JP2011095170A - Fuel oil analysis method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel oil analysis method, capable of speedily determining an oxygenated compound in fuel oil with high accuracy. <P>SOLUTION: The fuel oil analysis method includes both of a step of measuring a<SP>1</SP>H-NMR spectrum of fuel oil and a step of determining a content ratio of an oxygenated compound having a hydrogen atom bound to a carbon atom at the α position of an oxygen atom in the fuel oil on the basis of an integrated value of peaks derived from the oxygenated compound in the<SP>1</SP>H-NMR spectrum. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for analyzing fuel oil.

  In Japan, compulsory standards based on the Act on Quality of Volatile Oil (Product Quality Act) regarding the proportion of oxygenated compounds such as methyl-tert-butyl ether (MTBE), methanol and ethanol in petroleum products such as gasoline Is stipulated. For this reason, it is not permitted to sell petroleum products that do not meet the standards. Therefore, high accuracy is required for quantitative analysis of oxygenated compounds in petroleum products.

  Conventionally, as a quantitative analysis method for oxygen-containing compounds in petroleum products, a measurement method using a gas chromatograph is known (for example, Non-Patent Document 1 and Non-Patent Document 2).

JIS Handbook 25 Petroleum 2007, pages 1428 to 1463 (JIS K2536-2) JIS Handbook 25 Petroleum 2007, 1491-1496 (JIS K2536-6)

  However, the quantitative analysis method for oxygen-containing compounds by the gas chromatographs of Non-Patent Documents 1 and 2 is complicated in operation and requires a long time for analysis. Therefore, it is required to establish an analysis method that can measure the content ratio of oxygen-containing compounds in many fuel oil samples in a short time.

  Then, an object of this invention is to provide the analysis method of the fuel oil which can measure the content rate of the oxygen-containing compound in fuel oil rapidly and with high precision.

That is, the present invention includes a first step of measuring a ¹ H-NMR spectrum of a fuel oil, and a peak derived from an oxygen-containing compound having a hydrogen atom bonded to the α-position carbon atom of the oxygen atom in the ¹ H-NMR spectrum. And a second step of determining the content ratio of the oxygen-containing compound in the fuel oil based on the integral value of the fuel oil. In the fuel oil analysis method of the present invention, since the integrated value of the peak obtained by ¹ H-NMR measurement is used, the content ratio of the oxygen-containing compound in the fuel oil can be measured quickly and accurately. it can.

  The oxygen-containing compound in the fuel oil analysis method of the present invention preferably contains at least one selected from the group consisting of methyl-tert-butyl ether, ethyl-tert-butyl ether, methanol, ethanol, isopropyl alcohol, and n-butanol. The content ratio of such an oxygen-containing compound can be measured with higher accuracy.

  The fuel oil analyzed in the present invention includes fuel oil containing gasoline. In gasoline, the content ratio of oxygen-containing compounds such as methyl-tert-butyl ether (MTBE), methanol, ethanol and the like is strictly defined by the method of accuracy. According to the fuel oil analysis method of the present invention, the content ratio of these oxygen-containing compounds can be measured quickly and with high accuracy, and fuel oil that satisfies the quality standards can be stably supplied. .

In the present invention, before the second step, the ¹ H-NMR spectrum of a plurality of samples containing the oxygen-containing compound and different from each other is measured, and a calibration curve is created based on the integrated value. In the second step, the oxygenated compound in the fuel oil is based on the integrated value of the peak in the ¹ H-NMR spectrum of the fuel oil and the calibration curve. Provided is a method for analyzing fuel oil, which determines the content ratio of. Such an analysis method for fuel oil uses the integral value of the peak obtained by ¹ H-NMR measurement, so that the content ratio of the oxygen-containing compound in the fuel oil can be measured quickly and accurately. . In addition, since a calibration curve is used, a plurality of analysis target fuel oils can be analyzed quickly and easily.

  ADVANTAGE OF THE INVENTION According to this invention, the analysis method of fuel oil which can measure the content rate of the oxygen-containing compound in fuel oil rapidly and with high precision is provided.

It is a figure which shows the calibration curve obtained in Example 1 of this invention. It is a figure which shows the calibration curve obtained in Example 2 of this invention. It is a figure which shows the calibration curve obtained in Example 3 of this invention. It is a figure which shows the calibration curve obtained in Example 4 of this invention. It is a figure which shows the calibration curve obtained in Example 5 of this invention. It is a figure which shows the calibration curve obtained in Example 6 of this invention. It is a figure which shows the calibration curve obtained in Example 8 of this invention. It is a figure which shows the calibration curve obtained in Example 9 of this invention. It is a figure which shows the calibration curve obtained in Example 10 of this invention. It is a figure which shows the calibration curve obtained in Example 11 of this invention. It is a figure which shows the calibration curve obtained in Example 12 of this invention. It is a figure which shows the calibration curve obtained in Example 13 of this invention. It is a diagram illustrating an example of a ¹ H-NMR spectrum of gasoline containing ETBE. It is a diagram illustrating an example of a ¹ H-NMR spectrum of gasoline containing MTBE. It is a diagram illustrating an example of a ¹ H-NMR spectrum of gasoline containing IPA. It is a diagram illustrating an example of a ^{1 H-NMR} spectrum of gasoline containing methanol. It is a diagram illustrating an example of a ^{1 H-NMR} spectrum of gasoline containing ethanol. It is a diagram illustrating an example of a ¹ H-NMR spectrum of gasoline containing n- butanol.

  A preferred embodiment of the fuel oil analysis method of the present invention will be described below.

The fuel oil analysis method according to the present embodiment includes a first step of measuring a ¹ H-NMR spectrum (hydrogen-nuclear magnetic resonance spectrum) of the fuel oil, and an α-position of an oxygen atom in the ¹ H-NMR spectrum. And a second step of determining a content ratio of the oxygenated compound in the fuel oil based on an integrated value of a peak derived from the oxygenated compound having a hydrogen atom bonded to a carbon atom.

  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.

  The fuel oil analysis method according to this embodiment can analyze any of the above-described various fuel oils and mixtures thereof, and is particularly excellent in analyzing fuel oil containing gasoline. Examples of gasoline include No. 1 gasoline and No. 2 gasoline defined by JISK2202 “Automobile gasoline”.

  The oxygen-containing compound in the present embodiment is a compound having, as constituent elements, an oxygen atom, a carbon atom bonded to the oxygen atom, and a hydrogen atom bonded to the carbon atom, and is represented by the following formula (1). A compound having the structure

  Examples of such oxygen-containing compounds include various ethers and alcohols. Among these oxygen-containing compounds, oxygen-containing compounds such as methyl-tert-butyl ether (MTBE), ethyl-tert-butyl ether (ETBE), methanol, ethanol, isopropyl alcohol, and n-butanol are contained with higher accuracy. Can be measured.

  According to the method for analyzing fuel oil according to this embodiment, even when a plurality of oxygen-containing compounds are present in the fuel oil, the content ratio of each oxygen-containing compound can be simultaneously measured with high accuracy and speed.

The “peak derived from the oxygen-containing compound” in the ¹ H-NMR spectrum of the present embodiment preferably has an observation position (chemical shift) of the peak at a position where no peaks of components other than the oxygen-containing compound are observed. As such a peak, for example, a peak derived from a hydrogen atom bonded to an α-position carbon hydrogen of an oxygen atom can be mentioned. By obtaining the content ratio of the oxygen-containing compound in the fuel oil based on the integrated value of the peak, high-precision analysis can be reliably performed on various fuel oils (particularly gasoline). In addition, as a position where the peak of components other than the oxygen-containing compound is not observed, specifically, in the range of 3.0 to 4.5 ppm with reference to tetramethylsilane, from the viewpoint of performing higher-precision analysis, 3. A range of 1 to 4.1 ppm is mentioned.

The ¹ H-NMR spectrum of the present embodiment is obtained by analyzing the above-described fuel oil by a usual method using a commercially available NMR apparatus. In the analysis by the NMR apparatus, the fuel oil is preferably 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 preferable from the viewpoint of safer analysis and excellent handleability.

  In the second step, the content ratio of the oxygen-containing compound in the fuel oil is determined based on the integrated value of the peak derived from the oxygen-containing compound. For example, by adding a predetermined amount of a standard substance to the fuel oil in the first step and comparing the peak integral value of the standard substance with the integral value of the peak derived from the oxygenate compound, the content ratio of the oxygenate compound Can be requested.

  In addition, a calibration curve can be obtained in advance, and the content ratio of the oxygenated compound contained in the fuel oil can be obtained based on the integrated value of the peak derived from the oxygenated compound and the calibration curve. By obtaining a calibration curve in advance, when analyzing a plurality of types of fuel oil, the analysis can be performed more quickly.

As an analytical method using a calibration curve, for example, ¹ H-NMR spectra of a plurality of samples having different content ratios of oxygen-containing compounds having a hydrogen atom bonded to the α-position carbon atom of an oxygen atom are measured, and the above-mentioned inclusion is performed. A step of obtaining an integrated value of the peak derived from the oxygen compound, a step of creating a calibration curve based on the integrated value of the peak derived from each of the oxygen-containing compounds obtained for the plurality of samples, and Measuring the ¹ H-NMR spectrum to determine the integrated value of the peak derived from the oxygenated compound, the integrated value of the peak derived from the oxygenated compound determined for the fuel oil to be analyzed, and the calibration curve; And a step of obtaining a content ratio of the oxygen-containing compound in the fuel oil to be analyzed.

  As a sample, it is preferable to use a mixture (hereinafter referred to as “fuel oil for preparing a calibration curve”) containing a fuel oil containing no oxygen-containing compound and an oxygen-containing compound.

  The plurality of samples can be prepared, for example, by adding a predetermined oxygen-containing compound to the fuel oil so that the content ratios are different from each other. The content ratio of the oxygen-containing compound in the plurality of samples can be determined by, for example, a quantitative analysis method of the oxygen-containing compound by gas chromatography (GC) (for example, JdIS K2536-2).

As a method for obtaining a calibration curve, for example, a standard substance is added to each of a plurality of calibration curve creating fuel oils having different oxygen-containing compound content ratios, and ¹ H-NMR spectra are measured. The ratio A ′ / B ′ of the integrated value A ′ of the peak derived from the oxygen-containing compound with respect to the integrated value B ′ of the peak is obtained. And the method of obtaining a calibration curve based on the ratio A ′ / B ′ and the content ratio of the oxygen-containing compound in the plurality of calibration curve creating fuel oils is mentioned.

When obtaining the content ratio of oxygen-containing compounds in the fuel oil to be analyzed based on the calibration curve thus obtained, a standard substance is added to the fuel oil to be analyzed and a ¹ H-NMR spectrum is measured. The above analysis is performed based on the ratio A / B and the calibration curve by determining the ratio A / B of the integrated value A of the peak derived from the oxygen-containing compound to the integrated value B of the peak derived from the standard substance. The content ratio of the oxygen-containing compound in the target fuel oil can be determined.

  As the standard substance, a silicon-containing compound is preferable. Examples of the silicon-containing compound include tetramethylsilane, hexamethyldisilane, hexamethyldisiloxane, and the like. Among these, tetramethylsilane is preferable from the viewpoint of obtaining a more accurate analysis result. The “peak derived from the standard substance” when the standard substance is a silicon-containing compound is preferably a peak derived from a hydrogen atom bonded to the α-position carbon atom of the silicon atom. 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.

  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 oxygen-containing compounds contained in fuel oil. Further, it goes without saying that the analysis method of the present embodiment can be applied not only to fuel oil containing an oxygen-containing compound but also to fuel oil not containing an oxygen-containing compound. In this case, it can be confirmed that the oxygen-containing compound is not contained by performing the analysis method of the present embodiment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

(Measurement method of ¹ H-NMR spectrum)
A sample was put in an NMR sample tube having a diameter of 5 mm, and then 800 μL of a deuterated chloroform (CDCl ₃ ) solution containing 0.03% by mass of tetramethylsilane was added using a micropipette. The NMR sample tube was sealed with a tetrafluoroethylene cap, and a ¹ H-NMR spectrum was measured using an NMR measurement apparatus and measurement conditions described later.

<NMR measurement apparatus and measurement conditions>
As the NMR measuring apparatus, NMR System 500 (trade name) 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: 32 times Detection sensitivity (Receiver Gain): 24

(Example 1: Determination of ethyl-tert-butyl ether (ETBE))
A sample in which ethyl-tert-butyl ether is diluted with a commercially available regular gasoline to which no oxygen-containing compound is added, and the content ratios of ethyl-tert-butyl ether are 0.9 mass%, 1.8 mass%, and 0.45 mass%, respectively. Was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, when the integrated value of the peak derived from tetramethylsilane is 1, the peak derived from ethyl-tert-butyl ether (the peak observed around 3.4 ppm based on tetramethylsilane) ) Was obtained. Subsequently, the mass correction value a ′ obtained by correcting the mass of the integral value a to a value per 100 mg of the sample was obtained. A calibration curve was prepared with the mass correction value a ′ obtained for each sample as the horizontal axis and the ethyl-tert-butyl ether content ratio in each sample as the vertical axis. The amount, integrated value a, and mass correction value a ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 1 below. The prepared calibration curve was as shown in FIG. In the figure, R ² represents a correlation coefficient.

Next, gasoline containing ethyl-tert-butyl ether was prepared as the measurement target sample 1, and the ¹ H-NMR spectrum was measured according to the measurement method, the integral value a was obtained, and the mass correction value a ′ was calculated. Using the obtained mass correction value a ′ and the calibration curve, the content ratio of ethyl-tert-butyl ether in the measurement target sample 1 was calculated. The amount of the sample put in the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value a, the mass correction value a ′, and the calculated ethyl-tert-butyl ether content were as shown in Table 2 below.

Using the following GC (gas chromatograph) apparatus and measurement conditions, all components were analyzed by gas chromatograph of the sample 1 to be measured, and the content ratio of ethyl-tert-butyl ether was measured. The measured values of the content ratio of ethyl-tert-butyl ether are as shown in Table 2 below, and the content ratio calculated based on the ¹ H-NMR spectrum may be in good agreement with the content ratio measured by gas chromatography. all right.

<GC device and measurement conditions>
As the GC apparatus, GC-2010 (trade name) manufactured by Shimadzu Corporation was used.
The total component analysis using the GC apparatus was performed under the following conditions.
Column: Petrocol DH (100m x 0.25mmφ) made by Superco
Carrier gas: He 277 kPa
Detector: FID (hydrogen flame ionization detector)
Detector temperature: 250 ° C
Inlet temperature: 250 ° C
Oven temperature: 5 ° C. (5 minutes) to 50 ° C. (43 minutes) to 250 ° C. (6 minutes)
Temperature increase rate: 5 ° C./min (5 to 50 ° C.), 1.6 ° C./min (50 to 250 ° C.)
Injection volume: 0.4 μL
Split ratio: 1: 100

(Example 2: Determination of methyl-tert-butyl ether (MTBE))
Samples with methyl-tert-butyl ether diluted with commercially available regular gasoline to which no oxygen-containing compound is added, and having a methyl-tert-butyl ether content of 2.08 mass%, 5.24 mass%, and 1.44 mass%, respectively. Was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, when the integrated value of the peak derived from tetramethylsilane is 1, the peak derived from methyl-tert-butyl ether (the peak observed around 3.2 ppm with reference to tetramethylsilane) ) Was obtained. Next, a mass correction value b ′ obtained by correcting the mass of the integral value b to a value per 100 mg of the sample was obtained. A calibration curve was prepared using the mass correction value b ′ obtained for each sample as the horizontal axis and the content ratio of methyl-tert-butyl ether in each sample as the vertical axis. The amount, integral value b, and mass correction value b ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 3 below. Moreover, the prepared calibration curve was as shown in FIG.

Next, gasoline containing methyl-tert-butyl ether was prepared as the sample 2 to be measured, and the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value b was determined, and the mass correction value b ′ was calculated. Using the obtained mass correction value b ′ and the calibration curve, the content ratio of methyl-tert-butyl ether in the measurement target sample 2 was calculated. The amount of sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value b, the mass correction value b ′, and the calculated content ratio of methyl-tert-butyl ether were as shown in Table 4 below.

Moreover, about the measurement object sample 2, it carried out similarly to Example 1, and performed the all-components analysis by the gas chromatograph, and measured the content rate of methyl-tert- butyl ether. The measured values of the content ratio of methyl-tert-butyl ether are as shown in Table 4 below, and the content ratio calculated based on the ¹ H-NMR spectrum may be in good agreement with the content ratio measured by the gas chromatograph. all right.

(Example 3: Determination of ethanol (EtOH))
Ethanol was diluted with commercially available regular gasoline to which no oxygen-containing compound was added to prepare samples having ethanol content ratios of 4.13 mass%, 2.63 mass%, and 1.13 mass%, respectively. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, when the integrated value of the tetramethylsilane-derived peak is 1, the integrated value of the ethanol-derived peak (peak observed around 3.7 ppm with respect to tetramethylsilane) c was determined. Subsequently, the mass correction value c ′ obtained by correcting the mass of the integral value c to a value per 100 mg of the sample was obtained. A calibration curve was prepared with the mass correction value c ′ obtained for each sample as the horizontal axis and the ethanol content in each sample as the vertical axis. The amount, integrated value c, and mass correction value c ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 5 below. Moreover, the created calibration curve was as shown in FIG.

Next, gasoline containing ethanol was prepared as the measurement target sample 3, and the ¹ H-NMR spectrum was measured according to the measurement method, the integral value c was obtained, and the mass correction value c ′ was calculated. Using the obtained mass correction value c ′ and the calibration curve, the content ratio of ethanol in the measurement target sample 3 was calculated. The amount of sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value c, the mass correction value c ′, and the calculated ethanol content were as shown in Table 6 below.

Further, the sample 3 to be measured was analyzed for all components by gas chromatography in the same manner as in Example 1, and the content ratio of ethanol was measured. The measured values of the ethanol content were as shown in Table 6 below, and it was found that the content calculated based on the ¹ H-NMR spectrum showed good agreement with the content measured by gas chromatography.

(Example 4: Determination of methanol (MeOH))
Methanol was diluted with commercially available regular gasoline to which no oxygen-containing compound was added to prepare samples having methanol content rates of 3.98% by mass, 1.72% by mass, and 1.18% by mass, respectively. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, when the integrated value of the peak derived from tetramethylsilane is 1, the integrated value of the peak derived from methanol (peak observed around 3.5 ppm with reference to tetramethylsilane) d was determined. Subsequently, a mass correction value d ′ obtained by correcting the mass of the integral value d to a value per 100 mg of the sample was obtained. A calibration curve was prepared with the mass correction value d ′ obtained for each sample as the horizontal axis and the methanol content in each sample as the vertical axis. The amount, integrated value d, and mass correction value d ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 7 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing methanol was prepared as the sample 4 to be measured, and a ¹ H-NMR spectrum was measured according to the measurement method described above, an integral value d was obtained, and a mass correction value d ′ was calculated. Using the obtained mass correction value d ′ and the calibration curve, the content ratio of methanol in the measurement target sample 4 was calculated. The amount of sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value d, the mass correction value d ′, and the calculated methanol content were as shown in Table 8 below.

Moreover, about the measurement object sample 4, it carried out similarly to Example 1, all component analysis by a gas chromatograph was performed, and the content rate of methanol was measured. The measured value of the content ratio of methanol is as shown in Table 8 below, and it was found that the content ratio calculated based on the ¹ H-NMR spectrum shows a good agreement with the content ratio measured by the gas chromatograph.

(Example 5: Determination of isopropyl alcohol (IPA))
Isopropyl alcohol was diluted with commercially available regular gasoline to which no oxygen-containing compound was added to prepare samples having isopropyl alcohol content rates of 3.59 mass%, 1.42 mass%, and 2.20 mass%, respectively. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, the integration of the peak derived from isopropyl alcohol (peak observed around 4.0 ppm with reference to tetramethylsilane) when the integrated value of the peak derived from tetramethylsilane is 1. The value e was determined. Next, a mass correction value e ′ obtained by correcting the mass of the integral value e to a value per 100 mg of the sample was obtained. A calibration curve was prepared with the mass correction value e ′ obtained for each sample as the horizontal axis and the isopropyl alcohol content in each sample as the vertical axis. The amount, integrated value e, and mass correction value e ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 9 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing isopropyl alcohol was prepared as the sample 5 to be measured, and the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value e was obtained, and the mass correction value e ′ was calculated. Using the obtained mass correction value e ′ and the calibration curve, the content ratio of isopropyl alcohol in the measurement target sample 5 was calculated. The amount of the sample put in the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value e, the mass correction value e ′, and the calculated content ratio of isopropyl alcohol were as shown in Table 10 below.

In addition, the sample 5 to be measured was analyzed for all components by gas chromatography in the same manner as in Example 1, and the content ratio of isopropyl alcohol was measured. The measured values of the content ratio of isopropyl alcohol are as shown in Table 10 below, and it was found that the content ratio calculated based on the ¹ H-NMR spectrum shows a good agreement with the content ratio measured by the gas chromatograph.

(Example 6: Determination of n-butanol (n-BuOH))
N-butanol was diluted with a commercially available regular gasoline to which no oxygen-containing compound was added to prepare samples having n-butanol content of 5.79% by mass, 3.13% by mass, and 1.09% by mass, respectively. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, when the integrated value of the peak derived from tetramethylsilane is 1, the peak derived from n-butanol (the peak observed around 3.6 ppm with reference to tetramethylsilane) An integral value f was obtained. Subsequently, the mass correction value f ′ obtained by correcting the mass of the integral value f to a value per 100 mg of the sample was obtained. Then, a calibration curve was prepared with the mass correction value f ′ obtained for each sample as the horizontal axis and the content ratio of n-butanol in each sample as the vertical axis. The amount, integrated value f, and mass correction value f ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 11 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing n-butanol was prepared as the measurement target sample 6, the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value f was obtained, and the mass correction value f ′ was calculated. Using the obtained mass correction value f ′ and the calibration curve, the content ratio of n-butanol in the measurement target sample 6 was calculated. The amount of the sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value f, the mass correction value f ′, and the calculated content ratio of n-butanol were as shown in Table 12 below.

Moreover, about the measurement object sample 6, it carried out similarly to Example 1, the all component analysis by the gas chromatograph was performed, and the content rate of n-butanol was measured. The measured values of the content ratio of n-butanol are as shown in Table 12 below, and the content ratio calculated based on the ¹ H-NMR spectrum was found to be in good agreement with the content ratio measured by the gas chromatograph. .

(Example 7)
For gasoline containing ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol, isopropyl alcohol and n-butanol (hereinafter, measurement target sample 7), ¹ H-NMR spectrum was measured according to the above measurement method. . The amount of the measurement target sample 7 used for the measurement was 32.7 mg. For each of ethyl tert-butyl ether, methyl tert-butyl ether, ethanol, methanol, isopropyl alcohol, and n-butanol, the integrated value of the peak derived from the hydrogen atom bonded to the α-position carbon atom of the oxygen atom is calculated as tetramethylsilane. The integration value of the peak derived from 1 was determined as the integration value when 1.

  The obtained integrated value of each peak was subjected to mass correction to a value of 100 mg of a sample to obtain a mass correction value. From the obtained mass correction values and the calibration curves obtained in Examples 1 to 6, measurement target materials for each of ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol, isopropyl alcohol and n-butanol The content ratio in 7 was calculated. The calculated content ratio was as shown in Table 13 below.

Next, the sample 7 to be measured was analyzed by gas chromatography in the same manner as in Example 1, and each of ethyl tert-butyl ether, methyl tert-butyl ether, ethanol, methanol, isopropyl alcohol, and n-butyl alcohol was analyzed. The content ratio was measured. The measured values of the content ratio are as shown in Table 13 below, and the content ratio calculated based on the ¹ H-NMR spectrum was found to be in good agreement with the content ratio measured by the gas chromatograph.

(Example 8: Determination of ethyl-tert-butyl ether (ETBE))
Ethyl-tert-butyl ether is diluted with a commercially available regular gasoline to which no oxygen-containing compound is added, and the content ratio of ethyl-tert-butyl ether is 19.9% by mass, 5.1% by mass, 2.6% by mass, Samples of 1% by mass and 0.6% by mass were prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integrated value g of a peak derived from ethyl-tert-butyl ether (peak observed around 3.4 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn, the height of the integration curve was measured, and the height was defined as the integration value of the peak. In the following examples, the peak integration value is obtained by the same method (the method of measuring the height of the integration curve drawn under the same integration curve drawing conditions and setting the height as the peak integration value). It was measured.

Next, the integrated value g of the peak obtained for each sample was subjected to mass correction to a value per 100 mg of the sample to obtain a mass correction value g ′. A calibration curve was prepared with the mass correction value g ′ obtained for each sample as the horizontal axis and the ethyl-tert-butyl ether content in each sample as the vertical axis. The amount, integrated value g, and mass correction value g ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 14 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing ethyl-tert-butyl ether was prepared as the measurement target sample 8, and the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value g was obtained, and the mass correction value g ′ was calculated. Using the obtained mass correction value g ′ and the calibration curve, the content ratio of ethyl-tert-butyl ether in the measurement target sample 8 was calculated. The amount of sample put in the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value g, the mass correction value g ′, and the calculated ethyl-tert-butyl ether content were as shown in Table 15 below.

Further, the sample 9 to be measured was subjected to a gas chromatograph all-component analysis in the same manner as in Example 1, and the content ratio of ethyl-tert-butyl ether was measured. The measured values of the content ratio of ethyl-tert-butyl ether are as shown in Table 15 below, and the content ratio calculated based on the ¹ H-NMR spectrum may be in good agreement with the content ratio measured by the gas chromatograph. all right.

(Example 9: Determination of methyl-tert-butyl ether (MTBE))
Methyl-tert-butyl ether is diluted with a commercially available regular gasoline to which no oxygen-containing compound is added, and the content ratio of methyl-tert-butyl ether is 20.1% by mass, 5.3% by mass, 2.7% by mass, Samples of 1% by mass and 0.5% by mass were prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integral value h of a peak derived from methyl-tert-butyl ether (a peak observed around 3.2 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

Next, the integrated value h of the peak obtained for each sample was subjected to mass correction to a value per 100 mg of the sample to obtain a mass correction value h ′. A calibration curve was prepared with the mass correction value h ′ obtained for each sample as the horizontal axis and the methyl-tert-butyl ether content in each sample as the vertical axis. The amount, integrated value h, and mass correction value h ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 16 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing methyl-tert-butyl ether was prepared as the measurement target sample 9, and the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value h was obtained, and the mass correction value h ′ was calculated. Using the obtained mass correction value h ′ and the calibration curve, the content ratio of methyl-tert-butyl ether in the measurement target sample 9 was calculated. The amount of the sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value h, the mass correction value h ′, and the calculated content ratio of methyl-tert-butyl ether were as shown in Table 17 below.

Further, with respect to the sample 9 to be measured, in the same manner as in Example 1, all components were analyzed by gas chromatography, and the content ratio of methyl-tert-butyl ether was measured. The measured values of the content ratio of methyl-tert-butyl ether are as shown in Table 17 below, and the content ratio calculated based on the ¹ H-NMR spectrum may be in good agreement with the content ratio measured by the gas chromatograph. all right.

(Example 10: Determination of isopropyl alcohol (IPA))
Dilute isopropyl alcohol with commercially available regular gasoline to which no oxygen-containing compound is added, and the content ratio of isopropyl alcohol is 20.2 mass%, 5.3 mass%, 2.6 mass%, 1.4 mass%, 1 A sample of 0.0% by weight was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integrated value i of a peak derived from isopropyl alcohol (a peak observed around 4.0 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

Next, the integrated value i of the peak obtained for each sample was mass corrected to a value per 100 mg of the sample to obtain a mass corrected value i ′. Then, a calibration curve was prepared with the mass correction value i ′ obtained for each sample as the horizontal axis and the isopropyl alcohol content in each sample as the vertical axis. The amount, integrated value i, and mass correction value i ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 18 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing isopropyl alcohol was prepared as the measurement target sample 10, and the ¹ H-NMR spectrum was measured according to the above measurement method, the integral value i was obtained, and the mass correction value i ′ was calculated. Using the obtained mass correction value i ′ and the calibration curve, the content ratio of isopropyl alcohol in the measurement target sample 10 was calculated. The amount of the sample put in the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value i, the mass correction value i ′, and the calculated content ratio of isopropyl alcohol were as shown in Table 19 below.

Further, the sample 10 to be measured was analyzed for all components by gas chromatography in the same manner as in Example 1, and the content ratio of isopropyl alcohol was measured. The measured values of the content ratio of isopropyl alcohol are as shown in Table 19 below, and it was found that the content ratio calculated based on the ¹ H-NMR spectrum shows a good agreement with the content ratio measured by the gas chromatograph.

(Example 11: Determination of methanol (MeOH))
Methanol is diluted with commercially available regular gasoline to which no oxygen-containing compound is added, and the methanol content ratio is 20.3%, 5.4%, 2.3%, 1.4%, 0.6%, respectively. A weight percent sample was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integral value j of a peak derived from methanol (a peak observed around 3.5 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

Next, the integrated value j of the peak obtained for each sample was subjected to mass correction to a value per 100 mg of the sample to obtain a mass correction value j ′. A calibration curve was created with the mass correction value j ′ obtained for each sample as the horizontal axis and the methanol content in each sample as the vertical axis. The amount, integrated value j, and mass correction value j ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 20 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing methanol was prepared as the measurement target sample 11, and the ¹ H-NMR spectrum was measured according to the measurement method described above, the integral value j was obtained, and the mass correction value j ′ was calculated. Using the obtained mass correction value j ′ and the calibration curve, the content ratio of methanol in the measurement target sample 11 was calculated. The amount of the sample put in the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value j, the mass correction value j ′, and the calculated methanol content ratio were as shown in Table 21 below.

Moreover, about the measurement object sample 11, it carried out similarly to Example 1, all component analysis by a gas chromatograph was performed, and the content rate of methanol was measured. The measured value of the content ratio of methanol is as shown in Table 21 below, and it was found that the content ratio calculated based on the ¹ H-NMR spectrum shows a good agreement with the content ratio measured by the gas chromatograph.

(Example 12: Determination of ethanol (EtOH))
Ethanol is diluted with commercially available regular gasoline to which no oxygen-containing compound is added, and the ethanol content is 20.2% by mass, 5.4% by mass, 3.2% by mass, 1.3% by mass, and 0.6%, respectively. A weight percent sample was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integral value k of an ethanol-derived peak (peak observed around 3.7 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

Next, the integrated value k of the peak obtained for each sample was subjected to mass correction to a value per 100 mg of the sample to obtain a mass correction value k ′. Then, a calibration curve was prepared with the mass correction value k ′ obtained for each sample as the horizontal axis and the ethanol content in each sample as the vertical axis. The amount, integral value k, and mass correction value k ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 22 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing ethanol was prepared as the measurement target sample 12, and the ¹ H-NMR spectrum was measured according to the measurement method, the integral value k was determined, and the mass correction value k ′ was calculated. Using the obtained mass correction value k ′ and the calibration curve, the content ratio of ethanol in the measurement target sample 12 was calculated. The amount of the sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value k, the mass correction value k ′, and the calculated ethanol content were as shown in Table 23 below.

Moreover, about the measurement object sample 12, it carried out similarly to Example 1, the all component analysis by the gas chromatograph was performed, and the content rate of ethanol was measured. The measured values of the ethanol content were as shown in Table 23 below, and it was found that the content calculated based on the ¹ H-NMR spectrum showed good agreement with the content measured by gas chromatography.

(Example 13: Determination of n-butanol (n-BuOH))
n-Butanol is diluted with a commercially available regular gasoline to which no oxygen-containing compound is added, and the content ratios of n-butanol are 19.5% by mass, 5.1% by mass, 2.6% by mass and 1.1% by mass, respectively. A sample of 0.5% by mass was prepared. About each prepared sample, the < ¹ > H-NMR spectrum was measured according to the said measuring method, respectively.

From the obtained ¹ H-NMR spectrum, an integral value l of a peak derived from n-butanol (a peak observed around 3.6 ppm with reference to tetramethylsilane) was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

Next, the integrated value l of the peak obtained for each sample was subjected to mass correction to a value per 100 mg of the sample to obtain a mass correction value l ′. A calibration curve was prepared with the mass correction value l ′ obtained for each sample as the horizontal axis and the n-butanol content in each sample as the vertical axis. The amount, integrated value l, and mass correction value l ′ of each sample put in the NMR sample tube by ¹ H-NMR spectrum measurement were as shown in Table 24 below. The prepared calibration curve was as shown in FIG.

Next, gasoline containing n-butanol was prepared as the measurement target sample 13, and a ¹ H-NMR spectrum was measured according to the measurement method described above, an integral value l was obtained, and a mass correction value l ′ was calculated. Using the obtained mass correction value l ′ and the calibration curve, the content ratio of n-butanol in the measurement target sample 13 was calculated. The amount of the sample put into the NMR sample tube by ¹ H-NMR spectrum measurement, the integral value l, the mass correction value l ′, and the calculated content ratio of n-butanol were as shown in Table 25 below.

Moreover, about the measurement object sample 13, it carried out similarly to Example 1, all the component analysis by a gas chromatograph was performed, and the content rate of n-butanol was measured. The measured value of the content ratio of n-butanol is as shown in Table 25 below, and it was found that the content ratio calculated based on the ¹ H-NMR spectrum shows a good agreement with the content ratio measured by the gas chromatograph. .

(Example 14)
A ¹ H-NMR spectrum was measured according to the above measurement method for gasoline containing ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol, and isopropyl alcohol (hereinafter, sample 14 to be measured). The amount of the measurement target sample 14 used for the measurement was 69.5 mg. For each of ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol and isopropyl alcohol, the integrated value of the peak derived from the hydrogen atom bonded to the α-position carbon atom of the oxygen atom was determined. Here, for the peak integration value, a peak integration curve was drawn under the same drawing conditions as in Example 1, the height of the integration curve was measured, and the height was taken as the integration value of the peak.

  The obtained integrated value of each peak was subjected to mass correction to a value of 100 mg of a sample to obtain a mass correction value. From the obtained mass correction values and the calibration curves obtained in Examples 8 to 12, the content ratio in the gasoline for each of ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol, and isopropyl alcohol was determined. Calculated. The calculated content ratio was as shown in Table 26 below.

Subsequently, all the components analysis by a gas chromatograph was performed about the measuring object sample 14 like Example 1, and each content rate of ethyl tert- butyl ether, methyl tert- butyl ether, ethanol, methanol, and isopropyl alcohol was measured. . The measured values of the content ratio are as shown in Table 26 below, and the content ratio calculated based on the ¹ H-NMR spectrum showed good agreement with the content ratio measured by the gas chromatograph.

(Example 15)
For gasoline containing ethyl-tert-butyl ether, methyl-tert-butyl ether, ethanol, methanol and isopropyl alcohol (hereinafter, measurement target sample 15), the content ratio of each oxygenated compound was set to ¹ H in the same manner as in Example 14. -Measured by NMR spectrum and gas chromatograph. The amount of the measurement target sample 15 used for the ¹ H-NMR spectrum measurement was 45.9 mg. The measured values of the content ratio are as shown in Table 27 below, and the content ratio calculated based on the ¹ H-NMR spectrum showed good agreement with the content ratio measured by the gas chromatograph.

(Example 16)
About the measuring object sample 14, the content rate of the oxygen-containing compound was computed by the method similar to Example 14 based on the < ¹ > H-NMR spectrum. This was performed four times, and the repeatability was verified. The calculation results of the content ratio of the oxygen-containing compound at each time were as shown in Table 28. With respect to the content ratio of any oxygen-containing compound, the standard deviation σ is within about 0.1, and it was confirmed that the fuel oil analysis method according to the present invention is excellent in repeatability.

Claims (4)

A first step of measuring the ¹ H-NMR spectrum of the fuel oil;
In the ¹ H-NMR spectrum, the content ratio of the oxygenated compound in the fuel oil is determined based on the integrated value of the peak derived from the oxygenated compound having a hydrogen atom bonded to the α-position carbon atom of the oxygen atom. A method for analyzing fuel oil, comprising two steps.   2. The fuel oil analysis method according to claim 1, wherein the oxygen-containing compound contains at least one selected from the group consisting of methyl-tert-butyl ether, ethyl-tert-butyl ether, methanol, ethanol, isopropyl alcohol, and n-butanol. .   The fuel oil analysis method according to claim 1, wherein the fuel oil includes gasoline. Before the second step,
Measuring the ¹ H-NMR spectrum of a plurality of samples containing the oxygen-containing compound and different in content ratio, and preparing a calibration curve based on the integrated value;
2. In the second step, the content ratio of the oxygen-containing compound in the fuel oil is obtained based on an integrated value of the peak in the ¹ H-NMR spectrum of the fuel oil and the calibration curve. The analysis method of the fuel oil as described in any one of -3.

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