JPH07270390A - Analysis of hydrocarbon oil - Google Patents

Abstract

PURPOSE:To measure the naphthene component, paraffin component or aromatic component among saturated components, especially, in lower olefinic hydrocarbon oil such as kerosene with high accuracy. CONSTITUTION:A gas chromatograph-microwave induction plasma atomic emission detector is used to obtain chromatograms of the carbon element mode and hydrogen element mode related to a known hydrocarbon compd. to actually measure the content ratio of carbon and hydrogen and an addition area to be added per a unit elution time of the chromatogram of the hydrogen element mode is calculated from the actually measured value of the content ratio and a theoretical content ratio and added to the area of the chromatogram of the hydrogen element mode to correct the area of the region of the hydrogen element mode. The content ratio of paraffin and naphthene components can be calculated on the basis of this correction with high accuracy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to composition analysis of hydrocarbon oils, and more particularly to analysis capable of measuring naphthene content and paraffin content in saturated components of low olefin hydrocarbon oils (eg kerosene) with high accuracy. Regarding the method.

[0002]

2. Description of the Related Art Low olefin hydrocarbon oils such as kerosene are refined liquid hydrocarbon mixtures, and are mainly used for lights, heating fuels, kitchen fuels, petroleum engines, solvents and the like. As a method of analyzing the composition of the above hydrocarbon oil, there is a method of classifying and quantifying a sample by three types of hydrocarbons including a saturated component, an aromatic component and a naphthene component by mass spectrometry (ASTM D2789). After separating the sample into saturated and aromatic components by column chromatography,
There is a method of classifying saturated components into 6 types and aromatic components into 21 types (ASTM D2786, 323).
9).

A high performance liquid chromatograph (HPL
C) is used to modify the column with silver ions, and the saturated, aromatic, and olefinic components in the sample are detected by a differential refractometer or a dielectric constant detector, and this is multiplied by a correction factor to quantify the sample. Known methods include an analysis method and a method in which the solubility of aniline varies depending on the composition of a solute to quantify a sample by type.

[0004]

However, the method of analyzing the composition of kerosene does not fall within the range of 210 ° C. or lower in the applicable distillation temperature according to the above-mentioned method of ASTM D2789. Further, the separation of saturated components and aromatic components by column chromatography has a drawback that low boiling point components are lost.
In the method of No. 86, D3239, very complicated operation is required at the previous stage of composition analysis such as calculation of average carbon number and calculation of correction coefficient. In addition, each of the above methods requires a magnetic field type mass spectrometer and requires very expensive equipment.

Further, the method using HPLC can only discriminate between paraffins, aromatics and olefins, and the detection method using a differential refractometer causes an error in the correction coefficient depending on the measurement sample. In the method using the rate detector, a low boiling point fluorine-based solvent must be used, and it is necessary to cool the entire system.

Moreover, even if a gas chromatograph (hereinafter referred to as "GC") is used to measure using a capillary column having high separation efficiency, peaks are not separated for each type of hydrocarbon oil, and therefore an analytical method has been established for GC. The current situation is that it has not been done.

On the other hand, recently, gas chromatograph-microwave induction plasma (hereinafter referred to as "GC
-AED ". ) Is used. The AED is a selective type detector, and can obtain a chromatogram for each element, has excellent linearity, and has a wide range. Further, from such characteristics, it is possible to calculate the composition formula by analyzing the measurement peak. However, the hydrogen element mode has a drawback of poor linearity because it reacts with the supplied reaction gas, which is a major obstacle to the analysis of hydrocarbon oils.

The present invention has been made in view of the above circumstances, and it is possible to accurately analyze a hydrocarbon oil by using a GC-AED, and particularly to measure the content ratio of naphthene content and paraffin content in the hydrocarbon oil. The purpose of the present invention is to provide an analysis method.

[0009]

Means for Solving the Problems The present inventors have found that the GC-AE
In the analytical method for determining the ratio of carbon atoms and hydrogen atoms contained in the sample using D and the content ratio of naphthene and paraffin based on these ratios, a part of the hydrogen atoms in the sample is chromatographed in the hydrogen element mode. We focused on the fact that this is an obstacle that cannot be accurately measured because it does not appear in the gram. Then, if it was possible to obtain an accurate value of the area of the chromatogram in the elemental hydrogen mode, it was convinced that highly accurate quantification was possible based on this. Then, as a result of diligent study, by adding a certain proportion of area according to the component elution time width (hereinafter also referred to as “baseline length”) to the obtained hydrogen element mode chromatogram, the hydrogen element mode We have found that the area can be corrected with high accuracy.

That is, the method for analyzing a hydrocarbon oil according to the present invention uses (1) a gas chromatograph-microwave induction plasma atomic emission detector and a chromatogram in a carbon element mode and a hydrogen element mode for a known hydrocarbon compound. Then, the content ratio of carbon and hydrogen is measured, and the added area to be added per unit elution time of the hydrogen element mode chromatogram is calculated from the measured value of this content ratio and the theoretical content ratio. Step, and (2) the area of the chromatogram in the hydrogen element mode of the measurement object,
Adding the additional areas obtained in the step (1) above to correct the area for the hydrogen element mode;
(3) The step of obtaining the composition of the hydrocarbon oil based on the area of the carbon element mode of the measurement object and the area after the correction of the hydrogen element mode corresponding to the area.

The method for analyzing hydrocarbon oil of the present invention is
(1) A gas chromatograph-microwave induction plasma atomic emission detector was used to obtain a carbon element mode and hydrogen element mode chromatogram of a known hydrocarbon compound, and the carbon and hydrogen content ratios were measured. A step of obtaining an additional area to be added per unit elution time of the hydrogen element mode chromatogram from the measured content rate and the theoretical content rate, and (2) gas chromatograph-microwave induction plasma atomic emission detector Using
Obtaining a chromatogram of its carbon element mode and hydrogen element mode for the saturated content of the measurement object,
(3) Add the additional area obtained in the step (1) above to the area of the chromatogram in the hydrogen element mode,
Correcting the area for the elemental hydrogen mode,
(4) The step of obtaining the content ratios of the paraffin content and the naphthene content based on the area for the carbon element mode and the corrected area for the hydrogen element mode corresponding thereto.

[0012]

The operation of the present invention will be described below with reference to FIG. In the following, among the hydrocarbon water oils, an example of kerosene will be mainly described, but not only hydrocarbon oils composed of paraffins having various carbon numbers, but also hydrocarbon oils composed of paraffins and naphthenes and other low olefins. It is also applicable to hydrocarbon oils.

Usually, a liquid chromatograph (hereinafter referred to as "L
"C". If a silica-based column is used in 1), the components in kerosene can be separated into a saturated component and an aromatic component. Here, first, using this method, the sample is separated into a saturated component and an aromatic component and each is separated into equal volumes (step 2). Here, when the sample contains an aromatic component, an olefin component, etc., the means for separating these components from the saturated component is not particularly limited. FIG. 1 shows an example in which the saturated component and the aromatic component are separated by using a column having a high polarity in LC, and the subsequent treatment is advanced. However, a preparative GC equipped with a collector has a low polarity. It is also possible to use a column as a sample by appropriately collecting in a certain boiling point range of the sample. In this case, if the sample contains aromatic components,
GC-AED is used to separate a paraffin and an aromatic component by using a highly polar column, and the method according to the present invention can be applied to the separated paraffin.

Next, in order to obtain the additional area to be added per unit elution time of the chromatogram in the elemental hydrogen mode, a known standard sample is measured by GC-AED. As a result, from the C / H ratio (ratio of carbon atoms to hydrogen atoms in the sample) and the length of the elution time of the standard sample, the additional area (that is, area correction) to be added per unit elution time of the chromatogram. The coefficient) is obtained (step 1). The added area thus obtained is applied not only to the correction of the single component peak of the chromatogram but also to the correction of the non-separated peak. As shown in FIG. 2, the additional area does not change from the load of the sample on the detector, that is, the peak size. Further, the value of the area to be added per unit elution time is constant (nearly "20" in the case of FIG. 3), regardless of the structure of the measurement compound. Since the additional area depends on the state of the detector of the GC-AED, it is preferable to measure it before measuring the sample.

The area to be added per unit elution time is determined roughly, specifically as follows. (1) Prepare two types of samples with different concentrations of standard substances, for example, n-decane (C ₁₀ H ₂₂ ), or use samples of two types of known substances. Hereinafter, chromatograms in the carbon element mode and the hydrogen element mode are obtained for two types of samples (Sample A and Sample B). Here, sample A,
Samples B, and C _A chromatogram area by carbon element _mode, C _B, and the chromatogram area by hydrogen elements mode H _A, H _B, and the elution time of the chromatogram obtained by hydrogen elements mode T _A,
The deficiencies of the chromatogram area in the T _B and hydrogen element modes are α and β, respectively. Here, since the additional area per unit time to be obtained is constant, the following formula is established.

[0016]

[Equation 1]

(2) When analyzing the chromatogram area of sample A and sample B, since the standard substance is C ₁₀ H ₂₂ , the response factor of each element is C _A / 10 for carbon element and for hydrogen element. Is (H _A
+ Α) / 22. Therefore, F _A is as follows when the ratio of the response factor for the sample A to F _A.

[0018]

[Equation 2]

Similarly, if the response factor ratio for sample B is F _B , then F _B is as follows.

[0020]

[Equation 3]

(3) Since the ratio of the response factors is constant regardless of the sample concentration, the formula [4] can be obtained from the formulas [2] and [3].

[0022]

[Equation 4]

Further, the following expression [5] is obtained from the expression [1].

[0024]

[Equation 5]

Equation [6] is obtained from equations [4] and [5].

[0026]

[Equation 6]

[7] can be obtained by rearranging the expression [6].

[0028]

[Equation 7]

Here, C _A , C _B , H _A , H _B , T _A ,
Since T _B is a value obtained by actual measurement, α can be calculated. Therefore, the _{S F} = _α / _{T A,} the area to be added per unit time is obtained.

(4) As described above, α can be obtained by measuring the peaks and determining C _A , C _B , H _A , H _B , T _A and T _B. FIG. 2 shows the results obtained by measuring various concentrations of the sample. Regardless of the size of the C _A, the value of S _F can be understood that the substantially constant.

Further, the saturated component obtained by LC is analyzed by using GC-AED to obtain chromatograms in carbon element mode and hydrogen element mode (step 3).

The obtained chromatogram is preferably fractionated into a suitable number within a suitable range. The accuracy of measurement is improved by dividing the chromatogram into an appropriate range. This is because the ratio of carbon atoms to hydrogen atoms of paraffin differs depending on the number of carbon atoms. In the case of kerosene, it is preferable to fractionate into about 6 to 8 based on the projected n-paraffin. The area of each fractionation region of the fractionated chromatogram is obtained for each of the carbon element mode and the hydrogen element mode (step 4).

Further, the above-mentioned additional area (value obtained by multiplying the elution time width by the area correction coefficient) is added to the area of the fraction obtained in the hydrogen element mode (step 5).

From the area of each fraction obtained as described above, the solution of the simultaneous equations using the H / C ratio is obtained (the solution method by this simultaneous equation will be described later). Quantification of naphthenic and paraffinic contents in can be performed (step 6).

The saturated and aromatic contents of the sample can be separately categorized (step 7), and the naphthene content and paraffin content of all the samples can be determined (step 8). If the column used here is a non-polar one in which the components generally elute in the order of the boiling points, the measurement sample will be fractionated in the order of the boiling points.
It is possible to know the content ratio of the naphthene component according to the boiling point distribution.

Furthermore, the presence or absence of naphthenebenzenes for each boiling point distribution can be confirmed by analyzing the aromatic content obtained by LC using GC-AED and performing the same analysis.

The above-mentioned processing in step 6 (classification and quantification of paraffins and naphthenes) is carried out as follows. First, a mixture of normal paraffins having about 8 to 25 carbon atoms is measured by GC-AED as an external standard substance.

As an example, when an equal mixture of normal paraffins having 9 and 10 carbon atoms (hereinafter referred to as nC9 and nC10) is measured as an external standard substance, the area in the carbon element mode is Cs and the area in the hydrogen element mode is Area is H
Assuming that s ′ (“′” indicates that the correction is performed by the added area), the area ratio Hps of hydrogen atoms to carbon atoms of nC9 and nC10 can be expressed by the following equation.

[0039]

[Equation 8] Hps = Hs ′ / Cs

The average number ratio of hydrogen atoms of nC9 and nC10 to carbon atoms is 2.21. on the other hand,
Since naphthenic hydrocarbons expressed by general formula _C n _{H 2n,}
The ratio of the number of hydrogen atoms to the number of carbon atoms is 2.00. Therefore, the area ratio Hns of hydrogen atoms to carbon atoms of the naphthene-based hydrocarbon can be expressed by the following equation.

[0041]

[Equation 9]

Therefore, assuming that the fractionated fraction is a fraction containing 9 and 10 carbon atoms as the main component in terms of normal paraffin, the saturated component area of the fraction in the carbon element mode is Ct and hydrogen element. Area in mode is H
As t ′ (“′” indicates that the correction by the additional area is performed), the area of the paraffins in the carbon element mode is Cp, the area of the hydrogen element mode is Hp,
When the area of the naphthenes in the carbon element mode is Cn and the area of the hydrogen element mode is Hn, the values of Cp and Cn in the carbon element mode can be obtained from the following simultaneous equations.

[0043]

[Equation 10] Cp + Cn = Ct Hps × Cp + Hns × Cn = Ht ′

For lighter fractions and heavier fractions, the ratio of the number of hydrogen atoms to the carbon atoms in terms of nomal paraffin equivalent of the fractions was calculated, and then calculated by the same method. You can get the value. The presence or absence of naphthenebenzenes can be confirmed by the same method.

However, since the presence of olefins seriously affects the analytical value, it is necessary to confirm the amount of olefins present in the measurement sample, and depending on the case, it is necessary to trap or hydrogenate the olefins. When the obtained chromatogram is fractionated to a proper number in a proper range, an external standard substance corresponding to the fractionated range is used to perform accurate fractionation by performing the same operation as above. Quantitative values of paraffins and naphthenes can be obtained for each of the fractions obtained.

Further, the treatment method in the case of fractionation is not limited to the above-mentioned method, and a method using the ratio of response factors of each element is also possible. For example, a case where n-decane (C ₁₀ H ₂₂ ) is used as the external standard substance will be described. The area in the carbon element mode of the obtained chromatogram is Cs, the area in the hydrogen element mode is Hs, and the corrected area is Hs'. When the ratio of the response factor of each element is F, F is expressed as follows.

[0047]

[Equation 11]

The formula [8] shows the area value occupied by the hydrogen element area with respect to the carbon element area 1. Therefore, in the case of a fraction containing 9 and 10 carbon atoms as a main component, the average value of the number ratio of carbon and hydrogen elements in paraffin is 2.21, and naphthene is 2.00. To establish.

[0049]

[Equation 12] Cp + Cn = Ct ...

[9] Cp × F × 2.21 + Cn × F × 2.00 = Ht ′ ... [10]

[0050]

Cp and Cn in this range can be obtained from the expressions [9] and [10]. Fractions other than this can be obtained by changing the average value of the carbon / hydrogen element number ratio of the paraffins of the fractionated fraction, and by measuring the external standard sample once, It is also possible to obtain Cp and Cn for the fractionated fraction.

The LC used in this method is intended to fractionate the measurement sample, but HPLC is desirable when sufficient separation is required. Further, the LC or HPLC column used for fractionation of the measurement sample is preferably a silica column because it is intended for fractionation and fractionation of saturated and aromatic components, and a column having a high resolution is preferable. .

As the mobile phase, it is possible to use a light polar organic solvent, but normal hexane, which has a large molecular diffusion and is excellent as a solvent for GC, is preferable, and its speed is 0. .1 to 100 ml / mi
The range of n is preferable. Further, the sample injection amount is preferably about 1 to 10 μl in the case of kerosene.

Since the column used for the GC-AED used in the present invention is a dilute solution for preparative separation by LC, a large volume of sample can be injected and an inner diameter of 0.32 to have a required separation ability. 1.2mm, length 5-40m
m, a film thickness of about 0.1 to 5.0 μm, and a capillary column in which a liquid phase is chemically bonded is desirable. Further, when the purpose is to classify quantitatively by boiling point distribution of a measurement sample, the liquid phase of the column is methyl silicon, Alternatively, a resin mainly containing methyl silicon and having a methyl silicon liquid phase crosslinked chemically is preferable. As the carrier gas at this time,
Since GC-AED is used, it is necessary to use helium. The speed is preferably in the range of 2 to 30 ml / min.

The amount of the sample injected is about 1 to 20 μl in the case of a fraction collected by HPLC, and the on-column injection method, the splitless injection method, or the direct injection method is preferable. Further, the GC oven is preferably one that can raise the temperature in order to shorten the analysis time and not impair the separability of the column. Since the temperature rising condition corresponds to, for example, a light fraction in a kerosene fraction, it is preferable that a cooling mechanism is attached, and the temperature is kept at an initial temperature of 0 to 40 ° C. for 1 to 10 minutes and then 5
It is desirable to raise the temperature to 250 to 280 ° C. at a temperature rising rate of 10 ° C./min and hold for 5 to 20 minutes.

[0055]

EXAMPLES Examples of the present invention will be described in detail below. Here, an example of a sample having a known composition will be described in (A), and an example of using kerosene as a sample will be described in (B). Table 1 shows the analysis conditions in these examples.

[0056]

[Table 1]

(A); Here, nC6 is used as a standard sample.
(N-hexane) is used. Further, since this example is for demonstrating the effect of the present invention, the measurement sample is a known mixture (equivalent mixture of cyclomethylhexane and nC6). Further, the additional area (that is, the area correction coefficient) to be added per unit elution time was obtained as 20.1 in step 1 according to the procedure described above. In addition, the peaks of the measurement sample are overlapped.

The procedure of measurement results will be described below. C _A , C _B , H _A , H for two types of samples with different concentrations
_B , T _A , and T _B were obtained, and S _F was obtained from those values.

[0059]

[Table 2]

From the above measured values, α = 1811, S _F = 2
A value of 0.1 was obtained.

In step 6, first, a standard sample (nC
Regarding 6), the area of the chromatogram for each of the carbon element mode and the hydrogen element mode (Cs for the carbon element mode and Hs for the hydrogen element mode)
For Hs, the baseline length BT (elution time width) is multiplied by the area correction coefficient, and the multiplication result is added to the Hs to obtain the corrected Hs (
s'). Specifically, it is as follows.

Cs: 26627 Hs: 15543 BT (second): 3.66 Hs': 15616

From the above values of Cs and Hs ', the ratio Hps of Hs' to Cs can be obtained. Specifically, it is as follows.

[0064]

[Equation 13] Hps = Hs ′ / Cs = 0.586

On the other hand, for the measurement sample, the areas of the chromatograms (Ct for the carbon element mode and Ht for the hydrogen element mode) were determined for the carbon element mode and the hydrogen element mode, and Ht was the same as above. , The baseline length BT (elution time width) is multiplied by the area correction coefficient, and the multiplication result is added to the Ht to obtain the corrected Ht (this is referred to as Ht ′). Specifically, it is as follows.

Ct: 3389 Ht: 1768 BT (seconds): 3.73 Ht ': 1843

On the other hand, in cyclomethylhexane, the ratio of the number of hydrogen atoms to the number of carbon atoms is 2.00, and in nC6, the ratio of the number of hydrogen atoms to the number of carbon atoms is 2.33. The ratio Hns of the area of the hydrogen element mode chromatogram to the area of the carbon element mode chromatogram of hexane is expressed as follows.

[0068]

Hns = (2.00 × Hs ′) / (2.33 × Cs) = 0.501

As described above, the amount of carbon atoms Cp and the amount of hydrogen atoms Hp of paraffin component, the amount Cn of carbon atoms and the amount Hn of hydrogen atom of naphthene contained in the measurement sample, and the above Ct, The following relationships are established between Hps, Hns and Ht '.

[0070]

[Equation 15] Cp + Cn = Ct Hps × Cp + Hns × Cn = Ht ′

From the above equation, Cp = 1691 is obtained, and Cp
The contents of Cn and Cn are 49.9 wt% and 50.
It becomes 1 wt%. In the present example, since the sample having the content ratio of Cp and Cn of 1: 1 was used, the above calculation result proves that the measurement accuracy is extremely high.

For the standard sample and the measurement sample similar to the above, Hs and Ht are simply multiplied by the correction coefficient,
A comparative example when the conventional method is applied is shown below. In this comparative example, Cs and Hs ″ (values after multiplying Hs by the correction coefficient) were measured as follows.

Cs: 26627 Hs ″: 15588

The correction coefficient here is handled as follows. First, known samples having different concentrations are measured, and a correction coefficient is calculated according to the size of the measured peak. Next, a correction table (graph) is created by connecting each point, and the actual area value is corrected by using the correction coefficient of the table according to the peak size of the actual sample.

Normally, the processing is performed as described above, but the correction coefficient is set to 1 on the assumption that the error can be ignored in the peak having a certain size or more. Therefore, in the case of overlapping peaks, for example, three small peaks overlapping, the total area value is targeted for correction, so the correction coefficient becomes 1, and the correction is substantially performed. There is a problem such as not.

From the above Cs and Hs ″ to Hps
Is as follows.

[0077]

(16) Hps = Hs ″ /Cs=0.585

Further, Ct and Ht were measured as follows.

Ct: 3389 Ht ″: 1884

Ht ″ is a value after Hs is multiplied by the correction coefficient. In this case, Hns will be expressed as follows.

[0081]

Hns = (2.00 × Hs ″) / (2.33 × Cs) = 0.503

Further, as in the above-mentioned embodiment, the following formulas are established.

[0083]

[Equation 18] Cp + Cn = Ct Hps × Cp + Hns × Cn = Ht ″

From the above equation, Cp = 2183 is obtained, and Cp
The contents of Cn and Cn are 64.4 wt% and 35.
It is 6 wt%, which means that there is a large difference from the original content ratio (theoretical 50 wt% each).

(B) In this example, in the hydrogen element mode, the added area per unit elution time is
It is similar to the case of (A). Analysis result of saturated component and aromatic component by LC First, kerosene was fractionated into saturated component and aromatic component by LC using a silica gel column and collected (step 2). Next, when the total area was calculated by GC-FID and the respective concentrations were calculated, the saturated content was 80.1 wt.
%, And the aromatic content was 19.9 wt% (step 7).

The saturated components collected in step 2 of the results of the GC-AED measurement for the saturated components were measured by the GC-AED to obtain chromatograms in the carbon element mode and the hydrogen element mode (step 3). Fraction, N
o. Fractionation into 6 ranges from 1 to 6 is performed, and the area of each fractionation region is measured for the carbon element mode, and the area of each fractionation region is determined for the hydrogen element mode at the same cut point as in the carbon element mode. Actually measured (step 4). Here, the area in each fractional region in the carbon element mode and the hydrogen element mode is defined as “C area (Cs)”.
And "measured H area (Hs)". It should be noted that in Tables 2 and 3, the respective densities of the respective fractionated regions are indicated by the “occupancy ratio”
It is shown as.

Next, the additional area is added to the actually measured H area (Hs) for correction (step 5). This added area is (baseline length of each fraction) × (area correction coefficient), and the area of each fraction area after correction is “corrected H area (H
s') ". The paraffin component and the naphthene component are obtained by using Cs as Ct in (A) and Hs' as Ht in (A) (step 6). Note that, here, n-decane (nC10) was used as a standard sample, and the method using the above-mentioned response factor was applied to all fractions to determine the paraffin content and the naphthene content.

Here, by multiplying the total value of the paraffin content and the naphthene content by the ratio of the saturated content to the entire sample, it is possible to obtain the quantitative value of each type in all samples (step 8). The results were as shown in Tables 3 to 5 below. In addition, Table 5 shows the average of the composition ratios of the fractionated hydrocarbons.

Paraffin content: 46.9 wt% Naphthene content: 33.2 wt% Aromatic content: 19.9 wt%

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

[Table 5]

[0093]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain highly accurate analysis results by hydrocarbon type for a low olefinic hydrocarbon oil without being affected by the capacity of each component.
This method is a method for categorizing naphthenes in saturated components
It is a completely new method.

Moreover, the microwave correction plasma atomic emission detector includes a new correction method corresponding to the non-linearization of the hydrogen element mode, which improves the accuracy of the composition formula calculation of a single peak component. Can be planned. This is extremely useful for a research institution that uses the detector.

Further, in the present invention, when a non-polar column is used, it is possible to classify and quantify by boiling point distribution, and in a hydrocarbon solvent treated with an aromatic component, which has recently become a problem in terms of safety and environment, Since it is possible to accurately know the detailed boiling point distribution of each category and the amount of components of each category, the industrial value thereof is extremely high for the industry using organic solvents such as petrochemicals and petroleum.

[Brief description of drawings]

FIG. 1 is a flow chart of an analysis method of the present invention.

FIG. 2 is a diagram showing a relationship between an added area and the number of carbon atoms.

Claims (2)

[Claims] (1) A gas chromatograph-microwave induction plasma atomic emission detector is used to obtain a carbon element mode and a hydrogen element mode chromatogram of a known hydrocarbon compound, and the content ratio of carbon and hydrogen is obtained. And a step of obtaining an additional area to be added per unit elution time of the hydrogen element mode chromatogram from the measured value of this content ratio and the theoretical content ratio, (2)
A step of adding the additional area obtained in the step (1) above to the area of the chromatogram in the hydrogen element mode of the measurement object to correct the area in the hydrogen element mode; and (3) a carbon element of the measurement object. Based on the area of the mode and the area after the correction of the corresponding hydrogen element mode,
A method for analyzing a hydrocarbon oil, comprising the step of determining the composition of the hydrocarbon oil. (1) A gas chromatograph-microwave induction plasma atomic emission detector is used to obtain a carbon element mode and a hydrogen element mode chromatogram of a known hydrocarbon compound to obtain the carbon and hydrogen content ratios. A step of performing an actual measurement and obtaining an additional area to be added per unit elution time of the hydrogen element mode chromatogram from the measured value of this content rate and the theoretical content rate, (2) Gas chromatograph-microwave induction Using a plasma atomic emission detector, the step of obtaining a chromatogram in the carbon element mode and the hydrogen element mode of the saturated content of the measurement object, and (3) the area of the chromatogram in the hydrogen element mode, Adding the additional areas obtained in step to correct the area for the hydrogen element mode, and (4) A method for analyzing a hydrocarbon oil, comprising: a step for obtaining a content ratio of a paraffin content and a naphthene content based on the area for the elementary element mode and the area after the correction for the corresponding hydrogen element mode. .