KR102166437B1 - Oil marker comprising carbamate group protected amine- derivative and identifying method of petroleum using it - Google Patents
Oil marker comprising carbamate group protected amine- derivative and identifying method of petroleum using it Download PDFInfo
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- KR102166437B1 KR102166437B1 KR1020140006987A KR20140006987A KR102166437B1 KR 102166437 B1 KR102166437 B1 KR 102166437B1 KR 1020140006987 A KR1020140006987 A KR 1020140006987A KR 20140006987 A KR20140006987 A KR 20140006987A KR 102166437 B1 KR102166437 B1 KR 102166437B1
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- South Korea
- Prior art keywords
- oil
- marker
- acid
- butyl
- carbamate
- Prior art date
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- 239000003550 marker Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 54
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003208 petroleum Substances 0.000 title description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- 238000002835 absorbance Methods 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims description 111
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 11
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 10
- -1 tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl) Amino}butyl)-N-methylcarbamate (tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate) Chemical compound 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- MXSNQMUVXLVDHI-UHFFFAOYSA-N tert-butyl n-butylcarbamate Chemical compound CCCCNC(=O)OC(C)(C)C MXSNQMUVXLVDHI-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000002199 base oil Substances 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 2
- OWOZLAYXMYQYNC-UHFFFAOYSA-N tert-butyl n-[4-[(2-methylpropan-2-yl)oxycarbonylamino]butyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCCNC(=O)OC(C)(C)C OWOZLAYXMYQYNC-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000011161 development Methods 0.000 abstract description 14
- 239000003463 adsorbent Substances 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 230000018109 developmental process Effects 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAWMUPTUBHPLTI-UHFFFAOYSA-N C1(=C(C=CC=C1)N(C(OC(C)(C)C)=O)C)N(C(OC(C)(C)C)=O)C Chemical compound C1(=C(C=CC=C1)N(C(OC(C)(C)C)=O)C)N(C(OC(C)(C)C)=O)C ZAWMUPTUBHPLTI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- VQJDBGSINGXXEB-UHFFFAOYSA-N benzyl n-butylcarbamate Chemical compound CCCCNC(=O)OCC1=CC=CC=C1 VQJDBGSINGXXEB-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 description 1
- 229940052881 quinhydrone Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SBFXRAQMZINCEI-UHFFFAOYSA-N tert-butyl N-methyl-N-[4-[methyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]butyl]carbamate Chemical compound C(CCCN(C(OC(C)(C)C)=O)C)N(C(OC(C)(C)C)=O)C SBFXRAQMZINCEI-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
-
- 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
- G01N33/22—Fuels, explosives
-
- 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
- G01N33/28—Oils, i.e. hydrocarbon liquids
Abstract
본 발명은 카바메이트기를 포함하는 아민계 유류 식별제(Marker)로 표지된 유류가 전개시약(Developer)과 반응하여 유도된 발색에 대한 흡광도를 측정하여 유류의 진위여부를 식별하는 방법을 제공할 수 있다.
본 발명은 흡착제에 의해 쉽게 제거되지 아니하며, 반응속도가 빠르고, 재현성이 우수한 카바메이트기를 포함하는 아민계 유류 식별제(Marker) 및 이를 이용한 유류식별방법을 제공할 수 있다.The present invention can provide a method for identifying the authenticity of the oil by measuring the absorbance for color development induced by reacting the oil labeled with an amine-based oil identifier (Marker) containing a carbamate group with a developer. have.
The present invention is not easily removed by the adsorbent, the reaction rate is fast, it is possible to provide an amine-based oil identifier (Marker) containing a carbamate group excellent in reproducibility, and an oil identification method using the same.
Description
본 발명은 카바메이트를 포함하는 아민계 유류 식별제(Marker) 및 이로 표지된 유류를 닌하이드린 전개시약과 반응시켜 발색을 통해 유류의 진위여부를 정량적 및 정성적으로 식별할 수 있는 방법에 관한 것이다. The present invention relates to a method for quantitatively and qualitatively identifying the authenticity of oil through color development by reacting an amine-based oil marker containing carbamate and an oil labeled therewith with a ninhydrin developing reagent. will be.
원유가격의 급격한 상승으로 인한 석유류의 불법적인 사용으로 인한 환경오염 및 자동차의 수명단축의 폐해를 방지하기 위해서, 가짜 휘발유의 사용방지 및 특수목적의 면세유의 불법사용을 방지하기 위해 석유제품 식별제(Marker)가 도입되어 사용 중에 있다. 또한, 석유화학기술의 발전으로 인한 석유정제기술의 고도화로 각 정유사의 품질경쟁 및 유지에 많은 비용이 소요되고 있다. 이에 각 정유사의 브랜드화 및 품질의 유지확인을 위해 석유제품 식별제(Marker)의 도입이 이루어졌으며, 초기에는 가솔린에 첨가되기 시작하여 현재는 LPG, 경유 및 등유까지 확대되고 있는 추세이다.In order to prevent environmental pollution caused by the illegal use of petroleum due to a sharp rise in crude oil prices and the harmful effects of shortening the lifespan of automobiles, to prevent the use of fake gasoline and to prevent the illegal use of duty-free oil for special purposes ( Marker) has been introduced and is in use. In addition, due to the advancement of petroleum refining technology due to the development of petrochemical technology, a lot of cost is required for quality competition and maintenance of each refinery. Accordingly, the introduction of a petroleum product identifier (Marker) was made to confirm the branding and quality maintenance of each refinery, and it started to be added to gasoline at the beginning, and is now expanding to LPG, diesel and kerosene.
석유제품의 식별을 위해 표지하는 방법에 대해서는 1980년대 이후 많은 발전을 하였으며, 현재에는 크게 3가지 형태의 표지 방법이 알려져 있다.As for the labeling method for identification of petroleum products, many developments have been made since the 1980s, and three types of labeling methods are currently known.
첫 번째 형태로, i) 디아조기가 포함된 방향족 물질을 첨가하고, 산 또는 염기를 가해 색을 발현시키는 방법, 또는 ii) 방향족 아민 또는 페놀류를 첨가한 다음 디아조늄을 가하는 방법으로, 색을 나타내는 물질을 석유류(유기용액)에서 추출하여 정성, 정량하는 방법 등이 있다. 위 방법들은 가격이 저렴하고 발색이 우수하지만, 기기적으로 측정이 어렵고 육안식별을 하여야 하며, 발색시약의 휴대가 어려운 단점 등이 있어서 사용되지 않고 있다.In the first form, i) a method of expressing color by adding an aromatic substance containing a diazo group and adding an acid or a base, or ii) adding an aromatic amine or phenol, followed by adding a diazonium. There are methods of extracting substances from petroleum (organic solutions), qualifying and quantifying. Although the above methods are inexpensive and have excellent color development, they are not used because of the disadvantages of being difficult to measure mechanically, requiring visual identification, and making it difficult to carry a color developing reagent.
두 번째 방법으로, 무색에 가까운 식별제(Marker)를 투입하여 석유류(유기용액)에 녹아있는 발색시약의 구조를 변화시켜 석유류(유기용액) 전체가 색변화를 나타내는 방법으로 현재 가장 많이 사용하고 있는 종류이다.The second method is to change the structure of the color developing reagent dissolved in petroleum (organic solution) by introducing a colorless marker (Marker), which is currently the most widely used method of showing color change of the entire petroleum (organic solution). It's kind.
세 번째 방법으로, 근적외선영역의 빛을 흡수하는 염료를 사용하여 기기적으로 정량하는 방법이 있다. 그러나, 사용기기의 가격이 매우 고가이고 고장이 잦으며, 석유류에 대한 용해성이 나빠 침전이 석출되기도 한다. As a third method, there is a method of quantifying mechanically using a dye that absorbs light in the near infrared region. However, the price of the equipment used is very expensive, frequent breakdowns, and solubility in petroleum is poor, so precipitation may be deposited.
유류의 진위를 식별하는 첫번째 형태에 있어서, 아민계 화합물 및 그 유도체를 이용한 유류의 진위여부를 식별하는 방법은 퀸하이드론 반응, 닌하이드린 반응 및 드라겐도르프 반응 등을 이용하여 발색을 유도함으로서 달성할 수 있다.In the first form of identifying the authenticity of oil, the method of identifying the authenticity of oil using amine compounds and their derivatives is by inducing color development using quinhydrone reaction, ninhydrin reaction, and dragendorf reaction. Can be achieved.
다만, 아민계 화합물 및 그 유도체와 닌하이드린을 전개시약으로 반응시켜 유류의 진위 식별방법의 경우, 아민계 유류 식별제(Marker)가 활성탄과 같은 흡착제에 흡착되므로 인하여 쉽게 제거될 수 있어, 유류의 진위여부 식별의 신뢰성 확보 측면에서 문제점이 존재하였다. However, in the case of a method of identifying the authenticity of oil by reacting an amine compound and its derivative with ninhydrin as a developing reagent, the amine oil marker is adsorbed by an adsorbent such as activated carbon, so it can be easily removed. There was a problem in securing the reliability of identification of the authenticity or not.
본 발명은 상기와 같은 문제를 해결하기 위하여 안출된 것으로서, 흡착제에 의해 쉽게 제거되지 않고, 소량으로도 정성적 및 정량적인 유류의 진위여부 측정이 가능한 카바메이트기를 포함하는 아민계 유류 식별제(Marker) 및 이를 이용한 유류식별방법을 제공하고자 함에 있다. The present invention has been devised to solve the above problems, and is not easily removed by an adsorbent, and an amine-based oil identifier containing a carbamate group capable of qualitative and quantitative determination of the authenticity of oil even with a small amount (Marker ) And an oil identification method using the same.
또한, 유류 내 소량으로 포함되어 있음에도 닌하이드린 반응을 통해 색변화를 뚜렷하게 일으키며, 흡착제에 의해 제거되기 어려운 카바메이트기를 포함하는 아민계 유류 식별제(Marker) 및 이를 이용한 유류식별방법을 제공하고자 함에 있다. In addition, even though it is contained in a small amount in oil, it causes a distinct color change through ninhydrin reaction, and it is intended to provide an amine-based oil marker containing carbamate groups that are difficult to remove by an adsorbent, and an oil identification method using the same. have.
본 발명은 상기 목적을 달성하기 위하여, 하기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)일 수 있다.In order to achieve the above object, the present invention may be an amine-based oil identifier (Marker) containing a carbamate group represented by the following formula (1).
화학식 (1)Formula (1)
(여기서, R1, R2, R3는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C20의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐원소를 포함하거나 포함하지 않는 헤테로 고리기이다.) (Wherein, R1, R2, R3 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a heteroalkyl group or aryl group including or not including a carbamate group, O,N,S,P, or a halogen element. It is a heterocyclic group containing or not containing.)
본 발명은 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)로 표지된 유류를 전처리 하는 단계; 및The present invention comprises the steps of pre-treating the oil labeled with an amine-based oil identifier (Marker) containing a carbamate group of the formula (1); And
전처리된 유류식별제를 닌하이드린과 반응시키는 단계;를 포함하는 유류식별방법일 수 있다. It may be an oil identification method including; reacting the pretreated oil identification agent with ninhydrin.
본 발명의 따른 유류내 포함되어 있는 카바메이트를 포함하는 아민계 유류 식별제(Marker)는 흡착제에 의해 쉽게 제거되지 않아 유류의 진위여부를 식별하는 방법에 있어서의 재현성 및 신뢰성을 확보할 수 있다.The amine-based oil marker (Marker) containing carbamate contained in the oil according to the present invention is not easily removed by the adsorbent, so that reproducibility and reliability in the method of identifying the authenticity of oil can be secured.
또한, 본 발명의 유류 내 포함되어 있는 카바메이트를 포함하는 아민계 유류 식별제(Marker)와 닌하이드린과의 반응을 통한 생성물은 구조적 안정성이 우수하며, 색 변화가 뚜렷하고 재현성이 뛰어나, 유류 내 소량으로 존재하여도 발색을 유도할 수 있는 이점이 있으며, 상온에서 닌하이드린과 빠른 반응을 통한 발색으로 유류의 진위여부를 정량적 및 정성적으로 측정할 수 있다. In addition, the product through the reaction of the amine-based oil marker (Marker) containing carbamate contained in the oil of the present invention with ninhydrin has excellent structural stability, has a distinct color change, and has excellent reproducibility. Even if it is present in a small amount, it has the advantage of inducing color development, and the authenticity of oil can be quantitatively and qualitatively measured by color development through rapid reaction with ninhydrin at room temperature.
이하 본 발명에 대해서 실시예 및 도면을 통해 보다 상세히 설명하겠지만, 본 발명의 요지에 국한된 실시예에 지나지 않는다. 한편 본 발명은 이하의 실시예에서 제시하는 공정조건에 제한되는 것이 아니며, 본 발명의 목적을 달성하기에 필요한 조건의 범위 안에서 임의로 선택할 수 있음은 당업자에게 자명하다. Hereinafter, the present invention will be described in more detail through examples and drawings, but they are only examples limited to the gist of the present invention. Meanwhile, it is apparent to those skilled in the art that the present invention is not limited to the process conditions presented in the following examples, and can be arbitrarily selected within the range of conditions necessary to achieve the object of the present invention.
이 때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다. In this case, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings A description of known functions and configurations that may unnecessarily obscure will be omitted.
본 발명은 카바메이트기를 포함하는 아민계 유류 식별제(Marker) 및 이를 이용한 유류의 식별방법을 제공할 수 있다. The present invention can provide an amine-based oil identifier (Marker) containing a carbamate group and a method for identifying oil using the same.
보다 구체적으로 카바메이트기를 포함하는 아민계 유류 식별제(Marker)로 표지된 유류를 산처리 등을 통하여 카바메이트기를 디프로텍션(Deprotection)한 후, 전개시약(Developer)인 닌하이드린과 반응시켜 발색하게 하고, 상기 색을 육안 또는 흡광도 측정장치를 이용하여 흡광도를 측정함으로써, 유류의 진위여부를 정성적 및 정량적으로 식별하는 방법을 제공할 수 있다.More specifically, deprotection of the carbamate group through acid treatment of oils labeled with an amine-based oil marker containing a carbamate group, and then reaction with ninhydrin, a developer, to develop color. And, by measuring the absorbance of the color with the naked eye or using an absorbance measuring device, it is possible to provide a method of qualitatively and quantitatively identifying the authenticity of oil.
또한, 본 발명은 유류 식별제(Marker)와 닌하이드린과의 반응을 통해 생성된 생성물이 구조적으로 안정하여, 가역반응이 존재하지 않으며, 재현성이 뛰어나고 소량으로도 발색여부를 육안으로 확인할 수 있는 유류 식별제 및 이의 식별방법을 제공할 수 있다.In addition, in the present invention, the product produced through the reaction of the oil marker (Marker) and ninhydrin is structurally stable, there is no reversible reaction, excellent reproducibility, and color development can be confirmed with the naked eye. Oil identification agents and methods of identification can be provided.
더욱이, 본 발명에 따른 유류 식별제(Marker)는 유통 중에 정량적인 검출이 가능하며, 저가품 또는 면세품 등과 혼합되었는지 여부를 확인할 수 있으며 흡착제 등에 의한 제거로부터 안전할 수 있는 유류 식별제 및 이의 식별방법을 제공할 수 있다.Moreover, the oil identification agent (Marker) according to the present invention can be quantitatively detected during distribution, and whether it is mixed with inexpensive or duty-free goods, etc., and is safe from removal by an adsorbent, and an identification method thereof. Can provide.
즉, 본 발명은 하기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)일 수 있다. That is, the present invention may be an amine-based oil identifier (Marker) containing a carbamate group represented by the following formula (1).
화학식 (1)Formula (1)
여기서, R1, R2, R3는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C20, 바람직하게는 C1 내지 C12, 보다 더 바람직하게는 C1 내지 C6의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐원소를 포함하거나 포함하지 않는 헤테로 고리 일 수 있다. Here, R1, R2, R3 are each independently hydrogen, substituted or unsubstituted C1 to C20, preferably C1 to C12, even more preferably a C1 to C6 alkyl group, a heteroalkyl group containing or not including a carbamate group Or it may be an aryl group, O,N,S,P, or a hetero ring containing or not containing a halogen element.
일반적으로 닌하이드린 반응을 통해 유류의 진위여부를 식별하기 위해 사용되는 노말 알킬 아민 또는 다이아민은 흡착제 등에 의한 제거가 용이하여 유류의 진위여부를 식별하는 방법에 있어서의 신뢰성 및 안정성 등의 문제가 존재하였다.In general, normal alkyl amines or diamines, which are used to identify the authenticity of oil through ninhydrin reaction, are easily removed by an adsorbent, so there are problems such as reliability and stability in the method of identifying the authenticity of oil. Existed.
그러나, 본 발명에 따른 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)는 카바메이트기를 포함함으로서 극성을 낮추어 흡착제 등에 의한 제거로부터 안전할 수 있으며, 유류내 소량으로 존재하여도 닌하이드린과 발색반응을 유도할 수 있고, 반응 후의 생성물이 구조적으로 안정하여 재현성이 우수한 장점이 있다. However, the amine-based oil marker (Marker) containing a carbamate group of the formula (1) according to the present invention can be safe from removal by an adsorbent or the like by lowering the polarity by containing a carbamate group. It is possible to induce a color reaction with doninhydrin, and the product after the reaction is structurally stable, and thus has an advantage of excellent reproducibility.
본 발명에 따른 헤테로 알킬기란 O,N,S,P 등 하나 이상의 헤테로 원자를 포함하는 알킬기를 의미한다.The heteroalkyl group according to the present invention means an alkyl group including one or more hetero atoms such as O,N,S,P.
상기 카바메이트기를 포함하는 아민계 유류 식별제(Marker)는 닌하이드린과 반응하는 일반적인 노말알킬 아민 유류식별제에 비하여 극성이 낮아 흡착제에 의해 제거되기 어렵기 때문에, 유류식별에 있어서의 신뢰성을 확보할 수 있다.The amine-based oil identifier (Marker) containing the carbamate group has a lower polarity than the general normal alkyl amine oil identifier that reacts with ninhydrin and is difficult to be removed by an adsorbent, thus securing reliability in oil identification. can do.
본 발명에 따른 유류 식별제(Marker)에 있어서, 헤테로 고리란 고리 내에 탄소 이외의 원소를 하나 이상 포함하고 있는 것을 의미하는 것으로서, 구체적으로 탄소원자 이외에 질소, 산소, 황, 인 원자 또는 할로겐 원소 등을 포함하거나 포함하지 않을 수 있다.In the oil discriminator (Marker) according to the present invention, a hetero ring means that one or more elements other than carbon are included in the ring, and specifically, nitrogen, oxygen, sulfur, phosphorus, or halogen elements other than carbon atoms. May or may not include.
본 발명에 따른 상기 화학식 (1)의 R1은 수소, 치환 또는 비치환된 C1 내지 C20, 바람직하게는 C1 내지 C12, 보다 더 바람직하게는 C1 내지 C6의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐 원소를 포함하거나 포함하지 않는 헤테로 고리 일 수 있으며, R1은 닌하이드린과의 반응을 위한 전처리 단계에서 제거될 수 있다.R1 of the formula (1) according to the present invention is hydrogen, a substituted or unsubstituted C1 to C20, preferably a C1 to C12, even more preferably a C1 to C6 alkyl group, a hetero containing or not containing a carbamate group. It may be an alkyl group or aryl group, O,N,S,P, or a hetero ring containing or not containing a halogen element, and R1 may be removed in a pretreatment step for reaction with ninhydrin.
본 발명에 따른 상기 화학식 (1)의 R2,R3는 수소, 치환 또는 비치환된 C1 내지 C20, 바람직하게는 C1 내지 C12, 보다 더 바람직하게는 C1 내지 C6의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐 원소를 포함하거나 포함하지 않는 헤테로 고리 일 수 있으며, 닌하이드린과의 반응을 위한 전처리 단계를 통해 제거되지 아니한다.R2, R3 of the formula (1) according to the present invention include or do not include hydrogen, substituted or unsubstituted C1 to C20, preferably C1 to C12, even more preferably a C1 to C6 alkyl group or carbamate group. It may be a heteroalkyl group or aryl group, O,N,S,P, or a hetero ring containing or not containing a halogen element, and is not removed through a pretreatment step for reaction with ninhydrin.
상기 전처리 단계는 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)를 닌하이드린과 반응시키기 위한 모든 전처리 방법을 포함할 수 있으며, 보다 구체적으로 상기 전처리 단계를 거치는 경우 유류 식별제(Marker)는 하기 화학식 (2)의 구조를 포함할 수 있다. The pretreatment step may include all pretreatment methods for reacting the amine-based oil identifier (Marker) containing the carbamate group of Formula (1) with ninhydrin, and more specifically, when passing through the pretreatment step, oil The identification agent (Marker) may include the structure of the following formula (2).
화학식 (2)Formula (2)
여기서 R2, R3는 각각 수소, 치환 또는 비치환된 C1 내지 C20, 바람직하게는 C1 내지 C12, 보다 더 바람직하게는 C1 내지 C6의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐 원소를 포함하거나 포함하지 않는 헤테로 고리 일 수 있다.Wherein R2 and R3 are each hydrogen, a substituted or unsubstituted C1 to C20, preferably a C1 to C12, even more preferably a C1 to C6 alkyl group, a heteroalkyl group or an aryl group including or not including a carbamate group, O It may be a hetero ring containing or not containing ,N,S,P or halogen elements.
보다 구체적으로, 본 발명에 따른 상기 화학식 (1)은 터트-뷰틸-N-뷰틸카바메이트(tert-butyl-N-butylcarbamate), 터트-뷰틸-N-(4-{[(터트-뷰톡시)카보닐]아미노}뷰틸)카바메이트( tert-butyl-N-(4-{[(tert-butoxy)carbonyl]amino}butyl)carbamate), 터트-뷰틸-N-(4-{[(터트-뷰톡시)카보닐](메틸)아미노}뷰틸)-N-메틸카바메이트(tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate), 터트-뷰틸-N-(2-{[(터트-뷰톡시)카보닐](메틸)아미노}페닐)-N-메틸카바메이트(tert-butyl-N-(2-{[(tert-butoxy)carbonyl](methyl)amino}phenyl)-N-methylcarbamate), 벤질-N-뷰틸카바메이트(Benzyl-N-butylcarbamate), 9H-플루오렌-9-일메틸-N-뷰틸카바메이트(9H-fluoren-9-ylmethyl-N-butylcarbamate), 프로프-2-엔-1-일-N-뷰틸카바메이트(Prop-2-en-1-yl-N-butylcarbamate), 뷰틸-N-(2,2,2,-트리클로로에틸)카바메이트(Butyl-N-(2,2,2,-trichloroethyl)carbamate), 9H-플루오렌-9-일메틸-N-(2-{[(9H-fluoren-9-일메톡시)카보닐]아미노}에틸)카바메이트(9H-fluoren-9-ylmethyl-N-(2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}ethyl)carbamate) 등 일 수 있으나 이에 제한되는 것은 아니다. More specifically, the formula (1) according to the present invention is tert-butyl-N-butylcarbamate, tert-butyl-N-(4-{[(tert-butoxy) Carbonyl]amino}butyl)carbamate (tert-butyl-N-(4-{[(tert-butoxy)carbonyl]amino}butyl)carbamate), tert-butyl-N-(4-{[(tert-view) Oxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate (tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate), Tert-butyl-N-(2-{[(tert-butoxy)carbonyl](methyl)amino}phenyl)-N-methylcarbamate (tert-butyl-N-(2-{[(tert-butoxy)) carbonyl](methyl)amino}phenyl)-N-methylcarbamate), benzyl-N-butylcarbamate, 9H-fluorene-9-ylmethyl-N-butylcarbamate (9H-fluoren- 9-ylmethyl-N-butylcarbamate), prop-2-en-1-yl-N-butylcarbamate (Prop-2-en-1-yl-N-butylcarbamate), butyl-N-(2,2, 2,-trichloroethyl)carbamate (Butyl-N-(2,2,2,-trichloroethyl)carbamate), 9H-fluoren-9-ylmethyl-N-(2-{[(9H-fluoren-9 -Ylmethoxy)carbonyl]amino}ethyl)carbamate (9H-fluoren-9-ylmethyl-N-(2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}ethyl)carbamate), etc. It is not limited thereto.
본 발명에 따른 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)는 노말 알킬 아민에 비하여, 유류내 소량으로 존재하여도 닌하이드린과 발색반응을 유도할 수 있고, 카바메이트기를 포함함으로써 흡착제 등에 의한 제거로부터 안전할 수 있는 이점이 있다.The amine-based oil identifier (Marker) containing a carbamate group of the formula (1) according to the present invention can induce a color reaction with ninhydrin even when it is present in a small amount in oil compared to normal alkyl amines. By including a mate group, there is an advantage of being safe from removal by an adsorbent or the like.
또한, 본 발명은 카바메이트기를 포함하는 식별제(Marker)로 표지된 유류를 닌하이드린과 반응시켜 발색을 유도함으로써, 유류의 진위여부를 정량적 또는 정성적으로 측정할 수 있는 식별방법에 관한 것일 수 있다. In addition, the present invention relates to an identification method capable of quantitatively or qualitatively measuring the authenticity of oil by inducing color development by reacting oil labeled with an identification agent (Marker) containing a carbamate group with ninhydrin. I can.
즉, 본 발명은 상기 화학식 (1)의 카바메이트를 포함하는 식별제(Marker)로 표지된 유류를 전처리 하는 단계; 및 전처리된 유류 식별제(Marker)를 닌하이드린과 반응시키는 단계;를 포함하는 유류식별방법일 수 있다. That is, the present invention comprises the steps of pre-treating the oil labeled with an identification agent (Marker) containing the carbamate of Formula (1); And reacting the pretreated oil identification agent (Marker) with ninhydrin.
본 발명에 따른 유류의 식별방법은 노말 알킬 아민(Normal alkyl amine) 및 그 유도체를 식별제(Marker)로 사용하는 유류의 식별방법에 비해 상온에서도 빠른 반응속도를 확보할 수 있고, 구조적으로 안정하여 재현성이 우수한 유류의 진위여부를 식별하는 방법을 제공할 수 있다.Compared to the oil identification method using normal alkyl amine and its derivatives as markers, the oil identification method according to the present invention can secure a faster reaction rate at room temperature and is structurally stable. It can provide a method of identifying the authenticity of oil with excellent reproducibility.
더욱이, 카바메이트기로 모노 또는 다이아민 및 그 유도체를 보호함으로서, 유류 식별제(Marker)의 극성을 낮추어 흡착제에 의한 제거로부터 안전할 수 있다. Moreover, by protecting the mono or diamine and its derivatives with a carbamate group, the polarity of the oil marker is lowered, so that it can be safe from removal by an adsorbent.
본 발명에 따른 유류식별방법에 사용되는 유류 식별제(Marker)는 상기 설명된 본 발명에 따른 카바메이트기를 포함하는 아민계 유류 식별제(Marker)를 모두 포함할 수 있다. The oil identification agent (Marker) used in the oil identification method according to the present invention may include all of the amine-based oil identification agent (Marker) including the carbamate group according to the present invention described above.
본 발명에 따른 유류식별방법은 유류 내 포함되어 있는 식별제(Marker)를 닌하이드린과 발색반응을 유도하기 위하여 전처리하는 단계를 포함할 수 있다.The oil identification method according to the present invention may include pre-treating a marker contained in the oil to induce a color reaction with ninhydrin.
상기 전처리 단계는 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)를 닌하이드린과 반응시키기 위한 모든 전처리 방법을 포함할 수 있으며, 일례로서 유기산 또는 무기산 등의 산을 통한 산처리, 염기성 처리 또는 전이금속 촉매를 이용한 처리 등을 포함할 수 있다.The pretreatment step may include all pretreatment methods for reacting the amine-based oil identifier (Marker) containing the carbamate group of Formula (1) with ninhydrin, as an example, through an acid such as an organic acid or an inorganic acid. It may include acid treatment, basic treatment, or treatment using a transition metal catalyst.
즉, 본 발명에 따른 유류식별방법에 있어서, 상기 전처리 단계는 산처리, 염기성 처리 및 전이금속 촉매를 이용한 처리 중 선택되는 어느 하나를 포함하는 것일 수 있다.That is, in the oil identification method according to the present invention, the pretreatment step may include any one selected from acid treatment, basic treatment, and treatment using a transition metal catalyst.
본 발명에 따른 상기 전처리 하는 단계의 일례인 산처리 단계에 이용되는 산은 상기 목적을 달성할 수 있는 것이면 제한없이 이용가능하며, 일례로서 유기산 또는 무기산일 수 있다.The acid used in the acid treatment step, which is an example of the pretreatment step according to the present invention, can be used without limitation as long as it can achieve the above object, and may be an organic acid or inorganic acid as an example.
보다 구체적으로 상기 유기산 또는 무기산은 황산, 트리플루오르아세트산, 염산, 브롬화수소, 요오드화 수소, 질산, 인산, 크롬산, 메탄술폰산, 초산, 보론산, 벤젠술폰산 중 선택되는 어느 하나 또는 이들의 혼합물 일 수 있으나 이에 제한되는 것은 아니다. More specifically, the organic acid or inorganic acid may be any one selected from sulfuric acid, trifluoroacetic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, nitric acid, phosphoric acid, chromic acid, methanesulfonic acid, acetic acid, boronic acid, benzenesulfonic acid, or a mixture thereof. It is not limited thereto.
본 발명에 따른 상기 전처리 하는 단계의 일례인 염기성처리 단계에서 이용되는 염기는 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류식별제를 닌하이드린과 반응하여 발색을 유도할 수 있는 모든 염기를 포함할 수 있다.The base used in the basic treatment step, which is an example of the pretreatment step according to the present invention, is any base capable of inducing color development by reacting an amine-based oil identifier containing a carbamate group of formula (1) with ninhydrin. It may include.
본 발명에 따른 상기 전처리 하는 단계의 일례인 전이금속 촉매를 이용한 처리에 사용되는 전이 금속에는 제한이 없으나, 바람직하게는 백금, 아연, 구리, 니켈, 철, 망간 촉매 또는 이들의 혼합촉매 등이 좋다.The transition metal used in the treatment using a transition metal catalyst, which is an example of the pretreatment step according to the present invention, is not limited, but preferably platinum, zinc, copper, nickel, iron, manganese catalyst, or a mixed catalyst thereof, etc. .
상기 전처리 단계를 통해 본 발명에 따른 유류 식별제(Marker)의 카바메이트기 일부가 디프로텍션(Deprotection)되고, 닌하이드린과 발색반응이 가능한 화학구조의 형태로 변화할 수 있으며, 전처리 단계를 거치는 경우 유류 식별제(Marker)는 하기 화학식 (2)의 구조를 포함할 수 있다. Through the pretreatment step, a part of the carbamate group of the oil identifier (Marker) according to the present invention is deprotected and can be changed into a form of a chemical structure capable of a color reaction with ninhydrin. In the case, the oil identifier (Marker) may include the structure of the following formula (2).
화학식 (2)Formula (2)
여기서 R2, R3는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C12, 보다 바람직하게는 C1 내지 C6의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐원소를 포함하거나 포함하지 않는 헤테로 고리기 일 수 있다.Wherein R2 and R3 are each independently hydrogen, a substituted or unsubstituted C1 to C12, more preferably a C1 to C6 alkyl group, a heteroalkyl group or an aryl group including or not including a carbamate group, O,N,S,P Or it may be a heterocyclic group containing or not containing a halogen element.
즉, 본 발명에 따른 유류식별방법에 있어서, 전처리된 유류 식별제(Marker)는 상기 화학식 (2)인 것을 특징으로 하는 유류식별방법일 수 있다. That is, in the oil identification method according to the present invention, the pretreated oil identification agent (Marker) may be an oil identification method, characterized in that the formula (2).
본 발명에 따른 카바메이트를 포함하는 유류 식별제(Marker)를 전처리 할 경우, 상기 화학식 (2)의 구조일 수 있으며, R2 또는 R3가 N을 포함하는 헤테로 알킬기 또는 카바메이트기를 포함하는 헤테로 알킬기 일 경우 다이아민계 유류 식별제(Marker)로서, 닌하이드린과 반응하여 생성되는 생성물의 구조적 안정성 및 닌하이드린과 소량으로도 빠르게 반응을 하는 등의 이점을 구비할 수 있다.In the case of pretreatment of the oil identifier (Marker) containing carbamate according to the present invention, it may have the structure of formula (2), wherein R2 or R3 is a heteroalkyl group containing N or a heteroalkyl group containing a carbamate group. In this case, as a diamine-based oil identifier (Marker), it may have advantages such as structural stability of a product produced by reacting with ninhydrin and rapid reaction with ninhydrin even in a small amount.
또한, 본 발명에 따른 카바메이트기를 포함하는 유류 식별제(Marker)의 전처리 단계의 일례인 상기 산처리 단계를 거친 이후 닌하이드린과의 발색반응 이전에 중화를 위하여 염기처리하는 단계를 더 포함할 수 있다. In addition, after the acid treatment step, which is an example of the pretreatment step of the oil identifier (Marker) containing a carbamate group according to the present invention, a step of base treatment for neutralization before the color reaction with ninhydrin may be further included. I can.
본 발명에 있어서, 상기 화학식 (1)의 카바메이트기를 포함하는 식별제(Marker)의 유류내 함유량은 제한이 없으나, 1 ppm 이상을 사용하는 것이 바람직하며, 그 이상 사용하는 것에는 제한이 없으나, 더 바람직하게는 1 ppm 내지 800 ppm, 보다 더 바람직하게는 1 ppm 내지 500ppm의 범위 내에서 사용하는 것이 좋으나 이에 제한되는 것은 아니다. In the present invention, the content in the oil of the marker containing the carbamate group of Formula (1) is not limited, but it is preferable to use 1 ppm or more, and there is no limitation on the use of more than that, More preferably, 1 ppm to 800 ppm, even more preferably 1 ppm to 500 ppm, but is not limited thereto.
본 발명에 따른 카바메이트기를 포함하는 식별제(Marker)로 표지된 유류를 전처리 한 후, 반응하는 전개시약(Developer)은 닌하이드린으로서, 하기 화학식 (3)로 표현될 수 있다.After pretreatment of the oil labeled with a marker containing a carbamate group according to the present invention, the reacting developer is ninhydrin, which may be represented by the following formula (3).
화학식 (3)Formula (3)
본 발명에 따른 카바메이트기를 포함하는 유류 식별제(Marker)와 반응하는 닌하이드린 전개시약(Developer)의 농도는 특별히 한정되지 아니하며, 광범위하게 적용할 수 있고, 식별제(Marker)를 포함하는 석유제품에서 취한 시료 중에 포함된 전처리된 카바메이트기를 포함하는 식별제(Marker)를 발색시키기에 충분한 양으로 존재하는 것은 바람직하다.The concentration of the ninhydrin developing reagent (Developer) reacting with the oil identifier (Marker) containing a carbamate group according to the present invention is not particularly limited, and can be widely applied, and petroleum containing a marker (Marker) It is preferable that it is present in an amount sufficient to develop a color of the marker containing the pretreated carbamate group contained in the sample taken from the product.
비제한적인 예로써, 상기 닌하이드린 전개시약(Developer)의 양은 1 ppm 이상이면 좋고 상한에는 제한이 없으나, 바람직하게는 1 내지 10,000 ppm, 더 바람직하게는 1 내지 5,000ppm 일 수 있으나 이에 제한되는 것은 아니다As a non-limiting example, the amount of the ninhydrin developing reagent (Developer) may be 1 ppm or more, and there is no upper limit, but preferably 1 to 10,000 ppm, more preferably 1 to 5,000 ppm, but is limited thereto. Not
본 발명에 따른 전처리된 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)는 닌하이드린 반응을 통해 육안으로 발색여부를 확인할 수 있으며, 상기 발색은 짙은 노란색 또는 보라색을 나타낼 수 있으나 이에 제한되는 것은 아니다. The pretreated amine-based oil marker (Marker) containing the carbamate group of the formula (1) according to the present invention can be visually confirmed whether or not color is developed through a ninhydrin reaction, and the color development is dark yellow or purple. However, it is not limited thereto.
즉, 본 발명에 따른 전처리된 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)로 표지된 유류가 전개시약(Developer)인 닌하이드린과 반응하는 경우 유류는 발색되고 상기 발색은 육안으로 정성적 식별이 가능하며, 흡광도 측정장치를 이용하면 정량적 측정이 가능하다.That is, when the oil labeled with the amine-based oil marker (Marker) containing the carbamate group of the formula (1) pretreated according to the present invention reacts with ninhydrin, the developer, the oil is colored and the above Color development can be qualitatively identified with the naked eye, and quantitative measurement is possible by using an absorbance measuring device.
따라서, 본 발명에 따른 유류 식별방법은 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)로 표지된 유류를 전처리 하는 단계; 전처리된 유류 식별제(Marker)를 닌하이드린과 반응시키는 단계; 및 흡광도 측정장치를 이용하여 흡광도를 측정하는 단계를 포함하는 유류식별 방법 일 수 있다. Accordingly, the oil identification method according to the present invention comprises the steps of pre-treating the oil labeled with an amine-based oil identifier (Marker) containing a carbamate group of Formula (1); Reacting the pretreated oil identification agent (Marker) with ninhydrin; And measuring absorbance by using an absorbance measuring device.
상기 발색의 정량적 측정을 가능하게 하는 흡광도 측정장치에는 제한이 없으나, 현장에서의 즉각적 진위식별이 가능하다는 측면을 고려해 볼 때, 이동성 자외선 가시분광광도계가 바람직하지만 이에 제한되는 것은 아니다. There is no limit to the absorbance measuring device that enables the quantitative measurement of the color development, but considering the aspect that immediate authenticity identification in the field is possible, a mobile ultraviolet visible spectrophotometer is preferable, but is not limited thereto.
본 발명에 따른 유류식별 방법에 있어 식별 가능한 유류는 식별제(Marker)로서 상기 화학식 (1)의 카바메이트기를 포함하는 아민계 유류 식별제(Marker)를 용해시킬 수 있는 모든 유류를 포함하며, 비제한적인 일례로써, 광유, 기유, 등유, 윤활유, 휘발유 등일 수 있으나 이에 제한되는 것은 아니다. The identifiable oil in the oil identification method according to the present invention includes all oils capable of dissolving the amine-based oil identification agent (Marker) containing the carbamate group of the formula (1) as a marker. As a limiting example, it may be mineral oil, base oil, kerosene, lubricating oil, gasoline, etc., but is not limited thereto.
이하, 본 발명에 따른 카바메이트기를 포함하는 아민계 유류 식별제(Marker)의 제조예 및 이로 표지된 유류를 닌하이드린과 반응시켜 흡광도를 측정하는 실시예에 대해서 설명하나, 하기 실시예는 본 발명에 따른 일례에 불과할 뿐이며, 본 발명의 기술적 사상을 제한하지 아니함은 이 기술분야의 통상의 지식을 가진 자에게 자명하다.
Hereinafter, an example of preparing an amine-based oil identifier (Marker) containing a carbamate group according to the present invention and an example of measuring the absorbance by reacting the labeled oil with ninhydrin will be described. It is only an example according to the invention, and does not limit the technical idea of the present invention is obvious to those of ordinary skill in the art.
[제조예 1] - 터트-뷰틸-N-뷰틸카바메이트(tert-butyl-N-butylcarbamate)의 제조[Preparation Example 1]-Preparation of tert-butyl-N-butylcarbamate
뷰틸아민 5 g 을 테트라하이드로퓨란 150 ml가 들어있는 500 ml 반응기 내에 넣고 교반하에 1.0 M의 농도로 테트라하이드로퓨란에 녹아 있는 디터트뷰틸에테인-1,2-디카보네이트 (Di-tert-butyl ethane-1,2-dicarbonate) 용액 85 ml을 천천히 가한다. 상온에서 3 시간 동안 교반하고, 감압 하에 용매를 제거하여 결과된 반응물을 염화메틸렌에 녹이고 물 60 g 및 염화나트륨 포화 수용액 30 g 으로 유기층을 분리한다. 용매를 감압 하에 제거하여, 흰색의 고체를 수득한다. Di-tert-butyl ethane-1,2-dicarbonate dissolved in tetrahydrofuran at a concentration of 1.0 M under stirring was added to 5 g of butylamine in a 500 ml reactor containing 150 ml of tetrahydrofuran. 1,2-dicarbonate) solution 85 ml is slowly added. After stirring at room temperature for 3 hours, the solvent was removed under reduced pressure, and the resulting reaction was dissolved in methylene chloride, and the organic layer was separated with 60 g of water and 30 g of a saturated aqueous sodium chloride solution. The solvent was removed under reduced pressure to obtain a white solid.
1H NMR (400 MHz, CDCl3) δ 4.52 (s, 1H, NH), 2.74-2.75 (m, 2H), 1.08 (s, 9H), 1.07-1.11 (m, 2H), 0.95-1.01 (m, 2H), 0.55 (t, J = 0.8 Hz, 3H)
1 H NMR (400 MHz, CDCl3) δ 4.52 (s, 1H, NH), 2.74-2.75 (m, 2H), 1.08 (s, 9H), 1.07-1.11 (m, 2H), 0.95-1.01 (m, 2H), 0.55 (t, J = 0.8 Hz, 3H)
[제조예 2] - 터트-뷰틸-N-(2-{[(터트-뷰톡시)카보닐]아미노}에틸)카바메이트(tert-butyl-N-(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamate)의 제조[Preparation Example 2]-Tert-butyl-N-(2-{[(tert-butoxy)carbonyl]amino}ethyl)carbamate (tert-butyl-N-(2-{[(tert-butoxy)carbonyl)carbonyl) ]amino}ethyl)carbamate)
에틸렌디아민 2 g 을 테트라하이드로퓨란 80 ml가 들어있는 250 ml 반응기 내에 넣고 교반하에 1.0 M의 농도로 테트라하이드로퓨란에 녹아 있는 디터트뷰틸에테인-1,2-디카보네이트 (Di-tert-butyl ethane-1,2-dicarbonate) 용액 67 ml을 천천히 가한다. 상온에서 3 시간 동안 교반하고, 감압 하에 용매를 제거하여 결과된 반응물을 염화메틸렌에 녹이고 물 30 g 및 염화나트륨 포화 수용액 15 g 으로 유기층을 분리한다. 용매를 감압 하에 제거하여, 흰색의 고체를 수득한다.Add 2 g of ethylenediamine into a 250 ml reactor containing 80 ml of tetrahydrofuran and di-tert-butyl ethane-1,2-dicarbonate dissolved in tetrahydrofuran at a concentration of 1.0 M under stirring. 1,2-dicarbonate) solution 67 ml is slowly added. After stirring at room temperature for 3 hours, the solvent was removed under reduced pressure, and the resulting reaction was dissolved in methylene chloride, and the organic layer was separated with 30 g of water and 15 g of a saturated aqueous sodium chloride solution. The solvent was removed under reduced pressure to obtain a white solid.
1H NMR (400 MHz, CDCl3) δ 4.85 (s, 2H), 3.22 (s, 4H), 1.44 (s, 18H)
1 H NMR (400 MHz, CDCl3) δ 4.85 (s, 2H), 3.22 (s, 4H), 1.44 (s, 18H)
[실시예 1][Example 1]
제조예 1에서 제조한 식별제 10 mg을 등유 1 kg에 첨가한다. 제조한 용액 10 mL를 20 mL 유리병에 담은 후, 트리플루오로아세트산 1 mL를 가하여 1분 동안 흔들고 트리에틸아민 2 mL를 가한다. 충분히 중화된 후 발색시약으로 닌하이드린 지시약을 0.2 mL 첨가하면 용액색이 보라색으로 변하며 분광기로 흡광도를 측정하였을 때, 420 nm에서 최대 흡광도를 나타낸다.
10 mg of the identification agent prepared in Preparation Example 1 was added to 1 kg of kerosene. Put 10 mL of the prepared solution in a 20 mL glass bottle, add 1 mL of trifluoroacetic acid, shake for 1 minute, and add 2 mL of triethylamine. After sufficiently neutralizing, when 0.2 mL of ninhydrin indicator is added as a color developing reagent, the color of the solution turns purple, and when absorbance is measured by a spectrometer, it shows the maximum absorbance at 420 nm.
[실시예 2][Example 2]
제조예 2에서 제조한 식별제 10 mg을 등유 1 kg에 첨가한다. 제조한 용액 10 mL를 20 mL 유리병에 담은 후, 트리플루오로아세트산 1 mL를 가하여 1분 동안 흔들고 트리에틸아민 2 mL를 가한다. 충분히 중화된 후 발색시약으로 닌하이드린 지시약을 0.2 mL 첨가하면 용액색이 보라색으로 변하며 분광기로 흡광도를 측정하였을 때, 420 nm에서 최대 흡광도를 나타낸다.10 mg of the identification agent prepared in Preparation Example 2 was added to 1 kg of kerosene. Put 10 mL of the prepared solution in a 20 mL glass bottle, add 1 mL of trifluoroacetic acid, shake for 1 minute, and add 2 mL of triethylamine. After sufficiently neutralizing, when 0.2 mL of ninhydrin indicator is added as a color developing reagent, the color of the solution turns purple, and when absorbance is measured by a spectrometer, it shows the maximum absorbance at 420 nm.
[실시예 3][Example 3]
실시예 1에서 제조한 등유 100 mL에 16 g의 활성탄을 첨가한 후 하루 동안 교반한다. 교반 후 활성탄을 여과하여 제거하면 무색의 용액을 얻을 수 있다. 흡착 테스트를 진행한 용액 10 mL를 20 mL 유리병에 담은 후, 트리플루오로아세트산 1 mL를 가하여 1분 동안 흔들고 트리에틸아민 2 mL를 가한다. 충분히 중화된 후 발색시약으로 닌하이드린을 첨가한다. 첨가 즉시 용액색이 보라색으로 변하며, 분광기로 흡광도를 확인해 보면 420 nm에서 가장 큰 흡광도를 나타낸다.
After adding 16 g of activated carbon to 100 mL of kerosene prepared in Example 1, the mixture was stirred for one day. After stirring, the activated carbon is filtered off to obtain a colorless solution. After 10 mL of the solution subjected to the adsorption test was put in a 20 mL glass bottle, 1 mL of trifluoroacetic acid was added, shaken for 1 minute, and 2 mL of triethylamine was added. After sufficiently neutralizing, ninhydrin is added as a color developing reagent. Immediately after addition, the color of the solution turns purple, and when the absorbance is checked with a spectrometer, it shows the largest absorbance at 420 nm.
[실시예 4][Example 4]
실시예 2에서 제조한 등유 100 mL에 16 g의 활성탄을 첨가한 후 하루 동안 교반한다. 교반 후 활성탄을 여과하여 제거하면 무색의 용액을 얻을 수 있다. 흡착 테스트를 진행한 용액 10 mL를 20 mL 유리병에 담은 후, 트리플루오로아세트산 1 mL를 가하여 1분 동안 흔들고 트리에틸아민 2 mL를 가한다. 충분히 중화된 후 발색시약으로 닌하이드린을 첨가한다. 첨가 즉시 용액색이 보라색으로 변하며, 분광기로 흡광도를 확인해 보면 420 nm에서 가장 큰 흡광도를 나타낸다.
After adding 16 g of activated carbon to 100 mL of kerosene prepared in Example 2, the mixture was stirred for one day. After stirring, the activated carbon is filtered off to obtain a colorless solution. After 10 mL of the solution subjected to the adsorption test was put in a 20 mL glass bottle, 1 mL of trifluoroacetic acid was added, shaken for 1 minute, and 2 mL of triethylamine was added. After sufficiently neutralizing, ninhydrin is added as a color developing reagent. Immediately after addition, the color of the solution turns purple, and when the absorbance is checked with a spectrometer, it shows the largest absorbance at 420 nm.
[비교예][Comparative Example]
UNIMARK®1494DB 식별제(UNITED COLOR MANUFACTURING, INC사 제품) 10 mg을 등유 1 kg에 첨가한다. 제조한 용액 100 mL에 16 g의 활성탄을 첨가한 후 하루 동안 교반한다. 교반 후 활성탄을 여과하여 제거하면 무색의 용액을 얻을 수 있다. 흡착 테스트를 진행한 용액 15 mL를 20 mL 유리병에 담은 후, 발색시약으로 벤질트리메틸암모늄 히드록사이드(Benzyltrimethylammonium hydroxide) 희석액을 첨가한다. 식별제가 모두 제거되어 용액의 색이 변하지 않는다.
10 mg of UNIMARK® 1494DB identification agent (manufactured by UNITED COLOR MANUFACTURING, INC) is added to 1 kg of kerosene. After adding 16 g of activated carbon to 100 mL of the prepared solution, the mixture was stirred for one day. After stirring, the activated carbon is filtered off to obtain a colorless solution. 15 mL of the solution subjected to the adsorption test is put in a 20 mL glass bottle, and then a diluted solution of benzyltrimethylammonium hydroxide is added as a color developing reagent. The color of the solution does not change as all of the identification agent is removed.
상기와 같이 실시예 1 내지2에 따라 제조된 카바메이트를 포함하는 아민계 유류 식별제(Marker)를 포함하는 등유에 활성탄을 첨가하여 교반한 후 여과하면 실시예 3 내지 4 에서와 같이 무색의 용액을 얻을 수 있고, 전처리 및 중화 처리 후에 발색 시약을 다시 투여하였을 경우, 발색이 되어 각 실시예에 대응하는 최대흡수 파장에서 동일한 흡광도를 얻을 수 있었다. When activated carbon is added to kerosene containing an amine-based oil marker (Marker) containing carbamate prepared according to Examples 1 to 2 as described above, stirred, and filtered, a colorless solution as in Examples 3 to 4 Can be obtained, and when the color developing reagent is administered again after the pretreatment and neutralization treatment, the color is developed and the same absorbance can be obtained at the maximum absorption wavelength corresponding to each example.
따라서, 본 발명에 따른 카바메이트를 포함하는 아민계 유류 식별제(Marker)는 활성탄에 의해 제거되지 아니함을 알 수 있고, 비교예와 같은 식별제(Marker)와는 달리 유류 제품에 대한 진위의 안정성을 도모할 수 있다. Therefore, it can be seen that the amine-based oil identifier (Marker) containing the carbamate according to the present invention is not removed by activated carbon, and unlike the marker such as the comparative example, the authenticity of the oil product is improved. I can plan.
Claims (13)
상기 유류 식별제는 상기 유류 내 함유량 1 ppm 이상으로 포함되어 사용되는 것을 특징으로 하는, 아민계 유류 식별제(Marker).
화학식 (1)
(여기서, R1, R2, R3는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C20의 알킬기, 또는 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기이다.)As an amine oil identifier (Marker) containing a carbamate group of the following formula (1),
The oil identification agent, characterized in that used by being included in the oil content of 1 ppm or more, amine oil identification agent (Marker).
Formula (1)
(Here, R1, R2, and R3 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a heteroalkyl group containing or not including a carbamate group.)
상기 화학식 (1)은 터트-뷰틸-N-뷰틸카바메이트(tert-butyl-N-butylcarbamate), 터트-뷰틸-N-(4-{[(터트-뷰톡시)카보닐]아미노}뷰틸)카바메이트( tert-butyl-N-(4-{[(tert-butoxy)carbonyl]amino}butyl)carbamate), 터트-뷰틸-N-(4-{[(터트-뷰톡시)카보닐](메틸)아미노}뷰틸)-N-메틸카바메이트(tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate), 9H-플루오렌-9-일메틸-N-뷰틸카바메이트(9H-fluoren-9-ylmethyl-N-butylcarbamate), 프로프-2-엔-1-일-N-뷰틸카바메이트(Prop-2-en-1-yl-N-butylcarbamate), 뷰틸-N-(2,2,2,-트리클로로에틸)카바메이트(Butyl-N-(2,2,2,-trichloroethyl)carbamate), 9H-플루오렌-9-일메틸-N-(2-{[(9H-fluoren-9-일메톡시)카보닐]아미노}에틸)카바메이트(9H-fluoren-9-ylmethyl-N-(2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}ethyl)carbamate) 중에서 선택되는 어느 하나인 카바메이트기를 포함하는 아민계 유류 식별제(Marker).
The method of claim 1,
Formula (1) is tert-butyl-N-butylcarbamate, tert-butyl-N-(4-{[(tert-butoxy)carbonyl]amino}butyl)carba Mate (tert-butyl-N-(4-{[(tert-butoxy)carbonyl]amino}butyl)carbamate), tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl) Amino}butyl)-N-methylcarbamate (tert-butyl-N-(4-{[(tert-butoxy)carbonyl](methyl)amino}butyl)-N-methylcarbamate), 9H-fluoren-9-yl Methyl-N-butylcarbamate (9H-fluoren-9-ylmethyl-N-butylcarbamate), prop-2-en-1-yl-N-butylcarbamate (Prop-2-en-1-yl-N- butylcarbamate), Butyl-N-(2,2,2,-trichloroethyl)carbamate), 9H-fluorene-9-ylmethyl-N -(2-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}ethyl)carbamate (9H-fluoren-9-ylmethyl-N-(2-{[(9H-fluoren-9-ylmethoxy) carbonyl]amino}ethyl)carbamate), an amine oil identifier (Marker) containing a carbamate group.
상기 전처리된 유류 식별제(Marker)를 닌하이드린과 반응시키는 단계;를 포함하는 유류식별방법.Pre-treating the oil labeled with an amine-based oil identifier (Marker) containing a carbamate group of the formula (1) of claim 1; And
Oil identification method comprising; reacting the pretreated oil identification agent (Marker) with ninhydrin.
상기 전처리된 유류 식별제(Marker)는 하기 화학식 (2)인 것을 특징으로 하는 유류식별방법.
화학식 (2)
(여기서 R2, R3는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C20의 알킬기, 카바메이트기를 포함하거나 포함하지 않는 헤테로 알킬기 또는 아릴기, O,N,S,P 또는 할로겐원소를 포함하거나 포함하지 않는 헤테로 고리기이다.)The method of claim 3,
The pretreated oil identification method (Marker) is an oil identification method, characterized in that the formula (2).
Formula (2)
(Where R2, R3 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a heteroalkyl group or an aryl group including or not including a carbamate group, O,N,S,P, or a halogen element It is not a heterocyclic group.)
상기 전처리는 산처리, 염기처리 및 전이금속 촉매를 이용한 처리 중 선택되는 어느 하나를 포함하는 것인 유류식별방법.The method of claim 4,
The pre-treatment comprises any one selected from acid treatment, base treatment, and treatment using a transition metal catalyst.
상기 산처리 단계는 유기산 또는 무기산으로 산처리 하는 것인 유류식별방법.The method of claim 5,
The acid treatment step is an oil identification method wherein the acid treatment is performed with an organic acid or an inorganic acid.
상기 유기산 또는 무기산은 황산, 트리플루오르아세트산, 염산, 브롬화수소, 요오드화 수소, 질산, 인산, 크롬산, 메탄술폰산 중 선택되는 어느 하나 또는 이들의 혼합물 인 것을 특징으로 하는 유류식별방법.The method of claim 6,
The organic acid or inorganic acid is any one selected from sulfuric acid, trifluoroacetic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, nitric acid, phosphoric acid, chromic acid, methanesulfonic acid, or a mixture thereof.
흡광도 측정장치를 이용하여 흡광도를 측정하는 단계;를 더 포함하는 유류 식별방법.The method according to any one of claims 3 to 7,
Measuring the absorbance using an absorbance measuring device; Oil identification method further comprising.
상기 유류식별제가 상기 유류 내 1 내지 800ppm 포함되어 있는 것을 특징으로 하는 유류 식별방법.The method of claim 8,
Oil identification method, characterized in that the oil identification agent is contained in the oil 1 to 800ppm.
상기 유류가 광유, 기유, 등유, 윤활유, 휘발유 중에서 선택되는 어느 하나인 유류 식별방법.The method of claim 9,
Oil identification method in which the oil is any one selected from mineral oil, base oil, kerosene, lubricating oil, and gasoline.
상기 흡광도 측정장치를 이용하여 측정한 흡광도의 최대흡수 파장이 400 내지 800nm인 유류 식별방법.The method of claim 10,
Oil identification method in which the maximum absorption wavelength of the absorbance measured using the absorbance measuring device is 400 to 800 nm.
상기 흡광도 측정장치는 이동성 자외선 가시분광 광도계인 것을 특징으로 하는 유류 식별방법.
The method of claim 11,
The absorbance measuring device is an oil identification method, characterized in that the mobile ultraviolet visible spectrophotometer.
상기 유류 식별제를 이용하여 전개시약인 닌하이드린과 반응시켜 발색하게 하는 것을 특징으로 하는, 아민계 유류 식별제(Marker).
The method of claim 1,
An amine-based oil identifier (Marker), characterized in that by reacting with ninhydrin, a developing reagent, using the oil identifier to develop color.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009120563A1 (en) | 2008-03-25 | 2009-10-01 | The Lubrizol Corporation | Marker dyes for petroleum products |
| 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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| JPS602056B2 (en) | 1979-10-11 | 1985-01-18 | 株式会社千代田製作所 | Gas removal method and device for gas sterilization containers for medical instruments |
| DE4238994A1 (en) * | 1992-11-19 | 1994-05-26 | Basf Ag | Aniline as a marking agent for mineral oils |
| KR20030040312A (en) * | 2003-04-24 | 2003-05-22 | (주)이노바이오시스템 | Reformulated gasoline test chip using dye array and method using it |
| KR101058120B1 (en) | 2009-10-09 | 2011-08-24 | 오리엔트화학 (주) | Identification method for petroleum products and identification agent for petroleum products used therein |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009120563A1 (en) | 2008-03-25 | 2009-10-01 | The Lubrizol Corporation | Marker dyes for petroleum products |
| 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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