JP5306955B2 - Analysis method of fuel oil - Google Patents
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 82
- 238000004458 analytical method Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 claims abstract description 27
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000002897 diene group Chemical group 0.000 claims abstract 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 32
- 238000011088 calibration curve Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 abstract description 7
- 238000001228 spectrum Methods 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 description 55
- 238000005259 measurement Methods 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000003502 gasoline Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003209 petroleum derivative Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- XRYKNRLGZZNWEE-UHFFFAOYSA-N 4-methyl-1,2,4-triazole-3,5-dione Chemical compound CN1C(=O)N=NC1=O XRYKNRLGZZNWEE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- -1 2-butanone Chemical class 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000451 chemical ionisation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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Abstract
Description
本発明は、燃料油の分析方法に関する。 The present invention relates to a method for analyzing fuel oil.
ガソリン等の石油製品の重要な性状の一つとして、ジエン価がある。ジエン価は石油製品中の共役ジエン構造の含有量に基づく値であり、当該石油製品１００ｇと反応する無水マレイン酸と当量のヨウ素のｇ数で表される。石油製品のジエン価が高い場合、すなわち石油製品中に共役ジエン構造が多く存在する場合、酸化安定性が悪化する等の問題が生じることが知られている。 One important property of petroleum products such as gasoline is the diene value. The diene value is a value based on the content of the conjugated diene structure in the petroleum product, and is represented by the number of g of iodine equivalent to maleic anhydride that reacts with 100 g of the petroleum product. It is known that when the diene value of a petroleum product is high, that is, when there are many conjugated diene structures in the petroleum product, problems such as deterioration in oxidation stability occur.
従来、ジエン価の測定方法としては、測定試料と無水マレイン酸とを反応させ、当該反応に供された無水マレイン酸の量を滴定により求める、ＵＯＰ法３２６−８２が知られている。 Conventionally, as a method for measuring the diene value, UOP method 326-82 is known in which a measurement sample is reacted with maleic anhydride and the amount of maleic anhydride subjected to the reaction is determined by titration.
また、ナフサ中の共役ジエン構造の定量方法として、４−メチル−１，２，４−トリアゾリン−３，５−ジオン（ＭＴＡＤ）により共役ジエン構造を選択的・定量的に化学誘導体化し、化学イオン化ガスクロマトグラフ／質量分析法（ＣＩ ＧＣ／ＭＳ）による炭素数に応じたＭＴＡＤ−ジエン付加物の選択的且つ定量的な測定を行う方法が知られている（特許文献１）。 As a method for quantifying the conjugated diene structure in naphtha, the conjugated diene structure is selectively and quantitatively chemically derivatized with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) to perform chemical ionization. A method for selectively and quantitatively measuring an MTAD-diene adduct according to the number of carbon atoms by gas chromatography / mass spectrometry (CI GC / MS) is known (Patent Document 1).
しかしながら、ＵＯＰ法３２６−８２及び特許文献１に記載の方法は、測定試料中の共役ジエン構造と無水マレイン酸又はＭＴＡＤとを反応させる前処理工程が必須であるため、操作が煩雑であり、分析に長時間を要する。そのため、多くの燃料油サンプルにおける共役ジエン構造の含有割合を短時間で測定することが可能な分析方法を確立することが求められている。
However, since the UOP method 326-82 and the method described in
そこで、本発明は、燃料油中の共役ジエン構造の含有割合を迅速に測定することが可能な燃料油の分析方法を提供することを目的とする。 Then, an object of this invention is to provide the analysis method of the fuel oil which can measure rapidly the content rate of the conjugated diene structure in fuel oil.
すなわち本発明は、燃料油の１Ｈ−ＮＭＲスペクトルを測定する工程と、上記１Ｈ−ＮＭＲスペクトルにおける、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａに基づいて、上記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法を提供する。このような燃料油の分析方法では、１Ｈ−ＮＭＲ測定によって得られるピークの積分値を用いていることから、迅速に燃料油中の共役ジエン構造の含有割合を測定することができる。 That is, the present invention includes a step of measuring a 1 H-NMR spectrum of a fuel oil, and an integral value of all peaks α observed at 6.1 to 6.6 ppm based on tetramethylsilane in the 1 H-NMR spectrum. And a step of obtaining the content ratio of the conjugated diene structure in the fuel oil based on the total A of the fuel oil. In such a fuel oil analysis method, since the integrated value of the peak obtained by 1 H-NMR measurement is used, the content ratio of the conjugated diene structure in the fuel oil can be measured quickly.
本発明はまた、燃料油と標準物質とを含有する試料の１Ｈ−ＮＭＲスペクトルを測定する工程と、上記１Ｈ−ＮＭＲスペクトルにおける、上記標準物質由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂに基づいて、上記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法を提供する。このような燃料油の分析方法は、１Ｈ−ＮＭＲ測定によって得られるピークの積分値を用いていることから、迅速に燃料油中の共役ジエン構造の含有割合を測定することができる。また、標準物質を用いていることから、共役ジエン構造の含有割合を、迅速且つ高精度で測定することができる。 The present invention also includes a step of measuring a 1 H-NMR spectrum of a sample containing fuel oil and a standard substance, and tetramethyl with respect to an integral value B of the peak β derived from the standard substance in the 1 H-NMR spectrum. Determining the content ratio of the conjugated diene structure in the fuel oil based on the ratio A / B of the total A of the integrated values of all peaks α observed at 6.1 to 6.6 ppm based on silane. The present invention provides a method for analyzing fuel oil. Such a fuel oil analysis method uses the integral value of the peak obtained by 1 H-NMR measurement, and thus can quickly measure the content ratio of the conjugated diene structure in the fuel oil. Further, since the standard substance is used, the content ratio of the conjugated diene structure can be measured quickly and with high accuracy.
本発明はまた、共役ジエン構造の含有割合が互いに異なる複数の燃料油について、それぞれ標準物質とともに１Ｈ−ＮＭＲスペクトルを測定して、上記標準物質由来のピークβ’の積分値Ｂ’に対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークα’の積分値の合計Ａ’の比Ａ’／Ｂ’を求める工程と、上記複数の燃料油について求めたそれぞれの上記比Ａ’／Ｂ’と上記含有割合との関係に基づいて、検量線を得る工程と、燃料油と標準物質とを含有する試料の１Ｈ−ＮＭＲスペクトルを測定する工程と、上記試料の１Ｈ−ＮＭＲスペクトルにおける、上記標準物質由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂと、上記検量線とに基づいて、上記試料に含まれる上記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法を提供する。このような燃料油の分析方法は、１Ｈ−ＮＭＲ測定によって得られるピークの積分値を用いていることから、迅速に燃料油中の共役ジエン構造の含有割合を測定することができる。また、標準物質を用いていることから、共役ジエン構造の含有割合を、迅速且つ高精度で測定することができる。また、検量線を用いていることから、複数の試料を迅速且つ簡便に測定することができる。 The present invention also measures the 1 H-NMR spectrum together with the standard substance for a plurality of fuel oils having different conjugated diene structure content ratios, and calculates the tetra value relative to the integral value B ′ of the peak β ′ derived from the standard substance. A step of obtaining a ratio A ′ / B ′ of total A ′ of integral values of all peaks α ′ observed at 6.1 to 6.6 ppm based on methylsilane; Based on the relationship between the ratio A ′ / B ′ and the content ratio, a step of obtaining a calibration curve, a step of measuring a 1 H-NMR spectrum of a sample containing fuel oil and a standard substance, and 1 of the sample The ratio A / B of the total value A of the integrated values of all peaks α observed at 6.1 to 6.6 ppm based on tetramethylsilane with respect to the integrated value B of the peak β derived from the standard substance in the H-NMR spectrum. When, And a step of obtaining a content ratio of a conjugated diene structure in the fuel oil contained in the sample based on the calibration curve. Such a fuel oil analysis method uses the integral value of the peak obtained by 1 H-NMR measurement, and thus can quickly measure the content ratio of the conjugated diene structure in the fuel oil. Further, since the standard substance is used, the content ratio of the conjugated diene structure can be measured quickly and with high accuracy. In addition, since a calibration curve is used, a plurality of samples can be measured quickly and easily.
本発明の分析方法において、上記標準物質は含酸素化合物又は含珪素化合物であることが好ましい。これらの標準物質を用いることで一層高精度の分析が可能となる。 In the analysis method of the present invention, the standard substance is preferably an oxygen-containing compound or a silicon-containing compound. By using these standard substances, analysis with higher accuracy becomes possible.
本発明によれば、燃料油中の共役ジエン構造の含有割合を迅速に測定することが可能な、燃料油の分析方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the analysis method of fuel oil which can measure rapidly the content rate of the conjugated diene structure in fuel oil is provided.
本発明の燃料油の分析方法の好適な実施形態について以下に説明する。 A preferred embodiment of the fuel oil analysis method of the present invention will be described below.
本実施形態に係る燃料油の分析方法は、燃料油の１Ｈ−ＮＭＲスペクトル（水素−核磁気共鳴スペクトル）を測定する第１工程と、上記１Ｈ−ＮＭＲスペクトルにおける、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａに基づいて、上記燃料油における共役ジエン構造の含有割合を求める第２工程と、を有する。 The fuel oil analysis method according to this embodiment includes a first step of measuring a 1 H-NMR spectrum (hydrogen-nuclear magnetic resonance spectrum) of the fuel oil and tetramethylsilane in the 1 H-NMR spectrum as a reference. And a second step of determining the content ratio of the conjugated diene structure in the fuel oil based on the total A of the integral values of all peaks α observed at 6.1 to 6.6 ppm.
第１工程では、まず燃料油を準備する。燃料油としては、原油又はその混合物に対して、蒸留、分解、改質、その他の精製処理等を適宜行うことによって得られる留分又は残渣が挙げられる。より具体的には、自動車エンジン用ガソリン、農業用内燃機関用ガソリン、林業用内燃機関用ガソリン等に代表されるガソリン留分；燃料用ナフサ等に代表されるナフサ留分（軽質ナフサ、重質ナフサ、ホールレンジナフサ等）；ジェット燃料、航空ガソリン等に代表されるジェット燃料留分；冷暖房用灯油、厨房用灯油、石油発動機用灯油、工業燃料用灯油等に代表される灯油留分；自動車ディーゼルエンジン用軽油、加熱燃料用軽油等に代表される軽油留分；ボイラー用重油、ビル暖房用重油、船舶ディーゼルエンジン用重油、窯業用重油等に代表される重油留分（Ａ重油、Ｂ重油、Ｃ重油等）；及びこれらの混合物等が挙げられる。 In the first step, fuel oil is first prepared. Examples of the fuel oil include fractions or residues obtained by appropriately subjecting crude oil or a mixture thereof to distillation, decomposition, reforming, and other purification treatments. More specifically, gasoline fractions represented by gasoline for automobile engines, gasoline for agricultural internal combustion engines, gasoline for forestry internal combustion engines, etc .; naphtha fractions represented by naphtha for fuel (light naphtha, heavy Naphtha, hall range naphtha, etc.); jet fuel fractions typified by jet fuel, aviation gasoline, etc .; kerosene fractions typified by kerosene for air conditioning, kitchen kerosene, kerosene for oil engines, kerosene for industrial fuels, etc .; Gas oil fraction represented by diesel oil for automobile diesel engines, diesel oil for heating fuel, etc .; heavy oil fraction represented by heavy oil for boilers, heavy oil for building heating, heavy oil for marine diesel engines, heavy oil for ceramics, etc. (A heavy oil, B Heavy oil, C heavy oil, etc.); and mixtures thereof.
本実施形態に係る燃料油の分析方法は、上述した各種の燃料油及びそれらの混合物の何れも分析可能であるが、特に、ガソリンを含有する燃料油や、ガソリンの基材であるガソリン基材を分析することに優れる。ここでガソリンとしては、ＪＩＳＫ２２０２「自動車ガソリン」で規定される１号ガソリンや２号ガソリン等が挙げられる。 The fuel oil analysis method according to the present embodiment can analyze any of the above-described various fuel oils and mixtures thereof. In particular, the fuel oil containing gasoline or the gasoline base material that is the base material of gasoline. It is excellent to analyze. Examples of gasoline include No. 1 gasoline and No. 2 gasoline defined by JISK2202 “Automobile gasoline”.
本実施形態に係る１Ｈ−ＮＭＲスペクトルは、上述の燃料油を、市販のＮＭＲ装置を用いて通常の方法で分析することによって得られる。例えば、燃料油が重溶媒で希釈された測定用溶液を用いて、燃料油の１Ｈ−ＮＭＲスペクトルを測定することが好ましい。重溶媒としては、重クロロホルム（ＣＤＣｌ３）、重ＤＭＳＯ（（Ｄ３Ｃ）２Ｓ＝Ｏ）、重水（Ｄ２Ｏ）、重メタノール（ＣＤ３ＯＤ）、重テトラヒドロフラン（Ｃ４Ｄ８Ｏ）、重アセトニトリル（ＣＤ３ＣＮ）、重ジクロロメタン（ＣＤ２ＣＣｌ２）、重ベンゼン（Ｃ６Ｄ６）、重トルエン（Ｃ６Ｄ５ＣＤ３）、重Ｎ，Ｎ−ジメチルホルムアミド（（ＣＤ３）２Ｎ−ＣＤＯ）等が挙げられる。これらのうち、より安全に分析を行う観点から、重クロロホルムが好ましい。 The 1 H-NMR spectrum according to this embodiment is obtained by analyzing the above-described fuel oil by a usual method using a commercially available NMR apparatus. For example, it is preferable to measure the 1 H-NMR spectrum of the fuel oil using a measurement solution in which the fuel oil is diluted with a heavy solvent. As heavy solvents, heavy chloroform (CDCl 3 ), heavy DMSO ((D 3 C) 2 S═O), heavy water (D 2 O), heavy methanol (CD 3 OD), heavy tetrahydrofuran (C 4 D 8 O) , Heavy acetonitrile (CD 3 CN), heavy dichloromethane (CD 2 CCl 2 ), heavy benzene (C 6 D 6 ), heavy toluene (C 6 D 5 CD 3 ), heavy N, N-dimethylformamide ((CD 3 ) 2 N-CDO) and the like. Of these, deuterated chloroform is preferred from the viewpoint of safer analysis.
また上記測定用溶液は、上記１Ｈ−ＮＭＲスペクトルにおいてケミカルシフトを定める基準となる化合物（以下、「基準化合物」という）を含有することが好ましい。このような基準化合物としては、テトラメチルシラン、ヘキサメチルジシラン、ヘキサメチルジシロキサン等が挙げられ、これらのうちテトラメチルシランが好ましい。測定用溶液がテトラメチルシランを含有する場合、上記１Ｈ−ＮＭＲスペクトルにおいてテトラメチルシラン由来のピークが観測され、当該ピークの位置を０ｐｐｍとすることで、確実に「テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａ」を得ることができる。 Moreover, it is preferable that the said measurement solution contains the compound (henceforth "reference | standard compound") used as the reference | standard which determines a chemical shift in the said < 1 > H-NMR spectrum. Examples of such a reference compound include tetramethylsilane, hexamethyldisilane, hexamethyldisiloxane, and the like, among which tetramethylsilane is preferable. When the measurement solution contains tetramethylsilane, a peak derived from tetramethylsilane is observed in the 1 H-NMR spectrum, and the position of the peak is set to 0 ppm. The total integrated value A ”of all peaks α observed at .1 to 6.6 ppm can be obtained.
第２工程では、上記１Ｈ−ＮＭＲスペクトルにおける、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａに基づいて、上記燃料油における共役ジエン構造の含有割合を求める。例えば、第１工程において上記測定用溶液に所定量の標準物質を添加し、当該標準物質由来のピークβの積分値Ｂと、６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａとを対比することにより、燃料油中の共役ジエン構造の含有割合を求めることができる。 In the second step, the conjugated diene structure in the fuel oil is based on the sum A of integral values of all peaks α observed at 6.1 to 6.6 ppm with reference to tetramethylsilane in the 1 H-NMR spectrum. Is determined. For example, a predetermined amount of a standard substance is added to the measurement solution in the first step, and the integral value B of the peak β derived from the standard substance and the integral value of all peaks α observed at 6.1 to 6.6 ppm. By comparing with the total A, the content ratio of the conjugated diene structure in the fuel oil can be obtained.
標準物質としては、含酸素化合物又は含珪素化合物が好ましく、含酸素化合物としては、酸素原子のα位の炭素原子に結合した水素原子を有する含酸素化合物が好ましい。本実施形態の１Ｈ−ＮＭＲスペクトルにおける「標準物質由来のピークβ」としては、標準物質以外の成分のピークが観測されない位置にあるピークを選択することが好ましい。このようなピークとしては、例えば、酸素原子のα位の炭素原子に結合した水素原子由来のピークが挙げられる。当該ピークの積分値を用いて燃料油中の共役ジエン構造の含有割合を求めることで、種々の燃料油（特にガソリン）に対して、高精度の分析を確実に行うことができる。 As the standard substance, an oxygen-containing compound or a silicon-containing compound is preferable, and as the oxygen-containing compound, an oxygen-containing compound having a hydrogen atom bonded to the α-position carbon atom of the oxygen atom is preferable. As the “peak β derived from the standard substance” in the 1 H-NMR spectrum of the present embodiment, it is preferable to select a peak at a position where a peak of a component other than the standard substance is not observed. Examples of such a peak include a peak derived from a hydrogen atom bonded to a carbon atom at the α-position of an oxygen atom. By obtaining the content ratio of the conjugated diene structure in the fuel oil using the integrated value of the peak, it is possible to reliably perform a highly accurate analysis on various fuel oils (particularly gasoline).
上記含酸素化合物としては、メタノール、エタノール等のアルコール類；イソ酪酸等のカルボン酸類；１，３−ジオキサン、１，４−ジオキサン、テトラヒドロフラン等の環状エーテル類；２−ブタノン等のケトン類、等が挙げられる。これらのうち、より高精度で容易に分析結果を得る観点からアルコール類が好ましく、燃料油由来のピークシグナルと重なりにくく且つ高精度の分析結果が得られる観点からメタノールがより好ましい。 Examples of the oxygen-containing compound include alcohols such as methanol and ethanol; carboxylic acids such as isobutyric acid; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; ketones such as 2-butanone, and the like. Is mentioned. Among these, alcohols are preferable from the viewpoint of easily obtaining analysis results with higher accuracy, and methanol is more preferable from the viewpoint of being difficult to overlap with the peak signal derived from fuel oil and obtaining highly accurate analysis results.
上記含珪素化合物としては、テトラメチルシラン、ヘキサメチルジシラン、ヘキサメチルジシロキサン等が挙げられ、これらのうち、より高精度の分析結果を得る観点から、テトラメチルシランが好ましい。なお、上記標準物質が含珪素化合物である場合の「標準物質由来のピークβ」としては、珪素原子のα位の炭素原子に結合した水素原子由来のピークが好ましい。当該ピークは、標準物質以外の成分のピークが観測されにくい位置にあるため、種々の燃料油に対して高精度の分析を確実に行うことができる。 Examples of the silicon-containing compound include tetramethylsilane, hexamethyldisilane, and hexamethyldisiloxane. Among these, tetramethylsilane is preferable from the viewpoint of obtaining a more accurate analysis result. In addition, as the “peak β derived from the standard substance” when the standard substance is a silicon-containing compound, a peak derived from a hydrogen atom bonded to a carbon atom at the α-position of the silicon atom is preferable. Since the peak is at a position where it is difficult to observe peaks of components other than the standard substance, high-precision analysis can be reliably performed on various fuel oils.
また、本実施形態に係る燃料油の分析方法は、検量線を求める工程を有していてもよい。このような工程を有することによって、標準物質由来のピークβの積分値Ｂとテトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂと、検量線とに基づいて、燃料油に含まれる共役ジエン構造の含有割合をより迅速に求めることができる。検量線は、例えば、次の通りにして求めることができる。まず複数の燃料油について、共役ジエン構造の含有割合（例えば、ジエン価）を公知の測定法（例えば、ＵＯＰ法３２６−８２）により求める。次いで、共役ジエン構造の含有割合が互いに異なる複数の燃料油に、それぞれ標準物質を所定の割合で混合し、検量線作成用の試料を複数調製する。次いで、当該複数の試料の１Ｈ−ＮＭＲスペクトルを測定して「標準物質由来のピークβ’の積分値Ｂ’に対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークα’の積分値の合計Ａ’の比Ａ’／Ｂ’」を求める。そして、前記複数の試料について求めたそれぞれの当該比Ａ’／Ｂ’と共役ジエン構造の含有割合との関係から、検量線を求めることができる。なお、１Ｈ−ＮＭＲスペクトルの測定に際し、上記複数の燃料油は、重溶媒で所定の濃度に希釈されていることが好ましい。事前に検量線を求めることにより、複数種類の燃料油の分析を行う場合に、一層迅速に共役ジエン構造の定量を行うことができる。 Further, the fuel oil analysis method according to the present embodiment may include a step of obtaining a calibration curve. By having such a process, the ratio A / A of the total value A of the integral value B of the peak β derived from the standard substance and the integral value of all the peaks α observed at 6.1 to 6.6 ppm based on tetramethylsilane. Based on B and the calibration curve, the content ratio of the conjugated diene structure contained in the fuel oil can be determined more quickly. The calibration curve can be obtained, for example, as follows. First, the content rate (for example, diene value) of a conjugated diene structure is calculated | required by a well-known measuring method (for example, UOP method 326-82) about several fuel oil. Subsequently, a plurality of samples for preparing a calibration curve are prepared by mixing a standard substance at a predetermined ratio with a plurality of fuel oils having different conjugated diene structure contents. Subsequently, 1 H-NMR spectra of the plurality of samples were measured, and “all peaks observed at 6.1 to 6.6 ppm based on tetramethylsilane with respect to the integral value B ′ of the peak β ′ derived from the standard substance. The ratio A ′ / B ′ of the total A ′ of the integrated values of α ′ is obtained. And a calibration curve can be calculated | required from the relationship of each said ratio A '/ B' calculated | required about the said some sample, and the content rate of a conjugated diene structure. In the measurement of 1 H-NMR spectrum, the plurality of fuel oils are preferably diluted to a predetermined concentration with a heavy solvent. By obtaining a calibration curve in advance, the conjugated diene structure can be quantified more rapidly when analyzing a plurality of types of fuel oil.
上記検量線作成用の試料の１Ｈ−ＮＭＲスペクトル測定及び分析対象の燃料油を含有する試料の１Ｈ−ＮＭＲスペクトル測定に際し、試料中の燃料油の含有割合が全て一定である場合、上記検量線で求められるジエン価は、例えば下記式（２）で表される。 Upon 1 H-NMR spectrum measurement of the sample containing the 1 H-NMR spectrum measurement and analyte fuel oil samples for preparing the calibration curve, if the content of the fuel oil in the sample are all constant, the calibration The diene value calculated | required with a line is represented, for example by following formula (2).
Ｙ＝ａＸ±ｂ …（２） Y = aX ± b (2)
式中、Ｙはジエン価を示し、ａは複数の燃料油における上記比Ａ’／Ｂ’とジエン価との関係から得られる検量線の傾きを表す係数であり、Ｘは上記比Ａ／Ｂを示し、ｂは誤差範囲を示す定数である。ここでａは、上記比Ａ／Ｂをジエン価Ｙに換算するための定数である。また式（２）における「±ｂ」とは、比Ａ／Ｂに定数ａを乗じて求められるジエン価の値と、別法（例えば、ＵＯＰ法３２６−８２）により求められるジエン価の値との誤差がｂ以下であることを意味する。 In the formula, Y represents a diene number, a is a coefficient representing the slope of a calibration curve obtained from the relationship between the ratio A ′ / B ′ and the diene number in a plurality of fuel oils, and X is the ratio A / B. B is a constant indicating the error range. Here, a is a constant for converting the ratio A / B to the diene value Y. In addition, “± b” in the formula (2) means a diene value obtained by multiplying the ratio A / B by a constant a, and a diene value obtained by another method (for example, UOP method 326-82). Means that the error is less than or equal to b.
上記検量線作成用の試料の１Ｈ−ＮＭＲスペクトル測定及び分析対象の燃料油を含有する試料の１Ｈ−ＮＭＲスペクトル測定に際し、試料中の燃料油の含有割合がそれぞれ異なる場合、検量線の傾きａは、比Ａ’／Ｂ’をそれぞれの燃料油の含有割合で補正した値Ｃ’に基づき求められる。例えば、上記検量線作成用の試料における燃料油の含有割合がｍ（ｇ／Ｌ）、上記分析対象の燃料油を含有する試料における燃料油の含有割合がｎ（ｇ／Ｌ）である場合、検量線で求められるジエン価は、下記式（２’）で表される。 Upon 1 H-NMR spectrum measurement of the sample containing the 1 H-NMR spectrum measurement and analyte fuel oil samples for preparing the calibration curve, if the content of the fuel oil in the sample are different, the slope of the calibration curve a is obtained based on a value C ′ obtained by correcting the ratio A ′ / B ′ with the content ratio of each fuel oil. For example, when the fuel oil content in the sample for preparing the calibration curve is m (g / L) and the fuel oil content in the sample containing the fuel oil to be analyzed is n (g / L), The diene value calculated | required with a calibration curve is represented by following formula (2 ').
Ｙ’＝（ａ’Ｘ’／ｎ）±ｂ’ …（２’） Y ′ = (a′X ′ / n) ± b ′ (2 ′)
式中、Ｙ’はジエン価を示し、ａ’は上記Ｃ’（ここでＣ’は、Ａ’／ｍＢ’で表される値を示す。）とジエン価との関係から得られる検量線の傾きを表す係数であり、Ｘ’は上記比Ａ／Ｂを示し、ｂ’は誤差範囲を示す定数である。 In the formula, Y ′ represents a diene value, a ′ represents a calibration curve obtained from the relationship between the above C ′ (where C ′ represents a value represented by A ′ / mB ′) and the diene value. It is a coefficient representing the slope, X ′ represents the ratio A / B, and b ′ is a constant representing the error range.
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。例えば、上記実施形態では燃料油の分析方法として説明したが、本発明は、燃料油に含まれる共役ジエン構造の定量方法であってもよい。また、本実施形態の分析方法は、共役ジエン構造を含む燃料油のみならず、共役ジエン構造を含有しない燃料油に対しても適用可能であることはいうまでもない。この場合、本実施形態の分析方法を行うことによって、共役ジエン構造を含有しないことを確認することができる。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, although the above embodiment has been described as a method for analyzing fuel oil, the present invention may be a method for quantifying a conjugated diene structure contained in fuel oil. Further, it goes without saying that the analysis method of the present embodiment can be applied not only to a fuel oil containing a conjugated diene structure but also to a fuel oil not containing a conjugated diene structure. In this case, it can be confirmed that the conjugated diene structure is not contained by performing the analysis method of the present embodiment.
以下、実施例により本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.
（実施例１）
測定試料として、ＵＯＰ法３２６−８２により求められたジエン価が下記表１のとおりであるガソリン（測定試料１）を準備した。直径５ｍｍのＮＭＲ試料管に、測定試料１を３９．４ｍｇを入れ、次いで、マイクロピペットを用いてＣＤＣｌ３（テトラメチルシラン０．０３％含有、Ａｌｄｒｉｃｈ社製）８００μＬと、メタノール（和光純薬工業（株）社製、特級）２μＬ（４．９４×１０−２ｍｍｏｌ）を加えた。当該ＮＭＲ試料管をテトラフルオロエチレン製のキャップで封止し、後述のＮＭＲ測定装置及び測定条件により、１Ｈ−ＮＭＲスペクトルを測定した。得られた１Ｈ−ＮＭＲスペクトルから、メタノールのメチル基の水素原子由来のピークβ（ケミカルシフト：３．４〜３．５ｐｐｍ）の積分値Ｂに対する、テトラメチルシランを基準としてケミカルシフト６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂを求めた。
Example 1
As a measurement sample, gasoline (measurement sample 1) having a diene value determined by the UOP method 326-82 as shown in Table 1 below was prepared. 39.4 mg of
（ＮＭＲ測定装置及び測定条件）
ＮＭＲ測定装置は、Ｖａｒｉａｎ社製ＮＭＲ Ｓｙｓｔｅｍ５００を用いた。
ＮＭＲ測定は、絶対値モードで以下の条件で行った。
待ち時間（Ｒｅｌａｘａｔｉｏｎ Ｄｅｌａｙ）：２秒間
積算回数（Ｎｕｍｂｅｒ ｏｆ Ｓｃａｎｓ）：３２回
検出感度（Ｒｅｃｅｉｖｅｒ Ｇａｉｎ）：２４
(NMR measurement apparatus and measurement conditions)
As the NMR measuring apparatus, NMR System 500 manufactured by Varian was used.
NMR measurement was performed in the absolute value mode under the following conditions.
Waiting time (Relaxation Delay): 2 seconds Number of scans (Number of Scans): 32 times Detection sensitivity (Receiver Gain): 24
（実施例２〜１１）
測定試料として下記表１に示す各測定試料を用いた以外は、実施例１と同様にして、メタノールのメチル基の水素原子由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂを求めた。
(Examples 2 to 11)
5. In the same manner as in Example 1 except that each measurement sample shown in Table 1 below was used as a measurement sample, with reference to tetramethylsilane with respect to the integral value B of the peak β derived from the hydrogen atom of the methyl group of methanol. The ratio A / B of the total A of integrated values of all peaks α observed at 1 to 6.6 ppm was determined.
実施例１〜１１で得られた比Ａ／Ｂを測定試料１００ｍｇあたりに換算した値（比Ａ／Ｂを測定試料の使用量（ｍｇ）で除して１００を乗じた値）を横軸にとり、ＵＯＰ法３２６−８２により求められたジエン価（ｇ／１００ｇ）を縦軸にとり、検量線を作成した。得られた検量線は、下記式（３）に示すとおりであった。図１は、実施例１〜１１で得られた検量線を示す図である。なお、図１中、Ｒは相関係数を示す。また、図２〜４は、それぞれ実施例１、９、１１で測定された１Ｈ−ＮＭＲスペクトルを示す図である。 The value obtained by converting the ratio A / B obtained in Examples 1 to 11 per 100 mg of the measurement sample (the value obtained by dividing the ratio A / B by the amount used of the measurement sample (mg) and multiplying by 100) is plotted on the horizontal axis. A calibration curve was prepared by taking the diene value (g / 100 g) determined by the UOP method 326-82 on the vertical axis. The obtained calibration curve was as shown in the following formula (3). FIG. 1 is a diagram showing the calibration curves obtained in Examples 1-11. In FIG. 1, R represents a correlation coefficient. 2 to 4 are diagrams showing 1 H-NMR spectra measured in Examples 1, 9, and 11, respectively.
ｙ＝１８．７５６ｘ …（３） y = 18.756x (3)
式中ｙはジエン価を示し、ｘは比Ａ／Ｂを測定試料１００ｍｇあたりに換算した値（比Ａ／Ｂを測定試料の使用量（ｍｇ）で除して１００を乗じた値）を示す。 In the formula, y represents the diene value, and x represents a value obtained by converting the ratio A / B per 100 mg of the measurement sample (a value obtained by dividing the ratio A / B by the amount (mg) of the measurement sample and multiplying by 100). .
実施例１〜１１で得られた比Ａ／Ｂと、それぞれの測定試料の使用量に基づき、式（３）からｙの値を求めた。得られた値は表１に示すとおりであった。ｙの値は、ＵＯＰ法２３６−８２で得られたジエン価と良い一致を示し、両者の誤差は２．０以下であった。 Based on the ratio A / B obtained in Examples 1 to 11 and the amount of each measurement sample used, the value of y was determined from Equation (3). The obtained values were as shown in Table 1. The value of y was in good agreement with the diene value obtained by UOP method 236-82, and the error between them was 2.0 or less.
（実施例１２）
測定試料１に代えて、共役ジエン構造を含有するガソリン（測定試料１２）３８．４ｍｇを用いた以外は、実施例１と同様にして、メタノールのメチル基の水素原子由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂを求めた。得られた比Ａ／Ｂと、上記実施例１〜１１で得られた検量線とから、ジエン価を算出したところ、１．９であり、測定試料１２についてＵＯＰ法３２６−８２によりジエン価を測定した結果（１．７ｇ／１００ｇ）と良い一致を示した。
(Example 12)
The integrated value of the peak β derived from the hydrogen atom of the methyl group of methanol in the same manner as in Example 1 except that 38.4 mg of gasoline (measurement sample 12) containing a conjugated diene structure was used instead of the
（比較例１〜１１）
比較例１〜１１では、実施例１〜１１における比Ａ／Ｂの代わりに、メタノールのメチル基の水素原子由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として４．５〜６．０ｐｐｍに観測される全ピークα’’の積分値の合計Ａ’’の比Ａ’’／Ｂをそれぞれ求めた。次いで、比較例１〜１１で得られた比Ａ’’／Ｂを測定試料１００ｍｇあたりに換算した値（比Ａ’’／Ｂを測定試料の使用量（ｍｇ）で除して１００を乗じた値）を横軸にとり、ＵＯＰ法３２６−８２により求められたジエン価（ｇ／１００ｇ）を縦軸にとり、検量線を作成した。得られた検量線は、下記式（４）に示すとおりであった。図５は、比較例１〜１１で得られた検量線を示す図である。なお、図５中、Ｒは相関係数を示す。
(Comparative Examples 1-11)
In Comparative Examples 1-11, instead of the ratio A / B in Examples 1-11, 4.5-6.4 based on tetramethylsilane with respect to the integral value B of the peak β derived from the hydrogen atom of the methyl group of methanol. The ratio A ″ / B of the total A ″ of integral values of all peaks α ″ observed at 0 ppm was determined. Subsequently, the value obtained by converting the ratio A ″ / B obtained in Comparative Examples 1 to 11 per 100 mg of the measurement sample (the ratio A ″ / B was divided by the amount of use (mg) of the measurement sample and multiplied by 100. Value) was taken on the horizontal axis, and the diene value (g / 100 g) determined by the UOP method 326-82 was taken on the vertical axis to create a calibration curve. The obtained calibration curve was as shown in the following formula (4). FIG. 5 is a diagram showing the calibration curves obtained in Comparative Examples 1-11. In FIG. 5, R represents a correlation coefficient.
ｙ＝１．３０４２ｘ …（４） y = 1.3042x (4)
式中ｙはジエン価を示し、ｘは比Ａ’’／Ｂを測定試料１００ｍｇあたりに換算した値（比Ａ’’／Ｂを測定試料の使用量（ｍｇ）で除して１００を乗じた値）を示す。 In the formula, y represents the diene value, and x is a value obtained by converting the ratio A ″ / B per 100 mg of the measurement sample (the ratio A ″ / B is divided by the amount of use (mg) of the measurement sample and multiplied by 100. Value).
比較例１〜１１で得られた比Ａ’’／Ｂと、測定試料１〜１１の使用量に基づき、式（４）からｙの値を求めた。得られた値は表２に示すとおりであった。ｙの値とＵＯＰ法２３６−８２で得られたジエン価との誤差は２．０より大きく、十分な精度でジエン価の測定を行うことができなかった。
Based on the ratio A ″ / B obtained in Comparative Examples 1 to 11 and the amount of the
１…メタノールのメチル基由来のピーク、２…テトラメチルシラン由来のピーク、１０、２０、３０…６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａ。
1 ... Peak derived from the methyl group of methanol, 2 ... Peak derived from tetramethylsilane, 10, 20, 30 ... Total A of integrated values of all peaks α observed at 6.1 to 6.6 ppm.
Claims (4)
前記１Ｈ−ＮＭＲスペクトルにおける、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａに基づいて、前記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法。 Measuring the 1 H-NMR spectrum of the fuel oil;
In the 1 H-NMR spectrum, the content ratio of the conjugated diene structure in the fuel oil is determined based on the sum A of integral values of all peaks α observed at 6.1 to 6.6 ppm with reference to tetramethylsilane. And a method for analyzing fuel oil.
前記１Ｈ−ＮＭＲスペクトルにおける、前記標準物質由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂに基づいて、前記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法。 Measuring a 1 H-NMR spectrum of a sample containing fuel oil and a standard substance;
Ratio A of total A of integrated values of all peaks α observed at 6.1 to 6.6 ppm based on tetramethylsilane with respect to integrated value B of peak β derived from the standard substance in the 1 H-NMR spectrum And a step of determining the content ratio of the conjugated diene structure in the fuel oil based on / B.
前記複数の燃料油について求めたそれぞれの前記比Ａ’／Ｂ’と前記含有割合との関係に基づいて、検量線を得る工程と、
燃料油と標準物質とを含有する試料の１Ｈ−ＮＭＲスペクトルを測定する工程と、
前記試料の１Ｈ−ＮＭＲスペクトルにおける、前記標準物質由来のピークβの積分値Ｂに対する、テトラメチルシランを基準として６．１〜６．６ｐｐｍに観測される全ピークαの積分値の合計Ａの比Ａ／Ｂと、前記検量線とに基づいて、前記試料に含まれる前記燃料油における共役ジエン構造の含有割合を求める工程と、を有する、燃料油の分析方法。 With respect to a plurality of fuel oils having different conjugated diene structure contents, 1 H-NMR spectra are measured together with a standard substance, and tetramethylsilane is used as a reference for the integral value B ′ of the peak β ′ derived from the standard substance. Obtaining a ratio A ′ / B ′ of the total A ′ of integrated values of all peaks α ′ observed at 6.1 to 6.6 ppm;
Obtaining a calibration curve based on the relationship between the ratio A ′ / B ′ and the content ratio obtained for the plurality of fuel oils;
Measuring a 1 H-NMR spectrum of a sample containing fuel oil and a standard substance;
In the 1 H-NMR spectrum of the sample, the total A of the integrated values of all peaks α observed at 6.1 to 6.6 ppm with respect to tetramethylsilane relative to the integrated value B of the peak β derived from the standard substance And a step of obtaining a content ratio of a conjugated diene structure in the fuel oil contained in the sample based on the ratio A / B and the calibration curve.
The fuel oil analysis method according to claim 2 or 3, wherein the standard substance is an oxygen-containing compound or a silicon-containing compound.
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