KR101418763B1 - Marker for oil product and method for marking oil product using the same - Google Patents
Marker for oil product and method for marking oil product using the same Download PDFInfo
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- 239000003550 marker Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 239000003086 colorant Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 21
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000001033 ether group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 84
- 238000004040 coloring Methods 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 amine compound Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical group C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical group C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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Abstract
본 발명의 유류 식별용 마커는 금속 이온 화합물이 용해된 발색제에 의해, 이온 선택적 반응으로 발색되는 것으로서, 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다:
[화학식 1]
상기 화학식 1에서, R1은 수소 원자, 또는 에테르기(-O-)를 포함하거나 포함하지 않는 탄소수 1 내지 12의 알킬기이고, R2 및 R3는 각각 독립적으로 수소 원자 또는 메틸기이며, X1 및 X2는 각각 독립적으로 히드록시기(-OH)기 또는 에틸아민(-NHC2H5)기이다.The marker for oil identification of the present invention is characterized by comprising a compound represented by the following formula (1), which is developed in an ion-selective reaction by a coloring agent in which a metal ion compound is dissolved:
[Chemical Formula 1]
Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms with or without an ether group (-O-), R 2 and R 3 are each independently a hydrogen atom or a methyl group, and X 1 And X 2 are each independently a hydroxy group (-OH) group or an ethylamine (-NHC 2 H 5 ) group.
Description
본 발명은 유류 식별용 마커 및 이를 이용한 유류 식별 방법에 관한 것이다. 보다 구체적으로, 본 발명은 금속 이온 화합물이 용해된 발색제에 의해 발색되는 유류 식별용 마커 및 이를 이용한 유류 식별 방법에 관한 것이다.
The present invention relates to a marker for identifying oil and a method for identifying oil using the same. More specifically, the present invention relates to a marker for identifying oil, which is developed by a coloring agent dissolved in a metal ion compound, and a method for identifying the oil using the same.
식별용 마커는 화학, 물리학적으로 동일 또는 유사한 액체를 명확히 구분하기 위하여 사용되는 것으로서, 이중, 유류 식별용 마커는 유류(연료)를 표지하고 이를 식별하기 위한 것이다. 연료를 표지하는 것은 상업적 이유뿐만 아니라 안정성 면에서 명확한 상표명과 등급을 표시해야할 필요가 있기 때문이다. Identification markers are used to clearly distinguish between chemically and physically identical or similar liquids. Markers for identifying oil are used to identify and identify oil (fuel). Fuel marking is not only for commercial reasons, but also because of the need to label the brand name and grade clearly in terms of stability.
석유를 비롯한 연료의 식별용 마커로서 다양한 화합물이 사용되어 왔으며, 일반적으로 안트라퀴논 계열, 디아조 계열, 락톤 계열 등이 사용되어 왔다. 특히, 사용 방법 및 실용성 측면에서 락톤 구조를 가지는 화합물이 널리 사용되고 있다. 예를 들면, 페놀프탈레인 구조의 방향족 고리에 에스테르기, 에테르기 등이 연결된 형태의 화합물은 테스트의 용이성으로 인해 유용하게 사용되고 있으나, 이의 농축용액을 안정화하기 위해 많은 양의 공용매가 사용된다는 단점이 있다.Various compounds have been used as markers for identification of fuels including petroleum, and in general, anthraquinone series, diazo series, and lactone series have been used. Particularly, compounds having a lactone structure are widely used from the viewpoints of use and practicality. For example, a compound in which an ester group, an ether group or the like is linked to an aromatic ring having a phenolphthalein structure is usefully used because of easiness of testing, but a disadvantage is that a large amount of co-solvent is used to stabilize the concentrated solution.
상기 락톤 구조 화합물에서, 방향족 고리에 에스테르기 및 에테르기의 치환기가 연결되도록 설계하는 이유는, 말단 치환기로 존재하는 에스테르기 및 에테르기가 색상 발현에 용이하기 때문이다. 그러나, 제한적 요건에 맞는 화학 구조를 가지는 화합물들을 매번 정교하게 합성하여야 하는 번거로움이 있고, 실제 발색에 의한 식별 시에 기대만큼의 효과를 느끼지 못하는 경우가 많다. 예를 들어, 발색 피크에 도달하기까지 5분 정도로 다소 긴 시간이 소요되는 단점이 있다.In the lactone structural compound, the reason why the substituent of the ester group and the ether group is connected to the aromatic ring is that the ester group and the ether group present in the terminal substituent are easy to express in color. However, it is troublesome to synthesize compounds each having a chemical structure satisfying the restrictive requirements every time, and in many cases, it does not feel the effect as expected when it is identified by the actual coloring. For example, there is a disadvantage in that it takes a somewhat longer time to reach the coloring peak in about 5 minutes.
또한, 상기 화합물들은 그 구조적인 특성상 특정 산-염기의 범위에서 특정 색상으로 발색 및 소색하는 특징이 있다. 그러나, 연료(휘발유, 경유, 석유 등) 중에 용해하여 산-염기에서 발색할 경우, 그 발색의 안정성을 유지하기가 매우 어려우며 실제로 연료 내에서 용해한 이후 발색을 진행할 경우, 유류 내 각종의 방향족 그룹에 의한 용해도 차이로 인하여 쉽게 침전이 발생하거나, 그 안정성이 매우 저하되는 단점이 있다. 또한, 외부의 산-염기 조건에 따라 발색 농도에 매우 민감하게 영향을 줌으로써 정밀한 정량적 특성을 파악하는데 어렵다는 단점이 있다. In addition, the compounds are characterized in that they are colored and discolored in a specific color in the range of a specific acid-base due to their structural characteristics. However, when it is dissolved in fuel (gasoline, light oil, petroleum, etc.) and color developed in an acid-base, it is very difficult to maintain the stability of color development. When coloring proceeds after dissolving in fuel, There is a disadvantage in that precipitation occurs easily due to the difference in solubility caused by the solubility, and the stability thereof is very low. In addition, it has a disadvantage that it is difficult to grasp precise quantitative characteristics by influencing the coloring concentration very sensitively according to the external acid-base condition.
또한, 상기 화합물들은 주로 염기성 환경에서 발색 특성을 가지는데, 이때 사용하는 발색제(developer)로서 주로 아민계 화합물을 사용한다. 이러한 발색제는 사용 중 심한 악취문제가 있고, 안정성이 낮아서 보존 및 운반의 어려움이 있다.In addition, the compounds have a coloring property mainly in a basic environment. In this case, an amine compound is mainly used as a developer. Such a coloring agent has a problem of bad odor during use and is low in stability, which makes it difficult to store and transport it.
이 외에도, 질량 스펙트로미터와 가스크로마토그래피를 이용하여, 유류를 식별 및 판정하는 식별제 시스템이 있으나, 이는 분석 및 판정 시간이 오래 걸리고 고가의 장비를 동원하여야 하는 번거로움이 있다.
In addition to this, there is an identification system for identifying and determining the oil using a mass spectrometer and gas chromatography, but it takes a long time for analysis and determination and it is troublesome to use expensive equipment.
본 발명의 목적은 금속 이온에 의해 발색을 하여, 유류 중에 용해된 후에도 발색 안정성이 우수하고, 식별이 용이한 유류 식별용 마커 및 이를 이용한 유류 식별 방법을 제공하는 것이다.An object of the present invention is to provide a marker for identifying oil, which is color-developed by metal ions and is excellent in color development stability even after being dissolved in an oil, and is easy to be identified, and a method of identifying an oil using the marker.
본 발명의 다른 목적은 악취가 없고 보존 및 운반이 용이한 금속 이온 화합물이 용해된 발색제를 사용하는 유류 식별용 마커 및 이를 이용한 유류 식별 방법을 제공하는 것이다.It is another object of the present invention to provide a marker for identifying a fuel using a coloring agent dissolved in a metal ionic compound free from odor and easy to store and transport, and a method for identifying a fuel using the same.
본 발명의 또 다른 목적은 상기 유류 식별용 마커로 표지된 유류를 제공하는 것이다.
Yet another object of the present invention is to provide the oil labeled with the marker for identifying the oil.
본 발명의 하나의 관점은 유류 식별용 마커에 관한 것이다. 상기 유류 식별용 마커는 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다:One aspect of the present invention relates to a marker for oil identification. Wherein the marker for identifying oil comprises a compound represented by the following Formula 1:
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1은 수소 원자, 또는 에테르기(-O-)를 포함하거나 포함하지 않는 탄소수 1 내지 12의 알킬기이고, R2 및 R3는 각각 독립적으로 수소 원자 또는 메틸기이며, X1 및 X2는 각각 독립적으로 히드록시기(-OH)기 또는 에틸아민(-NHC2H5)기이다.Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms with or without an ether group (-O-), R 2 and R 3 are each independently a hydrogen atom or a methyl group, and X 1 And X 2 are each independently a hydroxy group (-OH) group or an ethylamine (-NHC 2 H 5 ) group.
구체예에서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 1a 내지 1l로 표시되는 화합물을 1종 이상 포함할 수 있다.In an embodiment, the compound represented by Formula 1 may include one or more compounds represented by the following Formulas 1a to 1l.
[화학식 1a] [Formula 1a]
[화학식 1b][Chemical Formula 1b]
[화학식 1c][Chemical Formula 1c]
[화학식 1d]≪ RTI ID = 0.0 &
[화학식 1e][Formula 1e]
[화학식 1f](1f)
[화학식 1g][Formula 1g]
[화학식 1h][Chemical Formula 1h]
[화학식 1i][Formula 1i]
[화학식 1j][Chemical Formula 1j]
[화학식 1k][Chemical Formula 1k]
[화학식 1l]≪ EMI ID =
구체예에서, 상기 유류 식별용 마커는 110 내지 270℃의 비점을 갖는 용매를 포함할 수 있다.In an embodiment, the oil identification marker may comprise a solvent having a boiling point of 110 to 270 < 0 > C.
바람직하게는 상기 용매는 헤테로 원자를 포함하거나 포함하지 않는 탄소수 3 내지 15의 탄화수소 용매를 1종 이상 포함할 수 있다.Preferably, the solvent may include at least one hydrocarbon solvent having 3 to 15 carbon atoms, which may or may not contain a hetero atom.
바람직하게는 상기 유류 식별용 마커는 상기 화학식 1로 표시되는 화합물 1 내지 20 중량%, 및 상기 용매 80 내지 99 중량%를 포함할 수 있다.Preferably, the marker for oil identification may contain 1 to 20% by weight of the compound represented by Formula 1 and 80 to 99% by weight of the solvent.
구체예에서, 상기 유류 식별용 마커는 금속 이온 화합물이 용해된 발색제에 의해 발색될 수 있다.In an embodiment, the oil identification marker may be developed by a coloring agent in which the metal ion compound is dissolved.
바람직하게는 상기 금속 이온 화합물은 용해 시 2가 금속 이온을 생성하는 것일 수 있다.Preferably, the metal ion compound may be one that produces a divalent metal ion upon dissolution.
본 발명의 다른 관점은 유류 식별 방법에 관한 것이다. 상기 유류 식별 방법은 상기 유류 식별용 마커를 유류에 첨가하여 표지된 유류를 제조하는 단계; 및 상기 표지된 유류에 금속 이온 화합물이 용해된 발색제를 첨가하여, 상기 유류 식별용 마커를 발색시키는 단계를 포함하는 것을 특징으로 한다.Another aspect of the invention relates to a method for identifying oil. The oil identification method comprises the steps of: preparing the labeled oil by adding the oil identification marker to the oil; And adding a coloring agent in which the metal ion compound is dissolved to the labeled oil to color the marker for identifying the oil.
구체예에서, 상기 금속 이온 화합물은 용해 시 2가 금속 이온을 생성하는 것일 수 있다.In an embodiment, the metal ion compound may be one that produces a divalent metal ion upon dissolution.
본 발명의 또 다른 관점은 상기 유류 식별용 마커로 표지된 유류에 관한 것이다.
Another aspect of the present invention relates to the oil labeled with the oil identification marker.
본 발명은 금속 이온에 의해 발색을 하여, 유류 중에 용해된 후에도 발색 안정성이 우수하고, 식별이 용이하며, 악취가 없고 보존 및 운반이 용이한 금속 이온 화합물이 용해된 발색제를 사용하는 유류 식별용 마커, 이를 이용한 유류 식별 방법 및 상기 유류 식별용 마커로 표지된 유류를 제공하는 발명의 효과를 갖는다.
The present invention relates to a marker for identifying a fuel using a coloring agent which is colored by metal ions and has excellent color stability even after dissolving in an oil, is easy to identify, has no odor, and is easy to store and transport , An oil identification method using the same, and an oil labeled with the marker for identifying the oil.
도 1은 본 발명의 실시예 2에 따라 발색시킨 유류 식별용 마커로 표지된 유류의 UV/VIS 스펙트럼이다.FIG. 1 is a UV / VIS spectrum of oil labeled with a marker for oil identification developed according to Example 2 of the present invention. FIG.
이하, 본 발명을 상세히 설명하면 다음과 같다. Hereinafter, the present invention will be described in detail.
본 발명에 따른 유류 식별용 마커는 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다.The marker for oil identification according to the present invention is characterized by containing a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1은 수소 원자, 또는 에테르기(-O-)를 포함하거나 포함하지 않는 탄소수 1 내지 12의 알킬기이고, R2 및 R3는 각각 독립적으로 수소 원자 또는 메틸기이며, X1 및 X2는 각각 독립적으로 히드록시기(-OH)기 또는 에틸아민(-NHC2H5)기이다.
Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms with or without an ether group (-O-), R 2 and R 3 are each independently a hydrogen atom or a methyl group, and X 1 And X 2 are each independently a hydroxy group (-OH) group or an ethylamine (-NHC 2 H 5 ) group.
본 발명에 사용되는 상기 화학식 1로 표시되는 화합물은 헤테로 고리 유기화합물이며 이중환식(bicyclic) 구조를 갖는 이소인돌린(isoindoline) 구조, 구체적으로, 질소를 함유하는 오각형 링 및 육각형의 벤젠 구조를 포함하며, 상기 이소인돌린(isoindoline) 구조의 N에 히드록시기, 또는 에테르기(-O-)를 포함하거나 포함하지 않는 알콕시기가 치환된 것이다. 상기 화학식 1로 표시되는 화합물은 예를 들면, 하기 제조예 1의 방법 및 이를 응용한 방법으로 제조될 수 있다. 이러한 제조방법은 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 잘 알려져 있다.
The compound represented by the formula (1) used in the present invention is a heterocyclic organic compound and includes an isoindoline structure having a bicyclic structure, specifically, a pentagonal ring containing nitrogen and a benzene structure having a hexagonal structure And the N in the isoindoline structure is substituted with an alkoxy group with or without a hydroxy group or an ether group (-O-). The compound represented by the above formula (1) can be prepared, for example, by the method of Preparation Example 1 and the method of application thereof. Such manufacturing methods are well known to those skilled in the art to which the present invention pertains.
상기 화학식 1로 표시되는 화합물의 구체적인 예로는 하기 화학식 1a 내지 1l로 표시되는 화합물, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다.Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1a) to (1l), mixtures thereof, and the like, but are not limited thereto.
[화학식 1a] [Formula 1a]
[화학식 1b][Chemical Formula 1b]
[화학식 1c][Chemical Formula 1c]
[화학식 1d]≪ RTI ID = 0.0 &
[화학식 1e][Formula 1e]
[화학식 1f](1f)
[화학식 1g][Formula 1g]
[화학식 1h][Chemical Formula 1h]
[화학식 1i][Formula 1i]
[화학식 1j][Chemical Formula 1j]
[화학식 1k][Chemical Formula 1k]
[화학식 1l]≪ EMI ID =
본 발명의 유류 식별용 마커는 유류를 표지하고 발색제에 의해 발색되어 유류 제품을 식별 가능하도록 하는 역할을 신뢰성있게 수행하기 위하여, 용매에 용해되어 있는 형태로 사용될 수 있다. 다만, 유류 식별용 마커가 불안정한 용해 상태로 존재하거나 과포화 상태로 존재할 경우, 장기간 보관에 의한 석출 및 이로 인한 발색농도의 변화를 초래하기 쉽고, 사용되는 용매에 따라 발색농도의 저하 현상이 발생하기도 하므로, 용매의 선택이 중요하다.The marker for identifying the oil of the present invention may be used in the form of being dissolved in a solvent to reliably perform the role of marking the oil and coloring the oil product by the coloring agent. However, when the marker for oil identification exists in an unstable dissolved state or exists in a supersaturated state, precipitation due to long-term storage and a change in the coloring density due to this tend to occur, and a phenomenon of lowering the coloring density may occur depending on the solvent used , The choice of solvent is important.
구체예에서, 상기 유류 식별용 마커에 사용되는 용매로서, 110 내지 270℃, 바람직하게는 140 내지 250℃의 비점을 갖는 용매(고비점 용매)를 사용할 수 있다. 상기 범위에서 유류 식별용 마커 또는 유류 식별용 마커로 표지된 유류를 장기간 보관 시에도 석출 등에 의한 발색농도 변화나 발색 농도 저하를 방지할 수 있다. In a specific example, a solvent (boiling point solvent) having a boiling point of from 110 to 270 캜, preferably from 140 to 250 캜, may be used as the solvent used for the oil discriminating marker. It is possible to prevent the change of the color development concentration or the color development concentration due to precipitation or the like even when the oil labeled with the oil identification marker or the oil identification marker is stored for a long period in the above range.
상기 용매로는 예를 들면, 비점이 110 내지 270℃인 산소 원자 등의 헤테로 원자를 포함하거나 포함하지 않는 탄소수 3 내지 15 탄화수소 용매, 바람직하게는 탄소수 6 내지 15의 방향족 탄화수소 용매를 1종 이상 사용할 수 있다.As the solvent, for example, there can be used at least one aromatic hydrocarbon solvent having 3 to 15 carbon atoms, preferably 6 to 15 carbon atoms, with or without a hetero atom such as an oxygen atom having a boiling point of 110 to 270 ° C .
상기 용매의 구체적인 예로는 2-부톡시에탄올(butyl cellosolve), 디이소부틸케톤(diisobutyl ketone), 크실렌(Xylene), 1-메틸나프탈렌(1-methyl naphthalene), 2-메틸나프탈렌(2-methyl naphthalene), 1-에틸나프탈렌(1-ethyl naphthalene), 2-에틸나프탈렌(2-ethyl naphthalene), 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다.Specific examples of the solvent include butyl cellosolve, diisobutyl ketone, xylene, 1-methyl naphthalene, 2-methyl naphthalene, ), 1-ethyl naphthalene, 2-ethyl naphthalene, mixtures thereof, and the like, but the present invention is not limited thereto.
일 실시예에서, 전체 용매 100 중량% 중, 1-메틸나프탈렌 50 내지 70 중량% 및 상용화된 방향족 용매인 Kocosol 200S을 30 내지 50 중량% 포함하는 용매를 사용할 수 있다. 상기 범위에서 유류 식별용 마커 또는 유류 식별용 마커로 표지된 유류를 장기간 보관 시에도 석출 등에 의한 발색농도 변화나 발색 농도 저하를 방지할 수 있다.
In one embodiment, a solvent comprising 50 to 70% by weight of 1-methylnaphthalene and 30 to 50% by weight of a commercialized aromatic solvent, Kocosol 200S, may be used in 100% by weight of the total solvent. It is possible to prevent the change of the color development concentration or the color development concentration due to precipitation or the like even when the oil labeled with the oil identification marker or the oil identification marker is stored for a long period in the above range.
본 발명의 유류 식별용 마커는 일 구체예에서, 상기 화학식 1로 표시되는 화합물 1 내지 20 중량%, 바람직하게는 5 내지 15 중량% 및 상기 용매 80 내지 99 중량%, 바람직하게는 85 내지 95 중량%를 포함할 수 있다. 상기 범위에서 유류 식별용 마커 또는 유류 식별용 마커로 표지된 유류를 장기간 보관 시에도 석출 등에 의한 발색농도 변화나 발색 농도 저하를 방지할 수 있다.
In one embodiment, the marker for oil identification of the present invention comprises 1 to 20% by weight, preferably 5 to 15% by weight of the compound represented by Formula 1 and 80 to 99% by weight, preferably 85 to 95% %. ≪ / RTI > It is possible to prevent the change of the color development concentration or the color development concentration due to precipitation or the like even when the oil labeled with the oil identification marker or the oil identification marker is stored for a long period in the above range.
본 발명의 유류 식별용 마커는 금속 이온 화합물이 용해된 발색제(developer)에 의해 발색될 수 있는 것이다.The marker for oil identification of the present invention can be developed by a developer in which a metal ion compound is dissolved.
구체예에서, 상기 금속 이온 화합물은 용해 시, Cu++, Al++, Ca++, Zn++, Fe++ 등의 2가 금속 이온을 생성하는 것일 수 있고, 예를 들면, CuCl2, AlCl2, CaCl2, ZnCl2, FeCl2 등일 수 있으나, 이에 제한되는 것은 아니다.In an embodiment, the metal ion compound may be one which produces a divalent metal ion such as Cu ++ , Al ++ , Ca ++ , Zn ++ or Fe ++ upon dissolution, for example CuCl 2 , AlCl 2 , CaCl 2 , ZnCl 2 , FeCl 2 And the like, but is not limited thereto.
또한, 일 구체예에서, 상기 발색제는 110 내지 190℃의 비점을 갖는 유기용매를 더욱 포함하는 것일 수 있다. 상기 유기용매로는 방향족 탄화수소 용매를 제외한 2-메톡시에탄올(methyl cellosolve), 2-부톡시에탄올(butyl cellosolve), 디이소부틸케톤(diisobutyl ketone) 등을 사용할 수 있으나, 이에 제한되지 않는다.Further, in one embodiment, the coloring agent may further comprise an organic solvent having a boiling point of 110 to 190 캜. Examples of the organic solvent include, but are not limited to, 2-methoxyethanol (methyl cellosolve), 2-butoxyethanol (butyl cellosolve), diisobutyl ketone and the like, except for an aromatic hydrocarbon solvent.
예를 들면, 상기 발색제는 에탄올 등의 알코올류에 상기 금속 이온 화합물을 첨가하고, 가열하여 용해시킨 다음, 이를 여과한 여액을 상기 유기 용매로 희석한 것일 수 있다. For example, the coloring agent may be obtained by adding the metal ion compound to an alcohol such as ethanol, dissolving the metal ion compound by heating, and then filtering the filtrate by diluting it with the organic solvent.
상기 발색제는 상기 금속 이온 화합물이 1 내지 20 ppm, 바람직하게는 2 내지 10 ppm로 용해된 것일 수 있다. 상기 범위에서 발색제를 장기간 보관 시에도 석출 등에 의한 발색농도 변화나 발색 농도 저하를 방지할 수 있다.The coloring agent may be one in which the metal ion compound is dissolved in 1 to 20 ppm, preferably 2 to 10 ppm. Even when the coloring agent is stored for a long period of time in the above range, it is possible to prevent the change of the coloring density and the decrease of the coloring density due to precipitation and the like.
상기 발색제는 자극적인 냄새가 없고, 안정하여 상온에서도 장기 보관이 가능하다. 상기 발색제는 상기 화학식 1로 표시되는 화합물을 포함하는 유류 식별용 마커와 반응하여, 석유 등 유류에서 미세한 농도 하에서도 뚜렷한 발색 특성을 가진다. 상기 발색은 상기 화학식 1로 표시되는 화합물과 상기 발색제의 2가 금속 이온(Me++)이 하기 반응식 1의 이온 선택적 반응을 거쳐 일어날 수 있다. 즉, 발색제의 2가 금속 이온이 상기 유류 식별용 마커 화합물(화학식 1)의 N 치환된 이소인돌린 구조와 반응하여 개환반응(Ring-opening)함으로써, 상기 유류 식별용 마커 화합물의 콘쥬게이션(conjugation) 구조에 영향을 주어서 발색이 안정적으로 나타나는 것이다.The coloring agent has no irritating odor and is stable and can be stored for a long time at room temperature. The coloring agent reacts with the marker for identifying the oil including the compound represented by the formula (1), and has a distinct coloring property even in a minute concentration in oil and the like. The color development can be achieved by the ion selective reaction of the compound represented by Formula 1 and the divalent metal ion (Me < ++ >) of the color developer with the following reaction formula (1). That is, the divalent metal ion of the coloring agent reacts with the N-substituted isoindoline structure of the oil recognition marker compound (Formula 1) to carry out ring-opening reaction, whereby the conjugation ) Structure, and the color development is stable.
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서, R1, R2, R3, X1 및 X2는 상기 화학식 1에서 정의한 바와 같다.
In the above Reaction Scheme 1, R 1 , R 2 , R 3 , X 1, and X 2 are as defined in Formula 1 above.
본 발명에 따른 유류 식별 방법은 상기 유류 식별용 마커를 유류에 첨가하여 표지된 유류를 제조하는 단계, 및 상기 표지된 유류에 금속 이온 화합물이 용해된 발색제를 첨가하여, 상기 유류 식별용 마커를 발색시키는 단계를 포함할 수 있다.The method for identifying oil according to the present invention comprises the steps of: preparing the labeled oil by adding the marker for oil identification to the oil; and adding a coloring agent in which the metal ion compound is dissolved to the labeled oil, . ≪ / RTI >
예를 들면, 상기 유류 식별용 마커로 표지된 유류는 휘발유, 경유 등의 연료유, 윤활유, 이들의 혼합물 등을 포함하는 유류에 상기 유류 식별용 마커를 상기 유류에 대하여 1 내지 30 ppm, 바람직하게는 5 내지 20 ppm의 중량으로 첨가 및 혼합하여 제조할 수 있다. 상기 유류 식별용 마커의 중량 범위에서 발색제에 의해 식별이 가능하며, 장기간 보관 시에도 석출 등에 의한 발색농도 변화나 발색 농도 저하를 방지할 수 있다.For example, the oil labeled with the oil identification marker may be added to the oil containing gas oil, light oil or other fuel oil, lubricating oil or a mixture thereof in an amount of 1 to 30 ppm relative to the oil, Can be prepared by adding and mixing at a weight of 5 to 20 ppm. It is possible to identify the marker by the coloring agent in the weight range of the marker for identifying the oil and to prevent the change of the coloring density and the decrease of the coloring density due to precipitation or the like even when stored for a long period of time.
다음으로, 상기 표지된 유류 100 중량부에 대하여, 상기 발색제를 1 내지 30중량부, 바람직하게는 5 내지 15 중량부를 첨가하여, 상기 유류 식별용 마커의 화합물(화학식 1)을 발색시킴으로써 식별할 수 있다. 상기 발색제의 중량 범위에서 유류 식별용 마커 화합물의 발색에 의한 유류 식별이 용이하다.
Next, 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of the coloring agent is added to 100 parts by weight of the above-mentioned labeled oil to identify the compound (Formula 1) of the oil identification marker have. It is easy to identify the oil by the coloring of the marker identifying compound for the oil in the weight range of the coloring agent.
본 발명의 유류 식별용 마커는 상기 발색제와 반응하여 나타내는 발색 성능이 우수하여 미량으로도 충분히 식별이 가능하다. 따라서, 육안으로도 충분히 식별할 수 있고, 보다 정확한 식별을 위해서는 자외선/가시광선 흡수분광광도계(UV/VIS Spectrophotometer), 비색계(colorimeter), 고성능 액체 크로마토그래피(HPLC) 등을 이용할 수도 있다.
The marker for oil identification of the present invention reacts with the coloring agent and is excellent in color development performance and can be sufficiently identified even in a very small amount. Therefore, it can be sufficiently visually recognized. For more accurate identification, an ultraviolet / visible spectrophotometer (UV / VIS Spectrophotometer), a colorimeter, and a high performance liquid chromatography (HPLC) may be used.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로서, 본 발명을 제한하는 것으로 해석되어서는 안 된다.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예Example
제조예Manufacturing example 1: 화학식 1a로 표시되는 화합물의 제조 1: Preparation of the compound represented by the formula (1a)
로다민 6G(Rhodamine 6G) 50.0g을 에탄올 200.0g에 용해시킨 후, 수산화나트륨(NaOH) 12.5g을 첨가하고, 4시간 동안 환류 반응을 통해 잔여 불순물이 제거된 안정한 형태로 중간체를 제조한 다음, 이를 필터로 여과하여 60℃의 온도에서 건조시켰다. 건조된 중간체 20.0g을 환류조에 넣고, 메틸렌클로라이드(methylene chloride) 용매 150.0g 및 옥시염화인(phosphorus oxychloride) 22.0g을 첨가한 후, 3시간 동안 환류반응을 진행하였다. 다음으로, 증발기(evaporator) 또는 가열을 통해 반응 용매를 제거한 뒤, 다시 상온에서 메틸렌클로라이드 용매 100.0g 및 히드록실아민 수염화물(hydroxylamine hydrochloride) 7.36g을 첨가하고, 교반을 진행하며 트리에틸아민(triethyl amine) 10.76g을 천천히 적하하고 3시간 동안 반응시켰다. 침전물을 여과하고 완전 건조하여, 약 20 내지 23g의 붉은색 분말 형태의 하기 화학식 1a로 표시되는 화합물을 얻었다.After dissolving 50.0 g of Rhodamine 6G in 200.0 g of ethanol, 12.5 g of sodium hydroxide (NaOH) was added, and the mixture was refluxed for 4 hours to prepare an intermediate in a stable form in which residual impurities were removed. It was filtered with a filter and dried at a temperature of 60 ° C. 20.0 g of the dried intermediate was placed in a reflux condenser, and 150.0 g of a methylene chloride solvent and 22.0 g of phosphorus oxychloride were added, followed by reflux reaction for 3 hours. Next, after removing the reaction solvent through an evaporator or heating, 100.0 g of a methylene chloride solvent and 7.36 g of a hydroxylamine hydrochloride were added at room temperature, and the mixture was stirred with triethylamine amine) was slowly added dropwise and reacted for 3 hours. The precipitate was filtered and completely dried to obtain a compound represented by the following formula (1a) in the form of a red powder of about 20 to 23 g.
[화학식 1a] [Formula 1a]
제조예Manufacturing example 2: 발색제의 제조 2: Preparation of color developer
500ml 비이커에 에탄올 89.6 중량%을 넣고, 구리 염화물(CuCl2, 제조사: 대정화금) 10.4중량%를 교반하면서 서서히 투입한 후, 30 내지 40℃에서 30분간 교반 및 용해시켰다. 이를 여과한 후, 여액에 28 내지 30배(중량비)의 2-메톡시에탄올(methyl cellosolve)를 넣고 희석함으로써 2가 금속 이온으로서 Cu++을 포함하는 발색제를 제조하였다.
89.6% by weight of ethanol was added to a 500 ml beaker, and 10.4% by weight of copper chloride (CuCl 2 , manufacturer: purified gold) was slowly added thereto with stirring, followed by stirring and dissolution at 30 to 40 ° C for 30 minutes. After filtration, a coloring agent containing Cu ++ as a divalent metal ion was prepared by adding 2-methoxyethanol (methyl cellosolve) of 28 to 30 times (weight ratio) to the filtrate and diluting.
실시예Example 1 One
2,000ml 비이커에 메틸나프탈렌(methyl naphthalene) 48.7중량%, Kocosol 200S(제조사: SK케미칼) 41.9중량%를 넣고, 상기 화학식 1a로 표시되는 화합물 9.4중량%를 교반하면서 서서히 넣은 후, 30 내지 40℃에서 30분간 교반하여 용해시켰다. 용해 후, 교반하면서 상온으로 냉각하고 동양여과지로 여과하여 유류 식별용 마커를 제조하였다.
48.7% by weight of methyl naphthalene and 41.9% by weight of Kocosol 200S (manufacturer: SK Chemicals) were added to a 2,000 ml beaker and 9.4% by weight of the compound represented by the above formula (1a) was slowly added thereto while stirring. And dissolved by stirring for 30 minutes. After dissolution, the solution was cooled to room temperature while stirring, and filtered with an oriental filter paper to prepare a marker for oil identification.
실시예Example 2 2
방향족 용매(유류)에 상기 실시예 1에서 제조된 유류 식별용 마커 10ppm이 첨가된 표지된 유류 15ml를 취한 후, 상기 제조예 2에서 제조된 발색제 2ml를 투입 및 혼합하여 발색 측정하였다. 상기 발색제에 의해 발색된 유류 식별용 마커로 표지된 유류는 적색을 나타내었으며, 이를 자외선/가시광선 흡수분광광도계(UV/VIS Spectrophotometer)로 측정한 UV/VIS 스펙트럼을 도 1에 나타내었다. 도 1에 도시된 바와 같이, 발색된 유류 식별용 마커로 표지된 유류는 530 내지 540 nm의 파장(wavelength)에서 0.15 내지 0.17의 흡광도(absortion: Abs.)를 나타낸다.
15 ml of the labeled oil to which 10 ppm of the oil identifying marker prepared in Example 1 was added was added to the aromatic solvent (oil) and 2 ml of the coloring agent prepared in Preparation Example 2 was added and mixed to measure the color. The oil labeled with the marker for identifying the oil developed by the color developer showed red color, and the UV / VIS spectrum of the oil was measured with an ultraviolet / visible spectrophotometer (UV / VIS Spectrophotometer). As shown in Fig. 1, the oil labeled with a colored marker for identifying oil shows an absorption (Abs.) Of 0.15 to 0.17 at a wavelength of 530 to 540 nm.
실험예Experimental Example
하기 표 1 및 2에 따라, 상기 실시예 1에서 제조된 유류 식별용 마커의 농도를 달리한 것을 제외하고는 상기 실시예 2와 동일한 방법으로 표지된 유류를 발색시켰으며, 발색 후, 초기 및 60일간 상온에서 저장 후의 UV/VIS 스펙트럼을 각각 5회씩 측정하여, 각각의 흡광도를 표 1(초기) 및 2(60일 저장 후)에 나타내었다. 상기 결과에 따라 검량선을 작성하고, 기울기(A), 절편(B) 및 상관계수(R2)을 구하여 표 1 및 2에 나타내었다.
According to Tables 1 and 2, the labeled oil was developed in the same manner as in Example 2 except that the concentration of the marker for identifying oil prepared in Example 1 was changed, The UV / VIS spectra after storage at room temperature for one day were measured five times each, and the respective absorbances were shown in Table 1 (initial) and 2 (after 60 days storage). The slope (A), the slice (B), and the correlation coefficient (R 2 ) were calculated and shown in Tables 1 and 2.
(ppm)Marker concentration
(ppm)
(ppm)Marker concentration
(ppm)
상기 표 1 및 2의 결과로부터, 본 발명에 따른 유류 식별용 마커는 발색제와 반응하여 나타내는 발색 성능이 우수하여, 5ppm 정도의 미량으로도 충분히 식별할 수 있음을 알 수 있고, 발색 초기 및 60일 후 검량선 측정 결과, 상관계수(R2)이 1에 가까우므로, 유류 식별용 마커가 유류에 용해된 후에도 발색 안정성이 우수하고, 석출 등에 의해 발색 농도 저하 등이 없음을 알 수 있다.
From the results shown in Tables 1 and 2, it can be seen that the marker for identifying oil according to the present invention reacts with a coloring agent to exhibit excellent color development performance and can be sufficiently identified even at a trace amount of about 5 ppm. As a result of the measurement of the calibration curve after the measurement, the correlation coefficient (R 2 ) is close to 1, so that the color development stability is excellent even after the marker for identifying oil is dissolved in the oil, and there is no decrease in color density due to precipitation or the like.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
[화학식 1]
상기 화학식 1에서, R1은 수소 원자, 또는 에테르기(-O-)를 포함하거나 포함하지 않는 탄소수 1 내지 12의 알킬기이고, R2 및 R3는 각각 독립적으로 수소 원자 또는 메틸기이며, X1 및 X2는 각각 독립적으로 히드록시기(-OH)기 또는 에틸아민(-NHC2H5)기이다.
1. A marker for identifying a fuel comprising a compound represented by the following formula (1):
[Chemical Formula 1]
Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms with or without an ether group (-O-), R 2 and R 3 are each independently a hydrogen atom or a methyl group, and X 1 And X 2 are each independently a hydroxy group (-OH) group or an ethylamine (-NHC 2 H 5 ) group.
[화학식 1a]
[화학식 1b]
[화학식 1c]
[화학식 1d]
[화학식 1e]
[화학식 1f]
[화학식 1g]
[화학식 1h]
[화학식 1i]
[화학식 1j]
[화학식 1k]
[화학식 1l]
The marker for identifying a fuel according to claim 1, wherein the compound represented by the formula (1) comprises at least one compound represented by any of the following formulas (1a) to (1l).
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
[Formula 1e]
(1f)
[Formula 1g]
[Chemical Formula 1h]
[Formula 1i]
[Chemical Formula 1j]
[Chemical Formula 1k]
≪ EMI ID =
The marker for oil identification according to claim 1, further comprising a solvent having a boiling point of 110 to 270 캜.
4. The marker according to claim 3, wherein the solvent comprises at least one hydrocarbon solvent having 3 to 15 carbon atoms, the hydrocarbon solvent including at least one heteroatom.
[4] The marker according to claim 3, wherein the marker for identifying oil comprises 1 to 20% by weight of the compound represented by Formula 1, and 80 to 99% by weight of the solvent.
The marker according to claim 1, wherein the marker for identifying oil is developed by a coloring agent dissolved in a metal ion compound.
The marker according to claim 6, wherein the metal ion compound generates bivalent metal ions upon dissolution.
상기 표지된 유류에 금속 이온 화합물이 용해된 발색제를 첨가하여, 상기 유류 식별용 마커를 발색시키는 단계를 포함하는 것을 특징으로 하는 유류 식별 방법.
8. A method of producing a labeled oil, comprising: adding a marker for identifying oil according to any one of claims 1 to 7 to the oil to produce a labeled oil; And
And adding a coloring agent in which the metal ion compound is dissolved to the labeled oil to color the marker for identifying the oil.
The method according to claim 8, wherein the metal ion compound produces bivalent metal ions upon dissolution.
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|---|---|---|---|---|
| US5498808A (en) * | 1995-01-20 | 1996-03-12 | United Color Manufacturing, Inc. | Fluorescent petroleum markers |
| KR20020033033A (en) * | 2001-06-13 | 2002-05-04 | 이인남 | Marker for idetification curable silicone composition having slip property |
| KR100953358B1 (en) * | 2008-10-14 | 2010-04-20 | 오리엔트화학 (주) | Marker for oil products to be developed with metal complex salts developer, and method for marking oil products using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498808A (en) * | 1995-01-20 | 1996-03-12 | United Color Manufacturing, Inc. | Fluorescent petroleum markers |
| KR20020033033A (en) * | 2001-06-13 | 2002-05-04 | 이인남 | Marker for idetification curable silicone composition having slip property |
| KR100953358B1 (en) * | 2008-10-14 | 2010-04-20 | 오리엔트화학 (주) | Marker for oil products to be developed with metal complex salts developer, and method for marking oil products using the same |
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|---|---|---|---|---|
| CN106967079A (en) * | 2017-03-29 | 2017-07-21 | 山东师范大学 | A kind of synthetic method of rhodamine 6G hydroxamic acid |
| CN106967079B (en) * | 2017-03-29 | 2019-05-28 | 山东师范大学 | A kind of synthetic method of rhodamine 6G hydroxamic acid |
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