invention is added in an amount of about 5% in petroleum products.
At concentrations of more than 1 ppm, petroleum products are colored yellow-green and have the performance as a coloring agent and can be identified with the naked eye, and at approximately 1 ppm
At +s, green fluorescence is generated by irradiation with excitation light and can be identified. Furthermore, petroleum products usually emit blue fluorescence due to impurities contained therein, but since the fluorescence wavelength is different from that of the identification agent of the present invention, there is no problem in identification.

In addition, regarding the stability of the identification agent of the present invention, petroleum products are usually kept in a dark place, and under such conditions, it has sufficient stability compared to furfural, diphenylamines, etc., and there is no problem in practical use. .

The compound of formula (1), which is the discriminating agent of the present invention, has the following formula (II
) in an organic solvent, if necessary with base support (II
> [R3 and R4 in the formula are the same as in formula (r)] In the presence of a medium, R10SO2R', R20SO1! R
It is synthesized by reacting with (R10)2SO2, (R20)ZSO2 alkyl sulfate, RIX1R2X alkyl halide, etc. Further, it can be synthesized by an ionic reaction radical reaction between the compound of formula (II) and a carbon double bond. The compound of formula (■) is synthesized by the reaction of succinic acid diester and benzonitriles, and the compound having substituents R1 and R3 is synthesized by alkylating sulfonic acid ester, sulfuric acid ester, or alkyl halide. It can be produced at low cost as a drug. Therefore, an increase in the cost of petroleum products, which are required to be inexpensive for both consumer and industrial use, can be minimized.

[Examples] The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these Examples.

(1) Synthesis of discriminating agent 2.5-dihydro-3,6-diphenylpyrrolo[3,4
-c ] ] 14.5 parts of virole-1,4-dione and 27.6 parts of potassium carbonate were added to 200 parts of dimethylformamide and stirred, and a solution of 27.4 parts of 1-bromobutane and 27.4 parts of dimethylformamide was heated at 140°C. was added over 60 minutes and reacted for approximately 30 minutes. After cooling, it was filtered, and water was added for crystallization. After washing with methanol, it was dried. Recrystallization from n-hexane gave 2,5-di-n-butyl-2,5-dihydro-3,6-diphenylpyrrolo[3,4-c]virol-1,4-dione (hereinafter , the double compound 1 (
R1 and R2 in I) are n-butyl &R, and R4
is a hydrogen atom).

(2) Additive compound 1 to petroleum products as an identification agent, each with a concentration of 10 ppm
, 0. 5ppm, 0. 2ppa+ was added to kerosene. Although the mixture was stirred at room temperature for 30 minutes, some of the mixture remained undissolved, so the mixture was heated slightly to dissolve it all. A yellow colored kerosene was obtained.

(3) Analysis of identification agents in petroleum products Kerosene to which Compound 1 was added and kerosene without additive were each sampled into a 50nl colorimeter, and the fluorescence generated was observed and compared by shining a black light in a dark place. Table 1 shows the results.
It was shown to.

Quinizarin, coumarin, furfural, and diphenylamine were used as discriminating agents in place of Compound 1, and each was added to kerosene in the same manner as in Example 1, and the discriminating agents in kerosene were analyzed. The results are shown in Table 1.

As is clear from Table 1, Compound 1 was colored yellow at 10 ppm, and at 0.0 ppm. At 5 ppm it shows a clear green color, and at 0.5 ppm it shows a clear green color. At 2 ppm, it showed a pale green color and could be clearly identified by comparison with the additive-free product. On the other hand, quinizarin was colored orange at 10 ppm, but at 0.
No difference was observed in 5pp+* compared to no additive, and no difference was observed in coumarin, furfural, and diphenylamine compared to no additive, and none of them could be identified.

From the above, Compound 1 has not only 10 ppm but also 0,
5-0. It is an excellent discriminating agent that can be identified by shining a black light in a dark place even at a low concentration of 2 ppm.

Table 1 *A color similar to that of kerosene without the addition of an identification agent was determined to be colorless.

Reference J - Example Compound 1 and Quinizarin, Coumarin 10 as discriminating agents
20 ml of 5% caustic soda aqueous solution was added to 5011 ppm of kerosene, stirred for 30 minutes, and allowed to stand still. The kerosene obtained by separating the solution was subjected to an identification test.

5% caustic soda solution of kerosene with quinizarin as identification agent 5
ml was added and extracted, but the extract showed only a faint purple color and the identifying agent had been removed.

Kerosene containing coumarin as an identifying agent was extracted by adding 5 liters of a 5% caustic soda solution, but the extract showed only a slight fluorescence and the identifying agent had been removed.

Kerosene using Compound 1 as an identification agent was not extracted by the 5% caustic soda aqueous solution and could not be removed.

Furthermore, this kerosene was mixed with a compound 1 concentration of 0. 5ppm+.

0, 21) When diluted with kerosene so as to give P-peng and tested in the same manner as in Example 1, it was possible to identify the same as in Example 1.

1 Direct Story-2 Add Compound 1 to 0.0% of automobile diesel oil. It was added at a concentration of 5 ppm. When compared with additive-free automobile diesel oil as in Example 1, it showed a clear green color and was distinguishable.

The identification of a petroleum product to which Uratane ■-Yu Compound 1 was mixed with a different petroleum product was investigated.

The compound of Example 1 was added to kerosene in an amount of 2 SpP, and one part thereof was mixed with 49 parts of automobile diesel oil. Similar to Example 1, when compared with additive-free automobile diesel oil,
It showed a clear green color and could be identified.

Fruit] 01-A.

We investigated the method of adding Compound 1 to petroleum products.

Compound 1 was dissolved in xylene to make a 15% by weight solution. When this solution was added to kerosene so that the concentration of the discriminating agent (compound 1) was 10PP hazy, it was quickly diffused and yellow colored kerosene was obtained.

Toru Kasumi-5 (1) Synthesis of iI separate agent 2,5-dihydro-3,6-diphenylpyrrolo[3,4
14.5 parts of -cl pyrrole-1,4-dione and 27.6 parts of anhydrous potassium carbonate were added to 200 parts of dimethylformamide and stirred, and the mixture was heated to 140°C with 41.0 parts of p-toluenesulfonic acid methyl ester and 50.9 parts of dimethylformamide. 0
of the solution was added over 60 minutes, and the reaction was continued for an additional 30 minutes. After cooling, it was filtered, and water was added for crystallization. After washing with methanol, it was dried. Mixed solution of ethanol and toluene 1 (3:2
) to give 2,5-dihydro-2,5-dimethyl-3,6-diphenylpyrrolo[3,4-cl pyrrolo-
1,4-dione (hereinafter referred to as compound 2 of formula 8 (I
), R1 and R2 are methyl & R3 and R4 are hydrogen atoms).

(2) Addition to petroleum products Compound 2 was dissolved in toluene in the same manner as in Example 4, and then added to kerosene at a concentration of 0.5 ppm.

(3) Analysis of identification agents in petroleum products Comparisons were made in the same manner as in Example 1 with additive-free kerosene. the result,
It showed green fluorescence and could be identified.

Uradane-1 As an identification agent, 2,5-di-n-butyl-2゜5-dihydro-3,6-bis(4-methylphenyl)pyrrolo[3
,4-c]virol-1,4-dione (hereinafter referred to as compound 3
referred to as: Ro and R2ban-butyl L in formula (I)
(R3 and R4 are methyl groups) was synthesized in the same manner as in Example 5.

Compound 3 was dissolved in toluene in the same manner as in Example 4, and then added to kerosene at a concentration of 0.5 ppm. The added kerosene was compared with additive-free kerosene in the same manner as in Example 1, and it was confirmed that they could be identified.

1 Seed ■-1 As an identification agent, 2.5-di(2-ethylhexyl')
-2,5-dihydro-3,6-diphenylpyrrolo[3
,4-c]virol-1,4-dione (hereinafter referred to as compound 4
In Example 5, R1 and R2 are 2-ethylhexyl L and R3 and R4 are hydrogen atoms in the 8 formula (I).
It was synthesized in the same manner.

Compound 4 was dissolved in toluene in the same manner as in Example 4, and then added to kerosene at a concentration of 0.5 ppm. The added kerosene was compared with additive-free kerosene in the same manner as in Example 1, and it was confirmed that they could be identified.

As a discriminating agent, 2,5-di-n-dodecyl-2゜5-dihydro-3,6-diphenylpyrrolo[3゜4-C]virol-1,4-dione (hereinafter, compound 5 8 formula (I
), R1 and R2 are n-dodecyl groups, R1 and R
4 is a hydrogen atom) was synthesized in the same manner as in Example 5.

Compound 5 was dissolved in toluene in the same manner as in Example 4, and then added to kerosene at a concentration of 0.5 ppm. The added kerosene was compared with additive-free kerosene in the same manner as in Example 1, and it was confirmed that they could be identified.

Mitate U As a discriminating agent, 2-n-butyl-2,5-dihydro-3
, 6-diphenylpyrrolo[3,4-c]pyrrole-1,
A 4-dione (hereinafter referred to as compound 6 in 8 formula (I), R8 is n-butyl L R+!, R3 and R4 are hydrogen atoms) was synthesized in the same manner as in Example 5.

Compound 6 was dissolved in toluene in the same manner as in Example 4, and then added to kerosene at a concentration of 0.5 ppm. The added kerosene was compared with additive-free kerosene in the same manner as in Example 1, and it was confirmed that they could be identified.

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R_3 and R_4 represent a hydrogen atom or Represents a methyl group (However, those in which R_1 and R_2 are both hydrogen atoms are excluded.) An identification agent for petroleum products represented by: 2 R_1 and R_2 in formula (I) have 1 to 1 carbon atoms
2. The petroleum product identification agent according to claim 1, which is a straight-chain or branched alkyl group. 3. A method for adding an identification agent to a petroleum product, which comprises dissolving the identification agent according to claim 1 in an organic solvent, and dissolving the organic solvent in the petroleum product.