Method for determining types of carbon and hydrogen in hydrocarbon sample by adopting gas chromatography-mass spectrometry

Abstract

The invention relates to a method for determining the types of carbon and hydrogen in a hydrocarbon sample by adopting gas chromatography-mass spectrometry. The method comprises the steps of carbon number cutting, calculation of mass fractions of various hydrocarbons in components with different carbon numbers in non-polar components and polar components, carbon number correction and the like. The method disclosed by the invention is low in requirement on an analysis instrument, relatively high in analysis efficiency, relatively low in analysis cost and relatively short in test time.

Description

Technical Field

[0001] The present application relates to a method for determining the types of carbon and hydrogen in a hydrocarbon sample by using gas chromatography-mass spectrometry. Background Art

[0002] Petroleum is a complex mixture of various hydrocarbon compounds. In recent years, with the increasing consumption of petroleum resources, the continuous development of fine chemicals, and the establishment of the "dual carbon" goal, the "rough" petroleum processing method is no longer applicable. Only by conducting a comprehensive and detailed analysis and characterization of petroleum samples and designing the most optimized processing plan based on their molecular composition characteristics can we achieve "oil as oil, aromatic as aromatic, olefin as olefin". The efficient use of petroleum is actually the efficient use of hydrocarbon compounds, carbon and hydrogen elements in hydrocarbon compounds. Different types of carbon, such as carbon on aromatic rings, carbon on cycloalkane rings, and carbon on alkanes, have different chemical properties and processing potentials. The proportion of different types of carbon in the sample directly reflects important information such as the number of carbons in the side chain and the number of aromatic rings. These carbon and hydrogen type information is of great significance for designing its processing plan.

[0003] Nuclear magnetic resonance spectroscopy (NMR) can determine the types of carbon and hydrogen in petroleum samples. The types of carbon include aromatic carbon and side chain and cycloalkane carbon; the types of hydrogen include: hydrogen directly connected to the aromatic ring, hydrogen on CH2 at the α position of the aromatic ring, hydrogen on CH2 at the β position and beyond the β position of the aromatic ring, and hydrogen on CH3 at the γ position and beyond the γ position of the aromatic ring. Using the above parameters, various structural parameters of the sample can be calculated according to the Brown-Lander formula, thereby reflecting the elemental composition characteristics and processing potential of the sample. This is also the main method for determining the structural parameters of petroleum samples. However, the current method of determining the specific types of carbon and hydrogen by nuclear magnetic resonance requires the determination of the "carbon spectrum" and "hydrogen spectrum" respectively, which takes a long time, generally about 10 to 15 hours, has high analysis costs, and has high requirements for analytical instruments and personnel.

[0004] Gas chromatography-mass spectrometry can provide information on the hydrocarbon composition of petroleum samples. Furthermore, high-resolution mass spectrometry can infer the molecular composition of hydrocarbons by measuring the precise molecular weight. However, various mass spectrometry analysis methods currently only analyze and infer the type, carbon number, and structure of hydrocarbons, and do not involve information on the type of carbon and hydrogen in the sample.

[0005] CN107219244A discloses a quantitative analysis method for detecting coal structure parameters using solid nuclear magnetic carbon spectrum. The method determines the carbon structure parameters of a model compound through the solid nuclear magnetic carbon spectrum of the model compound, and regresses the aliphatic carbon and aromatic carbon fitting values ​​of the carbon spectrum peak fitting of the model compound with the theoretical values ​​to obtain a regression curve equation for correcting the solid nuclear magnetic carbon spectrum test error, and corrects the fitting parameters of the coal sample to be tested to achieve quantitative analysis of the solid nuclear magnetic carbon spectrum.

[0006] CN107704720B discloses a method for constructing an average molecular structure model of petroleum and a method for predicting properties. The method uses nuclear magnetic resonance to determine the hydrogen type distribution, that is, the aromatic hydrogen rate. An elemental analyzer is used to determine the total carbon and hydrogen elements, and a gel permeation chromatography is used to determine the molecular weight. Based on the above information, the structural parameters are calculated, and a method for constructing an average molecular structure model is established, so that the physical properties of the petroleum sample are predicted using the group construction method.

[0007] CN112577987A discloses a method for characterizing the molecular structure of lubricating base oil. The method requires using high-resolution mass spectrometry to determine the carbon number distribution of the sample, using nuclear magnetic resonance to determine the type distribution of carbon and hydrogen, and then making certain assumptions about the molecular structure, so that the chain structure length, number of substituents, and number of side chains of various types of hydrocarbons in the lubricating base oil can be characterized.

[0008] In summary, the current analysis of carbon and hydrogen types in petroleum samples generally uses nuclear magnetic resonance methods, and mass spectrometry can only analyze hydrocarbon types, but cannot quantitatively attribute carbon and hydrogen types. The content of various types of carbon and hydrogen is the basic data for calculating the structural information of petroleum samples, which is of great significance for in-depth research on sample composition characteristics, finding processing directions, and tapping processing potential. Summary of the invention

[0009] The purpose of the present invention is to provide a method for determining the types of carbon and hydrogen in hydrocarbon samples using gas chromatography-mass spectrometry. The method has low requirements for analytical instruments and can be implemented using low-resolution mass spectrometry. The analysis efficiency is high, the test time is less than 30 minutes, and the analysis cost is low.

[0010] In order to achieve the above object, the present disclosure provides a method for determining the types of carbon and hydrogen in a hydrocarbon sample by gas chromatography-mass spectrometry, the method comprising:

[0011] S1. Using a gas chromatography-EI source quadrupole mass spectrometer to detect polar components and non-polar components in the hydrocarbon sample to be tested, respectively, and using normal alkanes with different carbon numbers to cut the chromatograms of the non-polar components and the chromatograms of the polar components according to the carbon number;

[0012] S2. Calculating the mass fractions of each type of hydrocarbons in different carbon number array components in the non-polar component and the mass fractions of each type of hydrocarbons in different carbon number array components in the polar component according to the actual distillation range of the hydrocarbon sample to be tested;

[0013] Wherein, the molecular formula of each type of hydrocarbon in the non-polar component conforms to C x H 2x+2 , C x H 2x , C x H 2x-2, C x H 2x-4 , C x H 2x-6 , C x H 2x-8 and C x H 2x-10 One or more of, wherein x is the carbon number, and x is any integer from 8 to 42;

[0014] The molecular formula of each type of hydrocarbon in the polar component conforms to C y H 2y-6 , C y H 2y-8 , C y H 2y-10 , C y H 2y-12 , C y H 2y-14 , C y H 2y-16 , C y H 2y-18 , C y H 2y-20 , C y H 2y-22 , C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 One or more of, wherein y is the carbon number, and y is any integer from 8 to 42;

[0015] S3, performing carbon number correction on hydrocarbons of different polarities in the polar components;

[0016] Among them, the molecular formula is C y H 2y-6 , C y H 2y-8 and C y H 2y-10 The mass content of the polar component with carbon number y is respectively taken as the mass content of the first polar component with carbon number y-1;

[0017] The molecular formula is C y H 2y-12 , C y H 2y-14 and C y H 2y-16 The mass content of the polar component with carbon number y is respectively taken as the mass content of the second polar component with carbon number y-2;

[0018] The molecular formula is C yH 2y-18 , C y H 2y-20 and C y H 2y-22 The mass content of the polar component with carbon number y is taken as the mass content of the third polar component with carbon number y-3;

[0019] The molecular formula is C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 The mass content of the polar component with carbon number y is respectively taken as the mass content of the fourth polar component with carbon number y-4;

[0020] The total carbon number of the polar component after the carbon number correction is not less than the carbon number of its aromatic hydrocarbon parent ring;

[0021] S4, the non-polar component is represented by the chemical composition of paraffin and cycloparaffin, wherein C X H 2X+2 represents chain alkane, C x H 2x represents a monocyclic cycloalkane, C x H 2x-2 represents a bicyclic cycloalkane, C x H 2x-4 Represents a tricyclic cycloalkane structure, C x H 2x-6 Represents a tetracyclic cycloalkane structure, C x H 2x-8 represents a pentacyclic cycloalkane structure and C x H 2x-10 represents a six-ring cycloalkane structure, wherein the cycloalkane has only one side chain;

[0022] S5. The polar component is represented by the chemical composition of aromatic hydrocarbons, wherein C y H 2y-6 Represents the alkylbenzene structure, C y H 2y-8 Represents the structure of tetralin, C y H 2y-10 For the dicycloalkylbenzene structure, C y H 2y-12 It is a naphthalene structure, C y H 2y-14 It is an acenaphthene-like structure, C y H 2y-16 It is a fluorene structure, C y H 2y-18 It is a phenanthrene structure, C y H 2y-20It is a cycloalkanephenanthrene structure, C y H 2y-22 It is a pyrene structure, C y H 2y-24 for Class structure, C y H 2y-26 Cycloalkane Class structure, C y H 2y-28 It is a perylene structure, C y H 2y-30 It is a dibenzanthracene structure;

[0023] The aromatic hydrocarbon has only one side chain and the side chain is on the aromatic ring of the aromatic hydrocarbon;

[0024] S6. Calculate the mass fraction of carbon and the mass fraction of hydrogen contained in each type of hydrocarbon in different carbon number groups in the hydrocarbon sample to be tested according to the mass content of each type of hydrocarbon after carbon number correction and the chemical composition of the corresponding hydrocarbon, and obtain the paraffin carbon rate, paraffin hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate and aromatic ring hydrogen rate;

[0025] Calculating the carbon types and hydrogen types in different carbon number array components in the hydrocarbon sample to be tested;

[0026] The carbon type, hydrogen type, total carbon content and total hydrogen content of the hydrocarbon sample to be tested are calculated.

[0027] Optionally, in step S1, the carbon number cutting method comprises: the chromatographic retention time of the paraffin with a normal carbon number of n is T Cn The chromatographic retention time of the normal chain alkane with carbon number n-1 is T Cn-1 , then the retention time in the chromatogram is T Cn -T Cn-1 The region is defined as the carbon n component, wherein n is any integer from 8 to 42.

[0028] Optionally, in step S1, solid phase extraction is used to separate the hydrocarbon sample to be tested into the polar component and the non-polar component.

[0029] Optionally, in step S1, when the hydrocarbon sample to be tested contains normal alkanes, it is used as the basis for the carbon number cutting;

[0030] When the hydrocarbon sample to be tested does not contain normal alkanes, a normal alkane mixed standard sample with the same distillation range as the hydrocarbon sample to be tested is prepared as the basis for the carbon number cutting, or other samples containing normal alkanes in the corresponding distillation range are used as the basis for the carbon number cutting.

[0031] Optionally, in step S1, the detection conditions include: the starting temperature of the chromatographic column oven is below 60°C, preferably 40-50°C, the chromatographic heating program is below 40°C / min, preferably 10-20°C / min; the ionization voltage of the EI source is 50-70eV, preferably 70eV, the ionization current is 10-70μA, the ratio of the intensity of the fragment ion 67 and the fragment ion 71 generated by the ionization of n-hexadecane is 0.2-0.4, preferably 0.25-0.35, and the mass number scanning range is 30-1000, preferably 50-500.

[0032] Optionally, in step S2, the mass fractions of components of different carbon numbers in the non-polar component are calculated respectively using formula (1):

[0033] M S-Cn =A S-Cn / (A S + A A )× 100 % (1)

[0034] In formula (1), M S-Cn is the mass fraction of the non-polar component with carbon number n in the hydrocarbon sample to be tested;

[0035] A S-Cn is the FID chromatogram area of ​​the non-polar component with carbon number n in the hydrocarbon sample to be tested;

[0036] A S is the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested;

[0037] A A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

[0038] Optionally, in step S2, the mass fractions of components of different carbon numbers in the polar component are calculated respectively using formula (2):

[0039] M A-Cn =A A-Cn / (A S + A A )× 100 % (2)

[0040] In formula (2), M A-Cn is the mass fraction of the polar component with carbon number n in the hydrocarbon sample to be tested;

[0041] A A-Cn is the FID chromatogram area of ​​the polar component with carbon number n in the hydrocarbon sample to be tested;

[0042] A Sis the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested;

[0043] A A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

[0044] Optionally, in step S2, the mass fraction of each type of hydrocarbon in different carbon number array components in the non-polar component is calculated using the SH / T 0606 method or the SH / T 0659 method;

[0045] The mass fraction of each type of hydrocarbon in different carbon number components in the polar component is calculated using the SH / T 0606 method or the GB / T 18340.4 method.

[0046] Optionally, the distillation range of the hydrocarbon sample to be tested is 10-600°C, preferably 120-540°C.

[0047] Optionally, the hydrocarbon sample to be tested is one or more of straight-run oil, catalytic cracking oil, alkylate oil, extraction oil, cracked refined oil, hydrocracking oil, isomerized oil, biomass oil and plastic oil.

[0048] Through the above technical solution, the present disclosure has the following technical effects:

[0049] (1) The method disclosed in the present invention has low requirements for analytical instruments. It uses a low-resolution quadrupole mass spectrometer with high popularity and simple operation to replace the more expensive nuclear magnetic resonance and high-resolution mass spectrometer to provide structural information of the sample, and realizes the determination of various types of carbon and hydrogen content in hydrocarbon samples such as petroleum, including the alkane carbon rate, alkane hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate, and aromatic ring hydrogen rate. It provides an analytical method for quickly and deeply studying the structural composition characteristics of various types of hydrocarbons in oil products and finding targeted processing methods.

[0050] (2) The method disclosed in the present invention can simultaneously provide the carbon number distribution of various types of hydrocarbons in the non-polar components and polar components in petroleum and hydrocarbon samples, that is, molecular composition characterization data.

[0051] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0053] Figure 1 are the TIC and FID spectra of the non-polar and polar components in sample M;

[0054] Figure 2 It is the carbon number cutting diagram of TIC and FID spectra of non-polar components and polar components in the hydrocarbon components to be measured. DETAILED DESCRIPTION

[0055] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0056] The present disclosure provides a method for determining the types of carbon and hydrogen in a hydrocarbon sample by using gas chromatography-mass spectrometry, the method comprising:

[0057] S1. Using a gas chromatography-EI source quadrupole mass spectrometer to detect polar components and non-polar components in the hydrocarbon sample to be tested, respectively, and using normal alkanes with different carbon numbers to cut the chromatograms of the non-polar components and the chromatograms of the polar components according to the carbon number;

[0058] S2. Calculating the mass fractions of each type of hydrocarbons in different carbon number array components in the non-polar component and the mass fractions of each type of hydrocarbons in different carbon number array components in the polar component according to the actual distillation range of the hydrocarbon sample to be tested;

[0059] Wherein, the molecular formula of each type of hydrocarbon in the non-polar component conforms to C x H 2x+2 , C x H 2x , C x H 2x-2 , C x H 2x-4 , C x H 2x-6 , C x H 2x-8 and C x H 2x-10 One or more of, wherein x is the carbon number, and x is any integer from 8 to 42;

[0060] The molecular formula of each type of hydrocarbon in the polar component conforms to C y H 2y-6 , C y H 2y-8 , C y H 2y-10 , C y H 2y-12 , C y H 2y-14 , C y H 2y-16 , C y H 2y-18 , C y H 2y-20 , C y H2y-22 , C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 One or more of, wherein y is the carbon number, and y is any integer from 8 to 42;

[0061] S3, performing carbon number correction on hydrocarbons of different polarities in the polar components;

[0062] Among them, the molecular formula is C y H 2y-6 , C y H 2y-8 and C y H 2y-10 The mass content of the polar component with carbon number y is respectively taken as the mass content of the first polar component with carbon number y-1;

[0063] The molecular formula is C y H 2y-12 , C y H 2y-14 and C y H 2y-16 The mass content of the polar component with carbon number y is respectively taken as the mass content of the second polar component with carbon number y-2;

[0064] The molecular formula is C y H 2y-18 , C y H 2y-20 and C y H 2y-22 The mass content of the polar component with carbon number y is taken as the mass content of the third polar component with carbon number y-3;

[0065] The molecular formula is C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 The mass content of the polar component with carbon number y is respectively taken as the mass content of the fourth polar component with carbon number y-4;

[0066] The total carbon number of the polar component after the carbon number correction is not less than the carbon number of its aromatic hydrocarbon parent ring;

[0067] S4, the non-polar component is represented by the chemical composition of paraffin and cycloparaffin, wherein C x H 2x+2 represents chain alkane, Cx H 2x represents a monocyclic cycloalkane, C x H 2x-2 represents a bicyclic cycloalkane, C x H 2x-4 Represents a tricyclic cycloalkane structure, C x H 2x-6 Represents a tetracyclic cycloalkane structure, C x H 2x-8 represents a pentacyclic cycloalkane structure and C x H 2x-10 represents a six-ring cycloalkane structure, wherein the cycloalkane has only one side chain;

[0068] S5. The polar component is represented by the chemical composition of aromatic hydrocarbons, wherein C y H 2y-6 Represents the alkylbenzene structure, C y H 2y-8 Represents the structure of tetralin, C y H 2y-10 For the dicycloalkylbenzene structure, C y H 2y-12 It is a naphthalene structure, C y H 2y-14 It is an acenaphthene-like structure, C y H 2y-16 It is a fluorene structure, C y H 2y-18 It is a phenanthrene structure, C y H 2y-20 It is a cycloalkanephenanthrene structure, C y H 2y-22 It is a pyrene structure, C y H 2y-24 for Class structure, C y H 2y-26 Cycloalkane Class structure, C y H 2y-28 It is a perylene structure, C y H 2y-30 It is a dibenzanthracene structure;

[0069] The aromatic hydrocarbon has only one side chain and the side chain is on the aromatic ring of the aromatic hydrocarbon;

[0070] S6. Calculate the mass fraction of carbon and the mass fraction of hydrogen contained in each type of hydrocarbon in different carbon number groups in the hydrocarbon sample to be tested according to the mass content of each type of hydrocarbon after carbon number correction and the chemical composition of the corresponding hydrocarbon, and obtain the paraffin carbon rate, paraffin hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate and aromatic ring hydrogen rate;

[0071] Calculating the carbon types and hydrogen types in different carbon number array components in the hydrocarbon sample to be tested;

[0072] The carbon type, hydrogen type, total carbon content and total hydrogen content of the hydrocarbon sample to be tested are calculated.

[0073] The method disclosed in the present invention has low requirements for analytical instruments. It uses a low-resolution quadrupole mass spectrometer that is widely used and easy to operate to replace the more expensive nuclear magnetic resonance and high-resolution mass spectrometer to provide structural information of the sample. It can also provide the carbon number distribution of various types of hydrocarbons in the non-polar components and polar components in petroleum and hydrocarbon samples, that is, molecular characterization data, with high analysis efficiency and low analysis cost and testing time.

[0074] The method disclosed in the present invention is applicable to the detection of various hydrocarbon samples, which may include but are not limited to one or more of straight-run oil, catalytic cracking oil, alkylate oil, extraction oil, cracked refined oil, hydrocracked oil, isomerized oil, biomass oil and plastic oil.

[0075] In a specific embodiment, the total ion current chromatogram (TIC) and the flame ionization detector chromatogram (FID) of the non-polar components and polar components of the hydrocarbon sample M to be tested are as follows: Figure 1 shown.

[0076] like Figure 2 As shown, in a specific embodiment of the present disclosure, in step S1, the carbon number cutting method includes: the chromatographic retention time of the paraffin with a normal carbon number of n is T Cn The chromatographic retention time of the normal chain alkane with carbon number n-1 is T Cn-1 , then the retention time in the chromatogram is T Cn -T Cn-1 The region is defined as the carbon n component, wherein n is any integer from 8 to 42.

[0077] In a specific embodiment of the present disclosure, in step S1, when the hydrocarbon sample to be tested contains normal alkanes, it is used as the basis for the carbon number cutting. In one embodiment, the hydrocarbon sample M to be tested itself contains normal alkanes with different carbon numbers, and the TIC spectrum and FID spectrum of its non-polar component and polar component can be directly cut by carbon number, such as Figure 2 shown.

[0078] In another specific embodiment of the present disclosure, in step S1, when the hydrocarbon sample to be tested does not contain normal alkanes, a mixed standard sample of normal alkanes with the same distillation range as the hydrocarbon sample to be tested is prepared as the basis for the carbon number cutting, or other samples containing normal alkanes in the corresponding distillation range are used as the basis for the carbon number cutting.

[0079] In a specific embodiment of the present disclosure, in step S1, solid phase extraction is used to separate the hydrocarbon sample to be tested into the polar component and the non-polar component; the conditions of the solid phase extraction include: using silica gel as the stationary phase, using n-hexane as the eluent for the non-polar component, and using dichloromethane as the eluent for the polar component. Solid phase extraction is an operation well known to those skilled in the art and will not be described in detail here.

[0080] In a specific embodiment of the present disclosure, in step S1, the detection conditions include: the starting temperature of the chromatographic column oven is below 60°C, preferably 40-50°C, the chromatographic heating program is below 40°C / min, preferably 10-20°C / min; the ionization voltage of the EI source is 50-70eV, preferably 70eV, the ionization current is 10-70μA, the ratio of the intensity of the fragment ion 67 and the fragment ion 71 generated by the ionization of n-hexadecane is 0.2-0.4, preferably 0.25-0.35, and the mass number scanning range is 30-1000, preferably 50-500.

[0081] In a specific embodiment of the present disclosure, in step S2, the mass fractions of components of different carbon numbers in the non-polar component are calculated respectively using formula (1):

[0082] M S-Cn =A S-Cn / (A S +A A )×100% (1)

[0083] In formula (1), M S-Cn A is the mass fraction of the non-polar component with carbon number n in the hydrocarbon sample to be tested; S-Cn A is the FID chromatogram area of ​​the non-polar component with carbon number n in the hydrocarbon sample to be tested; S A is the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested; A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

[0084] In a specific embodiment of the present disclosure, in step S2, the mass fractions of components of different carbon numbers in the polar component are calculated respectively using formula (2):

[0085] M A-Cn =A A-Cn / (A S +A A )×100% (2)

[0086] In formula (2), M A-Cn A is the mass fraction of the polar component with carbon number n in the hydrocarbon sample to be tested; A-CnA is the FID chromatogram area of ​​the polar component with carbon number n in the hydrocarbon sample to be tested; S A is the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested; A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

[0087] According to the present disclosure, the mass fractions of the non-polar components and the polar components in different carbon number components in the hydrocarbon sample M to be tested are calculated using formula (1) and formula (2), respectively, as shown in Table 1.

[0088] Table 1 Mass fractions of non-polar components and polar components in different carbon number groups in the hydrocarbon sample M to be tested, %

[0089] Carbon number 11 12 13 14 15 16 17 18 19 20 21 22 <![CDATA[M S-Cn ]]> 3.5 4.7 7.8 11.6 9.3 4.4 3.0 3.9 3.7 2.3 1.2 0.7 <![CDATA[M A-Cn ]]> 7.2 10.1 7.8 6.9 4.2 2.5 2.2 1.4 0.8 0.4 0.2 0.2

[0090] In a specific embodiment of the present disclosure, in step S2, the mass fraction of each type of hydrocarbon in different carbon number components in the non-polar component is calculated by SH / T 0606 method or SH / T 0659 method. In a specific embodiment of the present disclosure, in step S2, the mass fraction of each type of hydrocarbon in different carbon number components in the polar component is calculated by SH / T 0606 method or GB / T 18340.4 method. The specific calculation methods using SH / T 0606 method, SH / T 0659 method and GB / T 18340.4 method are well known to those skilled in the art. The SH / T 0606 method can be used to calculate the hydrocarbon composition of different carbon number components of samples with a distillation range of 120°C to 350°C, and the SH / T 0659 and GB / T18340.4 methods can be used to calculate the hydrocarbon composition of different carbon number components of samples with a distillation range of 350°C to 540°C. For samples with a wide distillation range, the corresponding methods are used in the corresponding distillation sections. In one embodiment, the final boiling point of the hydrocarbon component M to be measured is less than 350° C. The mass fractions of various types of hydrocarbons between carbon 11 and carbon 22 are calculated using the SH / T 0606 method, as shown in Table 2.

[0091] Table 2 Hydrocarbon composition of non-polar components and polar components in different carbon number groups in the hydrocarbon sample M to be tested

[0092]

[0093] According to the present disclosure, the purpose of "carbon number correction" is to correct the carbon number deviation problem caused by polarity. Since the polarity of polar components is higher than that of non-polar components, when both polar components and non-polar components use non-polar normal alkanes as the basis for carbon number cutting, after carbon number division, the actual carbon number of polar components in the same carbon number component will be lower than the actual carbon number of non-polar components, and this phenomenon of carbon number deviation will increase with the strengthening of polarity. Therefore, the hydrocarbons in the polar components should be "carbon number corrected" to varying degrees according to the size of their polarity.

[0094] In the present disclosure, the molecular formula is C y H 2y-6 , C y H 2y-8 and C y H 2y-10 The mass content of the polar component with carbon number y as the mass content of the first polar component with carbon number y-1 means: y H 2y-6 , C y H 2y-8 and C y H 2y-10 The mass content of the polar component with carbon number y in the above molecular formula is respectively taken as the mass content of the polar component with carbon number y-1 that conforms to the above molecular formula. y H 2y-8 The mass fraction of the polar component is a, and the molecular formula is C y H 2y-10 If the mass fraction of the polar component is b, then the mass fraction a is taken as the molecular formula C after the carbon number correction. y- 1H 2(y-1)-8 The mass fraction of the polar component is taken as the mass fraction b, and the molecular formula is C after the carbon number correction. y-1 H 2(y-1)-10 The mass fraction of polar components.

[0095] In the present disclosure, the molecular formula is C y H 2y-12 , C y H 2y-14 and C y H 2y-16 The mass content of the polar component with carbon number y as the mass content of the second polar component with carbon number y-2 means: y H 2y-12 , C y H 2y-14 and C y H 2y-16The mass content of the polar component with carbon number y in the above molecular formula is respectively taken as the mass content of the polar component with carbon number y-2 that conforms to the above molecular formula. y H 2y-14 The mass fraction of the polar component is a, and the molecular formula is C y H 2y-16 If the mass fraction of the polar component is b, then the mass fraction a is taken as the molecular formula C after the carbon number correction. y-2 H 2(y-2)-14 The mass fraction of the polar component is then taken as the mass fraction b after the carbon number correction and the molecular formula is C y- 2H 2(y-2)-16 The mass fraction of polar components.

[0096] In the present disclosure, the molecular formula is C y H 2y-18 , C y H 2y-20 and C y H 2y-22 The mass content of the polar component with carbon number y as the mass content of the third polar component with carbon number y-3 means: y H 2y-18 , C y H 2y-20 and C y H 2y-22 The mass content of the polar component with carbon number y in the above molecular formula is respectively taken as the mass content of the polar component with carbon number y-3 that conforms to the above molecular formula. y H 2y-18 The mass fraction of the polar component is a, and the molecular formula is C y H 2y-20 If the mass fraction of the polar component is b, then the mass fraction a is taken as the molecular formula C after the carbon number correction. y-3 H 2(y-3)-18 The mass fraction of the polar component is then taken as the mass fraction b after the carbon number correction and the molecular formula is C y-3 H 2(y-3)-20 The mass fraction of polar components.

[0097] In one embodiment, the lowest carbon number of various polar components after "carbon number correction" should not be less than the carbon number of its aromatic parent ring structure, otherwise, the degree of "carbon number correction" should be reduced, that is, "reverse correction" should be performed to make the lowest carbon of various polar components equal to the carbon number of its aromatic parent ring structure.

[0098] For example, tricyclic aromatic hydrocarbons C y H 2y-18 The number of carbon atoms in the aromatic parent ring structure is 14. After the carbon number correction, the data results show that yH 2y-18 The lowest carbon number of the class is 12, that is, when y=12, C y H 2y-18 When the content of compounds is greater than 0, when y<12, C y H 2y-18 The content of the compound is 0. Since 12 is less than 14, a "reverse correction" is performed at this time, and the C y H 2y-18 The mass fraction is corrected to C with carbon number 14. y H 2y-18 The mass fraction of carbon number 13 y H 2y-18 The mass fraction is corrected to C with carbon number 15. y H 2y-18 The mass fraction of carbon number 14 y H 2y-18 The mass fraction is corrected to C with carbon number 16 y H 2y-18 The mass fraction of C y H 2y-18 Mass fraction of the highest carbon number.

[0099] The hydrocarbon compositions of the non-polar components and polar components in the hydrocarbon sample M to be tested in different carbon number components after “carbon number correction” are shown in Table 3.

[0100] Table 3 Hydrocarbon composition after carbon number correction

[0101]

[0102] In the present disclosure, in step S4, the non-polar components are expressed as the chemical composition of chain alkanes and cycloalkanes; in step S5, the polar components are expressed as the chemical composition of aromatic hydrocarbons according to the composition characteristics of the petroleum sample, and the chain alkane carbon rate, chain alkane hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate and aromatic ring hydrogen rate of each compound with different carbon numbers in the polar components and non-polar components can be directly calculated according to the specified molecular structure as shown in Table 4-13. Combined with the mass fraction of the corresponding compound in Table 3, the distribution of various types of carbon and hydrogen in components of different polarities, different types of hydrocarbons, and different carbon numbers can be obtained, as well as the distribution and total content of carbon and hydrogen types in the overall sample.

[0103] Table 4 Alkane carbon ratio of various types of hydrocarbons with different carbon numbers in non-polar components

[0104] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 8 0.84 0.21 9 0.84 0.29 10 0.85 0.34 11 0.85 0.39 0.08 12 0.85 0.43 0.14 13 0.85 0.46 0.20 14 0.85 0.49 0.25 15 0.85 0.51 0.29 0.06 16 0.85 0.54 0.32 0.11 17 0.85 0.55 0.36 0.15 18 0.85 0.57 0.38 0.19 19 0.85 0.59 0.41 0.23 0.05 20 0.85 0.60 0.43 0.26 0.09 21 0.85 0.61 0.45 0.29 0.13 22 0.85 0.62 0.47 0.32 0.16 23 0.85 0.63 0.49 0.34 0.19 0.04 24 0.85 0.64 0.50 0.36 0.22 0.07 25 0.85 0.65 0.52 0.38 0.24 0.11 26 0.85 0.66 0.53 0.40 0.27 0.13 27 0.85 0.67 0.54 0.42 0.29 0.16 0.03 28 0.85 0.67 0.55 0.43 0.31 0.19 0.06 29 0.85 0.68 0.56 0.45 0.33 0.21 0.09 30 0.85 0.69 0.57 0.46 0.35 0.23 0.12 31 0.85 0.69 0.58 0.47 0.36 0.25 0.14 32 0.85 0.70 0.59 0.49 0.38 0.27 0.16 33 0.85 0.70 0.60 0.50 0.39 0.29 0.19 34 0.85 0.71 0.61 0.51 0.41 0.31 0.21 35 0.85 0.71 0.61 0.52 0.42 0.32 0.23 36 0.85 0.71 0.62 0.53 0.43 0.34 0.24 37 0.85 0.72 0.63 0.54 0.45 0.35 0.26 38 0.85 0.72 0.63 0.55 0.46 0.37 0.28 39 0.85 0.73 0.64 0.55 0.47 0.38 0.29 40 0.85 0.73 0.65 0.56 0.48 0.39 0.31 41 0.85 0.73 0.65 0.57 0.49 0.40 0.32 42 0.85 0.73 0.66 0.58 0.49 0.41 0.33

[0105] Table 5 Alkane hydrogen ratio of various types of hydrocarbons with different carbon numbers in non-polar components

[0106] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 8 0.16 0.04 9 0.16 0.06 10 0.15 0.06 11 0.15 0.07 0.02 12 0.15 0.08 0.03 13 0.15 0.08 0.04 14 0.15 0.09 0.05 15 0.15 0.09 0.05 0.01 16 0.15 0.09 0.06 0.02 17 0.15 0.10 0.06 0.03 18 0.15 0.10 0.07 0.04 19 0.15 0.10 0.07 0.04 0.01 20 0.15 0.10 0.08 0.05 0.02 21 0.15 0.11 0.08 0.05 0.02 22 0.15 0.11 0.08 0.06 0.03 23 0.15 0.11 0.08 0.06 0.03 0.01 24 0.15 0.11 0.09 0.06 0.04 0.02 25 0.15 0.11 0.09 0.07 0.04 0.02 26 0.15 0.11 0.09 0.07 0.05 0.03 27 0.15 0.11 0.09 0.07 0.05 0.03 0.01 28 0.15 0.11 0.09 0.07 0.05 0.03 0.01 29 0.15 0.12 0.10 0.08 0.06 0.04 0.02 30 0.15 0.12 0.10 0.08 0.06 0.04 0.02 31 0.15 0.12 0.10 0.08 0.06 0.04 0.03 32 0.15 0.12 0.10 0.08 0.07 0.05 0.03 33 0.15 0.12 0.10 0.09 0.07 0.05 0.03 34 0.15 0.12 0.10 0.09 0.07 0.05 0.04 35 0.15 0.12 0.10 0.09 0.07 0.06 0.04 36 0.15 0.12 0.11 0.09 0.07 0.06 0.04 37 0.15 0.12 0.11 0.09 0.08 0.06 0.05 38 0.15 0.12 0.11 0.09 0.08 0.06 0.05 39 0.15 0.12 0.11 0.09 0.08 0.07 0.05 40 0.15 0.12 0.11 0.10 0.08 0.07 0.05 41 0.15 0.12 0.11 0.10 0.08 0.07 0.05 42 0.15 0.12 0.11 0.10 0.08 0.07 0.06

[0107] Table 6 Cycloalkane carbon ratio of various types of hydrocarbons with different carbon numbers in non-polar components

[0108] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 8 0.64 9 0.57 10 0.51 11 0.47 0.79 12 0.43 0.72 13 0.40 0.67 14 0.37 0.62 15 0.34 0.58 0.82 16 0.32 0.54 0.76 17 0.30 0.51 0.72 18 0.29 0.48 0.68 19 0.27 0.45 0.64 0.83 20 0.26 0.43 0.61 0.79 21 0.24 0.41 0.58 0.75 22 0.23 0.39 0.55 0.72 23 0.22 0.38 0.53 0.68 0.84 24 0.21 0.36 0.51 0.65 0.80 25 0.21 0.34 0.49 0.63 0.77 26 0.20 0.33 0.47 0.60 0.74 27 0.19 0.32 0.45 0.58 0.71 0.85 28 0.18 0.31 0.43 0.56 0.69 0.82 29 0.18 0.30 0.42 0.54 0.66 0.79 30 0.17 0.29 0.40 0.52 0.64 0.76 31 0.17 0.28 0.39 0.50 0.62 0.74 32 0.16 0.27 0.38 0.49 0.60 0.71 33 0.16 0.26 0.37 0.47 0.58 0.69 34 0.15 0.25 0.36 0.46 0.56 0.67 35 0.15 0.25 0.35 0.45 0.55 0.65 36 0.14 0.24 0.34 0.43 0.53 0.63 37 0.14 0.23 0.33 0.42 0.52 0.61 38 0.14 0.23 0.32 0.41 0.50 0.60 39 0.13 0.22 0.31 0.40 0.49 0.58 40 0.13 0.22 0.30 0.39 0.48 0.57 41 0.13 0.21 0.29 0.38 0.47 0.55 42 0.12 0.20 0.29 0.37 0.46 0.54

[0109] Table 7 Cycloalkane hydrogen ratio of various types of hydrocarbons with different carbon numbers in non-polar components

[0110] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 8 0.10 9 0.09 10 0.08 11 0.07 0.11 12 0.07 0.10 13 0.06 0.09 14 0.06 0.09 15 0.05 0.08 0.11 16 0.05 0.08 0.10 17 0.05 0.07 0.10 18 0.04 0.07 0.09 19 0.04 0.06 0.09 0.11 20 0.04 0.06 0.08 0.11 21 0.04 0.06 0.08 0.10 22 0.04 0.06 0.08 0.10 23 0.03 0.05 0.07 0.09 0.11 24 0.03 0.05 0.07 0.09 0.11 25 0.03 0.05 0.07 0.08 0.10 26 0.03 0.05 0.06 0.08 0.10 27 0.03 0.05 0.06 0.08 0.09 0.11 28 0.03 0.04 0.06 0.08 0.09 0.11 29 0.03 0.04 0.06 0.07 0.09 0.10 30 0.03 0.04 0.06 0.07 0.08 0.10 31 0.03 0.04 0.05 0.07 0.08 0.10 32 0.02 0.04 0.05 0.07 0.08 0.09 33 0.02 0.04 0.05 0.06 0.08 0.09 34 0.02 0.04 0.05 0.06 0.07 0.09 35 0.02 0.03 0.05 0.06 0.07 0.09 36 0.02 0.03 0.05 0.06 0.07 0.08 37 0.02 0.03 0.04 0.06 0.07 0.08 38 0.02 0.03 0.04 0.06 0.07 0.08 39 0.02 0.03 0.04 0.05 0.07 0.08 40 0.02 0.03 0.04 0.05 0.06 0.07 41 0.02 0.03 0.04 0.05 0.06 0.07 42 0.02 0.03 0.04 0.05 0.06 0.07

[0111] Table 8 Alkane carbon ratio of various types of hydrocarbons with different carbon numbers in polar components

[0112]

[0113] Table 9 Alkane hydrogen ratio of various types of hydrocarbons with different carbon numbers in polar components

[0114]

[0115] Table 10 Cycloalkane carbon ratio of various types of hydrocarbons with different carbon numbers in polar components

[0116]

[0117] Table 11 Cycloalkane hydrogen ratio of various types of hydrocarbons with different carbon numbers in polar components

[0118]

[0119] Table 12 Aromatic ring carbon ratio of various types of hydrocarbons with different carbon numbers in polar components

[0120]

[0121] Table 13 Aromatic ring hydrogen ratio of various types of hydrocarbons with different carbon numbers in polar components

[0122]

[0123] According to the present disclosure, in step S6, the total carbon content of the sample is obtained by adding the paraffin carbon rate, cycloalkane carbon rate and aromatic ring carbon rate of the polar component and the non-polar component in the hydrocarbon component M to be tested, and the total hydrogen content is obtained by adding the paraffin hydrogen rate, cycloalkane hydrogen rate and cycloalkane hydrogen rate. For example, Table 14 shows the carbon and hydrogen types in the hydrocarbon sample M to be tested measured by nuclear magnetic resonance and the elemental composition measured by an element analyzer. Table 15 shows the carbon type and hydrogen type of each carbon number component in the hydrocarbon sample M to be tested measured by the method of the present disclosure.

[0124] Table 14 The carbon and hydrogen types of the hydrocarbon samples M to be tested and each type of hydrocarbon therein

[0125]

[0126] Table 15 Carbon and hydrogen types of each carbon group component in the hydrocarbon sample M to be tested

[0127]

[0128]

[0129] In a specific embodiment of the present disclosure, the distillation range of the hydrocarbon sample to be tested is 10-600°C, preferably 120-540°C.

[0130] The present disclosure is further illustrated below by way of examples, but the present disclosure is not limited thereby.

[0131] Example 1

[0132] S1. A heavy straight-run oil Z with a distillation range of 270°C to 430°C was subjected to solid phase extraction technology, using a silica gel extraction column, using n-hexane and dichloromethane as mobile phases, and pre-separated into non-polar components and polar components. The sample was then analyzed using a gas chromatography-quadrupole mass spectrometer (GC-MS) equipped with an FID detector, with an inlet temperature of 320°C, carrier gas helium, column flow rate (constant flow mode) of 1 mL / min, a temperature program of an initial temperature of 60°C, maintained for 2 min, and then heated to 310°C at a rate of 20°C / min. The chromatographic column was HP-5MS, 30m×0.25mm×0.25μm, an EI source ionization voltage of 70eV, an ionization current of 70μA, an intensity ratio of fragment ion 67 to fragment ion 71 generated by n-hexadecane ionization of 0.2, and a mass number scanning range of 50 to 500.

[0133] Heavy straight-run oil Z contains normal alkanes with carbon numbers of 16 to 30, which are used as the basis for carbon number cutting.

[0134] S2, using formula M S-Cn =A S-Cn / (A S +A A )×100% to calculate the mass fractions of different carbon number groups in the non-polar component of heavy straight-run oil Z in the carbon 16 to carbon 30 components, using the formula M A-Cn =A A-Cn / (A S +A A )×100% to calculate the mass fractions of components with different carbon numbers in the polar components of heavy straight-run oil Z in the carbon 16 to carbon 30 components. The results are shown in Table 16.

[0135] Table 16 Mass fractions of components of different carbon numbers in non-polar components and polar components in sample Z, %

[0136] Carbon number 17 18 19 20 21 22 23 24 25 26 27 28 29 <![CDATA[M S-Cn ]]> 0.0 0.3 0.7 1.4 3.5 6.0 7.1 6.6 7.1 6.9 8.3 8.4 7.5 <![CDATA[M A-Cn ]]> 0.0 0.1 0.2 0.3 0.4 0.5 0.5 0.6 0.6 0.6 0.7 0.8 0.9 Carbon number 30 31 32 33 34 35 36 37 38 39 40 41 42 <![CDATA[M S-Cn ]]> 5.4 3.6 2.1 1.3 0.7 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 <![CDATA[M A-Cn ]]> 1.1 1.3 1.6 1.7 1.7 1.8 1.7 1.5 1.3 1.1 0.9 0.6 0.5

[0137] The hydrocarbon composition of non-polar components in carbon 16 to carbon 30 in heavy straight-run oil Z was calculated using the method of SH / T 0659, and the hydrocarbon composition of polar components was calculated using GB / T 18340.4. The carbon number distribution of non-polar components is shown in Table 17.

[0138] Table 17 Hydrocarbon composition of non-polar components in sample Z in different carbon number groups

[0139] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 17 0.05 0.00 0.00 0.00 0.00 0.00 0.00 18 0.19 0.12 0.00 0.00 0.00 0.00 0.00 19 0.42 0.19 0.02 0.03 0.00 0.00 0.00 20 0.91 0.39 0.04 0.05 0.00 0.00 0.00 21 2.53 0.59 0.11 0.08 0.05 0.00 0.00 22 4.69 0.99 0.17 0.15 0.07 0.00 0.00 23 5.34 1.07 0.32 0.17 0.09 0.00 0.09 24 4.57 1.22 0.37 0.21 0.10 0.03 0.15 25 4.78 1.19 0.46 0.20 0.09 0.10 0.24 26 4.38 1.38 0.49 0.19 0.12 0.05 0.25 27 5.33 1.62 0.51 0.22 0.24 0.13 0.25 28 5.27 1.79 0.52 0.25 0.25 0.08 0.22 29 3.86 1.65 0.61 0.32 0.51 0.28 0.26 30 1.97 1.24 0.55 0.35 0.50 0.43 0.33 31 1.06 0.81 0.57 0.21 0.27 0.23 0.41 32 0.67 0.48 0.35 0.14 0.17 0.15 0.15 33 0.39 0.34 0.23 0.11 0.10 0.07 0.08 34 0.15 0.17 0.19 0.07 0.05 0.03 0.06 35 0.06 0.07 0.12 0.00 0.00 0.00 0.00 36 0.00 0.00 0.04 0.00 0.00 0.00 0.00 Total 46.6 15.3 5.7 2.7 2.6 1.6 2.5

[0140] S3. Carbon number correction is performed on hydrocarbons of different polarities in the polar components. The carbon number distribution of the polar components after carbon number correction is shown in Table 18.

[0141] Table 18 Hydrocarbon composition after correction of carbon number of polar components in sample Z

[0142]

[0143] S4-S6, Table 17, Table 18 and Table 4 to Table 13 corresponding to the carbon number, the corresponding hydrocarbon type of the paraffin carbon rate, paraffin hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate, aromatic ring hydrogen rate, can be combined to obtain the carbon and hydrogen type distribution of each type of hydrocarbon in the Z sample, the results are shown in Table 19, Table 19 lists the sample structure parameters measured by nuclear magnetic resonance and the element data measured by the element analyzer, and the changes of carbon and hydrogen types with carbon number are shown in Table 20. The total test time of the method of this embodiment is less than 30 minutes.

[0144] Table 19 Carbon and hydrogen types of Z samples and each type of hydrocarbon in them

[0145]

[0146] Table 2 Carbon and hydrogen types of each carbon group component in the 0Z sample

[0147]

[0148]

[0149] Example 2

[0150] This example is used to illustrate that the method can determine the carbon and hydrogen types of various types of hydrocarbons in the wide-fraction oil produced by hydrocracking.

[0151] S1. A wide-cut hydrocracked oil L with a distillation range of 30°C to 540°C was pre-separated into a non-polar component and a polar component by a solid phase separation method, and then analyzed by a gas chromatography-quadrupole mass spectrometer (GC-MS) equipped with an FID detector, with an inlet temperature of 320°C, a carrier gas of helium, a column flow rate (constant flow mode) of 1.5 mL / min, a temperature rise program, an initial temperature of 50°C, maintained for 2 min, and then heated to 310°C at a rate of 20°C / min. The chromatographic column was HP-1MS, 30m×0.25mm×0.25μm, an EI source ionization voltage of 70eV, an ionization current of 70μA, and an intensity ratio of fragment ion 67 to fragment ion 71 generated by n-hexadecane ionization was 0.2, and the mass number scanning range was 50 to 500.

[0152] Wide-fraction hydrocracking oil L contains normal alkanes with carbon numbers of 8 to 30, which can be used as the basis for carbon number cutting.

[0153] S2. Through experiments, it was found that the content of non-polar components in wide-fraction hydrocracking oil L is as high as 97% or more, so only formula M S-Cn =A S-Cn / (A S +A A )×100% to calculate the mass fractions of different carbon numbers in the non-polar components from carbon 8 to carbon 30, as shown in Table 21.

[0154] Table 21 Mass fraction of non-polar components in sample L in different carbon number groups

[0155] Carbon number 8 9 10 11 12 13 14 15 16 17 18 <![CDATA[M S-Cn ]]> 13.8％ 3.8％ 4.1％ 3.6％ 3.5％ 3.1％ 3.5％ 5.6％ 9.8％ 15.8％ 16.4％ Carbon number 19 20 21 22 23 24 25 26 27 28 29 <![CDATA[M S-Cn ]]> 1.3％ 1.7％ 1.4％ 1.0％ 1.7％ 1.0％ 1.7％ 0.9％ 3.8％ 2.8％ 0.1％

[0156] The hydrocarbon composition of non-polar components with carbon numbers from 8 to 20 in L oil was calculated using the SH / T 0606 method, and the hydrocarbon composition of non-polar components with carbon numbers from 21 to 29 in L oil was calculated using the SH / T 0659 method. The carbon number distribution of hydrocarbons in non-polar components in L oil is shown in Table 22.

[0157] Table 22 Hydrocarbon composition of non-polar components in sample L in different carbon number groups

[0158] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> 8 13.76 0.00 0.00 0.00 0.00 0.00 9 3.72 0.02 0.00 0.00 0.00 0.00 10 4.03 0.00 0.00 0.00 0.00 0.00 11 3.60 0.00 0.03 0.00 0.00 0.00 12 3.38 0.00 0.09 0.00 0.00 0.00 13 2.98 0.00 0.12 0.00 0.00 0.00 14 3.41 0.00 0.10 0.01 0.00 0.00 15 5.20 0.17 0.09 0.11 0.00 0.00 16 9.16 0.35 0.11 0.18 0.00 0.00 17 14.74 0.65 0.18 0.19 0.01 0.00 18 14.17 1.35 0.45 0.26 0.13 0.00 19 0.83 0.07 0.13 0.09 0.13 0.00 20 0.82 0.07 0.21 0.16 0.43 0.00 21 0.72 0.08 0.13 0.11 0.34 0.00 22 0.66 0.06 0.11 0.09 0.11 0.01 23 1.14 0.07 0.16 0.14 0.12 0.02 24 0.57 0.08 0.12 0.09 0.06 0.02 25 1.03 0.20 0.22 0.13 0.06 0.03 26 0.34 0.23 0.18 0.09 0.04 0.02 27 1.16 0.84 0.84 0.48 0.35 0.06 28 0.47 0.36 0.70 0.52 0.63 0.06 29 0.00 0.00 0.00 0.00 0.00 0.00 30 0.00 0.00 0.00 0.00 0.00 0.00

[0159] S3, None (Since this sample has no polar components, no carbon number correction is required).

[0160] S4-S6, combining Table 22 with the corresponding polarity, corresponding carbon number, and corresponding hydrocarbon type of paraffin carbon rate, paraffin hydrogen rate, cycloalkane carbon rate, and cycloalkane hydrogen rate in Tables 4 to 13, the carbon and hydrogen type distribution of each type of hydrocarbon and each carbon number component in the L sample can be obtained, as shown in Tables 24 and 25. Table 24 lists the sample structure parameters determined by nuclear magnetic resonance and the element data determined by the element analyzer at the same time. The total test time of the method in this embodiment is less than 30 minutes.

[0161] Table 24 Structural parameters of L samples and each type of hydrocarbon in them

[0162]

[0163] Table 2 Carbon and hydrogen types of each carbon group component in 5L samples

[0164]

[0165]

[0166] Comparative Example 1

[0167] S1. The hydrocracked oil K oil with a distillation range of 320°C to 420°C was pre-separated into non-polar components and polar components by a solid phase separation method, and then analyzed by a gas chromatography-quadrupole mass spectrometer (GC-MS) equipped with an FID detector, with an inlet temperature of 300°C, a carrier gas of helium, a column flow rate (constant flow mode) of 1.5 mL / min, a temperature rise program, an initial temperature of 50°C, maintained for 2 min, and then heated to 310°C at a rate of 20°C / min. The chromatographic column was HP-1MS, 30m×0.25mm×0.25μm, an EI source ionization voltage of 70eV, an ionization current of 70μA, and an intensity ratio of fragment ion 67 to fragment ion 71 generated by n-hexadecane ionization was 0.2, and the mass number scanning range was 50 to 500.

[0168] The narrow-fraction hydrocracking oil K itself contains normal alkanes with carbon numbers of 17 to 28, which can be used as the basis for carbon number cutting.

[0169] Through experiments, it was found that the content of non-polar components in narrow-fraction hydrocracking oil K oil is as high as more than 98%, so only formula M S-Cn =A S-Cn / (A S +A A )×100% to calculate the mass fractions of different carbon numbers in the non-polar components from carbon 17 to carbon 28, as shown in Table 26.

[0170] Table 26 Mass fraction of non-polar components in sample K oil in different carbon number components

[0171] Carbon number 17 18 19 20 21 22 23 24 25 26 27 28 <![CDATA[M S-Cn ]]> 1.4 3.8 6.7 9.9 13.5 16.6 16.9 14.4 9.3 3.9 1.9 0.6

[0172] The hydrocarbon composition of non-polar components with carbon numbers from 17 to 28 in K oil was calculated using the SH / T 0659 method. The carbon number distribution of hydrocarbons in non-polar components in K oil is shown in Table 27.

[0173] The carbon number distribution of hydrocarbons in K oil was determined by gas chromatography time-of-flight mass spectrometry (GC FI ​​TOFMS) equipped with a soft ionization source, and the total test time was greater than 30 minutes. The injection port temperature was 300°C, the column box temperature was 60°C, maintained for 2 minutes, increased to 310°C at 40°C / min, maintained for 5 minutes, the carrier gas flow rate was 1.5 mL / min, the GC-MS interface temperature was 300°C, the soft ionization source was in FI ionization mode, the multi-channel detector (MCP) voltage was 2200V, the emitter voltage was -10000V, the filament current was 30mA, the full scan mode, the relative molecular mass range was 50-500, and the carbon number distribution of hydrocarbons in K oil was determined as shown in Table 28. The data in Table 27 are basically consistent with the data in Table 28, which can reflect the trend of different types of hydrocarbons in K oil with carbon number.

[0174] Table 27 GC-MS determination of hydrocarbon composition in different carbon number groups of non-polar components of K oil

[0175] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 17 0.43 0.27 0.26 0.35 0.05 0.01 0 18 1.37 0.81 0.71 0.69 0.23 0.01 0 19 2.42 1.48 1.25 0.96 0.54 0.03 0 20 3.81 2.23 1.88 1.17 0.74 0.04 0 21 5.59 3.22 2.52 1.25 0.88 0.06 0 22 7.85 3.76 2.63 1.51 0.74 0.09 0 23 8.5 3.2 3.09 1.43 0.64 0.06 0 24 7.17 2.93 2.57 1.2 0.48 0.05 0 25 4.24 1.74 2.41 0.65 0.24 0.03 0 26 1.44 0.58 1.5 0.27 0.1 0.01 0 27 0.92 0.32 0.45 0.18 0.04 0.01 0 28 0.28 0.11 0.09 0.07 0.01 0 0 Total 44.02 20.65 19.36 9.73 4.69 0.4 0

[0176] Table 28 Hydrocarbon composition of different carbon number groups in non-polar components of K oil determined by GC FI ​​TOFMS

[0177] Carbon number <![CDATA[C x H 2x+2 ]]> <![CDATA[C x H 2x ]]> <![CDATA[C x H 2x-2 ]]> <![CDATA[C x H 2x-4 ]]> <![CDATA[C x H 2x-6 ]]> <![CDATA[C x H 2x-8 ]]> <![CDATA[C x H 2x-10 ]]> 17 0.26 0.18 0.07 0.22 0.08 0.02 0.00 18 0.88 0.47 0.21 0.47 0.29 0.03 0.00 19 1.97 1.01 0.61 0.81 0.52 0.05 0.00 20 3.78 1.69 1.17 1.24 0.71 0.06 0.00 21 5.67 2.57 1.88 1.47 0.84 0.07 0.00 22 7.06 3.09 2.50 1.54 0.83 0.08 0.00 23 8.04 3.39 2.94 1.49 0.67 0.06 0.00 24 7.63 3.01 3.00 1.13 0.46 0.05 0.00 25 5.00 2.11 2.55 0.82 0.30 0.03 0.00 26 2.62 1.20 1.94 0.51 0.19 0.02 0.00 27 1.05 0.55 1.11 0.26 0.08 0.01 0.00 28 0.36 0.22 0.57 0.11 0.03 0.00 0.00 Total 44.31 19.48 18.55 10.09 4.97 0.49 0.00

[0178] Comparative Example 2

[0179] The straight-run oil O oil with a distillation range of 150°C to 270°C was pre-separated into non-polar components and polar components by a solid phase separation method, and then analyzed by a gas chromatography-quadrupole mass spectrometer (GC-MS) equipped with an FID detector, with an inlet temperature of 270°C, a carrier gas of helium, a column flow rate (constant flow mode) of 1.5 mL / min, a temperature program of an initial temperature of 50°C, maintained for 2 min, and then heated to 250°C at a rate of 10°C / min, a chromatographic column HP-5MS, 30m×0.25mm×0.25μm, an EI source ionization voltage of 70eV, an ionization current of 70μA, an intensity ratio of fragment ion 67 generated by n-hexadecane ionization to fragment ion 71 of 0.2, and a mass number scanning range of 50 to 300.

[0180] Often, first-line straight-run oil O oil contains normal alkanes with carbon numbers of 9 to 15, which can be used as the basis for carbon number cutting.

[0181] Using formula M S-Cn =A S-Cn / (A S +AA )×100% to calculate the mass fractions of different carbon number groups in the non-polar components of the regular straight-run oil O oil in the carbon 9 to carbon 15 components, using the formula M A-Cn =A A-Cn / (A S +A A )×100% were used to calculate the mass fractions of components with different carbon numbers in the polar components of the regular straight-run oil O oil in the carbon 9 to carbon 15 components. The results are shown in Table 29.

[0182] Table 29 Mass fractions of non-polar and polar components in sample O oil at different carbon numbers

[0183] Carbon number 9 10 11 12 13 14 15 <![CDATA[M S-Cn ]]> 5.7 7.4 9.8 25.6 24.1 6.8 0.1 <![CDATA[M A-Cn ]]> 1.3 2.4 4.3 6.4 4.9 1.2 0.1

[0184] The hydrocarbon composition of each component from carbon 9 to carbon 15 in O oil was calculated using the SH / T 0606 method, see Table 30.

[0185] The carbon number distribution of hydrocarbons in O oil was determined by gas chromatography time of flight (GC FI ​​TOFMS) equipped with a soft ionization source, and the total test time was greater than 30 minutes. The injection port temperature was 300°C, the column box temperature was 60°C, maintained for 2 minutes, increased to 310°C at 40°C / min, maintained for 5 minutes, the carrier gas flow rate was 1.5 mL / min, the GC-MS interface temperature was 300°C, the soft ionization source was in FI ionization mode, the multi-channel detector (MCP) voltage was 2200V, the emitter voltage was -10000V, the filament current was 30mA, the full scan mode, the relative molecular mass range was 50-300, and the carbon number distribution of hydrocarbons in O oil was determined as shown in Table 31. The data in Table 30 are basically consistent with the data in Table 31, which can reflect the trend of different types of hydrocarbons in O oil with carbon number.

[0186] Table 30 Hydrocarbon composition of different carbon number groups in O oil determined by GC-MS

[0187]

[0188]

[0189] Table 31 GC FI ​​TOFMS determination of hydrocarbon composition in different carbon number groups of O oil

[0190]

[0191] Comparative Example 3

[0192] Heavy aromatic oil A with a distillation range of 450°C to 520°C was pre-separated into non-polar components and polar components by a solid phase separation method, and then analyzed by a gas chromatography-quadrupole mass spectrometer (GC-MS) equipped with an FID detector, with an inlet temperature of 320°C, a carrier gas of helium, a column flow rate (constant flow mode) of 1.5 mL / min, a temperature rise program, an initial temperature of 60°C, maintained for 2 min, and then heated to 310°C at a rate of 10°C / min, a chromatographic column HP-5MS, 30m×0.25mm×0.25μm, an EI source ionization voltage of 70eV, an ionization current of 70μA, an intensity ratio of fragment ion 67 generated by n-hexadecane ionization to fragment ion 71 of 0.2, and a mass number scanning range of 50 to 700.

[0193] Heavy aromatic oil A does not contain normal alkanes, so a mixed standard sample of normal paraffins with carbon numbers of 30 to 40 is used as the basis for carbon number cutting.

[0194] Through experiments, it was found that the content of polar components in heavy aromatic oil A oil is as high as more than 97%, so only formula M A-Cn =A A-Cn / (A S +A A )×100% to calculate the mass fractions of different carbon numbers in the polar components from carbon 32 to carbon 38, as shown in Table 32.

[0195] Table 32 Mass fraction of polar components in sample A oil in different carbon number components

[0196] Carbon number 32 and before 33 34 35 36 37 38 and beyond <![CDATA[M S-Cn ]]> 8.2 23.3 26.0 20.6 12.1 6.9 3.0

[0197] The hydrocarbon composition of each component from carbon 32 to carbon 38 in oil A was calculated using the GB / T 18340.4 method, see Table 33.

[0198] The carbon number distribution of hydrocarbons in oil A was determined by gas chromatography time of flight (GC FI ​​TOFMS) equipped with a soft ionization source, and the total test time was greater than 30 minutes. The injection port temperature was 320°C, the column box temperature was 60°C, maintained for 2 minutes, increased to 310°C at 40°C / min, maintained for 5 minutes, the carrier gas flow rate was 1.5mL / min, the GC-MS interface temperature was 300°C, the soft ionization source was in FI ionization mode, the multi-channel detector (MCP) voltage was 2200V, the emitter voltage was -10000V, the filament current was 30mA, the full scan mode, the relative molecular mass range was 50-700, and the carbon number distribution of hydrocarbons in oil A was determined as shown in Table 34. The data in Table 33 are basically consistent with the data in Table 34, which can reflect the trend of different types of hydrocarbons in oil A with carbon number.

[0199] Table 33 Hydrocarbon composition of different carbon number groups in oil A determined by GC-MS

[0200]

[0201] Table 34 Hydrocarbon composition of different carbon number groups in oil A determined by GC-MS

[0202]

[0203]

[0204] As can be seen from the above, the method for determining the carbon and hydrogen types in hydrocarbon samples using GC-MS provided by the present disclosure is basically consistent with the data determined by medium-resolution gas chromatography time-of-flight mass spectrometry configured with a soft ionization source. The former has a low instrument price, is easy to operate and maintain, and the total test time is less than 30 minutes. The carbon number distribution data can be used to directly calculate the carbon and hydrogen types of the sample without further testing. Therefore, the method for determining the carbon and hydrogen types in hydrocarbon samples using gas chromatography-mass spectrometry provided by the present disclosure has low requirements for analytical instruments, high analysis efficiency, low analysis cost, and less testing time.

[0205] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0206] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0207] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A method for determining the types of carbon and hydrogen in a hydrocarbon sample using gas chromatography-mass spectrometry, the method comprising: S1. Using a gas chromatography-EI source quadrupole mass spectrometer to detect polar components and non-polar components in the hydrocarbon sample to be tested, respectively, and using normal alkanes with different carbon numbers to cut the chromatograms of the non-polar components and the chromatograms of the polar components according to the carbon number; S2. Calculating the mass fraction of each type of hydrocarbon in different carbon number array components in the non-polar component and the mass fraction of each type of hydrocarbon in different carbon number array components in the polar component according to the distillation range of the hydrocarbon sample to be tested; Wherein, the molecular formula of each type of hydrocarbon in the non-polar component conforms to C x H 2x+2 , C x H 2x , C x H 2x-2 , C x H 2x-4 , C x H 2x-6 , C x H 2x-8 and C x H 2x-10 One or more of, wherein x is the carbon number, and x is any integer from 8 to 42; The molecular formula of each type of hydrocarbon in the polar component conforms to C y H 2y-6 , C y H 2y-8 , C y H 2y-10 , C y H 2y-12 , C y H 2y-14 , C y H 2y-16 , C y H 2y-18 , C y H 2y-20 , C y H 2y-22 , C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 One or more of, wherein y is the carbon number, and y is any integer from 8 to 42; S3, performing carbon number correction on hydrocarbons of different polarities in the polar components; Among them, the molecular formula is C y H 2y-6 , C y H 2y-8 and C y H 2y-10 The mass content of the polar component with carbon number y is respectively taken as the mass content of the first polar component with carbon number y-1; The molecular formula is C y H 2y-12 , C y H 2y-14 and C y H 2y-16 The mass content of the polar component with carbon number y is respectively taken as the mass content of the second polar component with carbon number y-2; The molecular formula is C y H 2y-18 , C y H 2y-20 and C y H 2y-22 The mass content of the polar component with carbon number y is taken as the mass content of the third polar component with carbon number y-3; The molecular formula is C y H 2y-24 , C y H 2y-26 , C y H 2y-28 and C y H 2y-30 The mass content of the polar component with carbon number y is respectively taken as the mass content of the fourth polar component with carbon number y-4; The total carbon number of the polar component after the carbon number correction is not less than the carbon number of its aromatic hydrocarbon parent ring; S4, the non-polar component is represented by the chemical composition of paraffin and cycloparaffin, wherein C x H 2x+2 represents chain alkane, C x H 2x represents a monocyclic cycloalkane, C x H 2x-2 represents a bicyclic cycloalkane, C x H 2x-4 Represents a tricyclic cycloalkane structure, C x H 2x-6 Represents a tetracyclic cycloalkane structure, C x H 2x-8 represents a pentacyclic cycloalkane structure and C x H 2x-10 represents a six-ring cycloalkane structure, wherein the cycloalkane has only one side chain; S5. The polar component is represented by the chemical composition of aromatic hydrocarbons, wherein C y H 2y-6 Represents the alkylbenzene structure, C y H 2y-8 Represents the structure of tetralin, C y H 2y-10 For the dicycloalkylbenzene structure, C y H 2y-12 It is a naphthalene structure, C y H 2y-14 It is an acenaphthene-like structure, C y H 2y-16 It is a fluorene structure, C y H 2y-18 It is a phenanthrene structure, C y H 2y-20 It is a cycloalkanephenanthrene structure, C y H 2y-22 It is a pyrene structure, C y H 2y-24 for Class structure, C y H 2y-26 Cycloalkane Class structure, C y H 2y-28 It is a perylene structure, C y H 2y -30 is a dibenzanthracene structure; The aromatic hydrocarbon has only one side chain and the side chain is on the aromatic ring of the aromatic hydrocarbon; S6. Calculate the mass fraction of carbon and the mass fraction of hydrogen contained in each type of hydrocarbon in different carbon number groups in the hydrocarbon sample to be tested according to the mass content of each type of hydrocarbon after carbon number correction and the chemical composition of the corresponding hydrocarbon, and obtain the paraffin carbon rate, paraffin hydrogen rate, cycloalkane carbon rate, cycloalkane hydrogen rate, aromatic ring carbon rate and aromatic ring hydrogen rate; Calculating the carbon types and hydrogen types in different carbon number array components in the hydrocarbon sample to be tested; The carbon type, hydrogen type, total carbon content and total hydrogen content of the hydrocarbon sample to be tested are calculated.

2. The method according to claim 1, wherein: In step S1, the carbon number cutting method comprises: the chromatographic retention time of the paraffin with a normal carbon number of n is T Cn The chromatographic retention time of the normal chain alkane with carbon number n-1 is T Cn-1 , then the retention time in the chromatogram is T Cn -T Cn-1 The region is defined as the carbon n component, wherein n is any integer from 8 to 42.

3. The method according to claim 1, wherein: In step S1, solid phase extraction is used to separate the hydrocarbon sample to be tested into the polar component and the non-polar component.

4. The method according to claim 1, wherein: In step S1, when the hydrocarbon sample to be tested contains normal alkanes, it is used as the basis for the carbon number cutting; When the hydrocarbon sample to be tested does not contain normal alkanes, a normal alkane mixed standard sample with the same distillation range as the hydrocarbon sample to be tested is prepared as the basis for the carbon number cutting, or other samples containing normal alkanes in the corresponding distillation range are used as the basis for the carbon number cutting.

5. The method according to claim 1, wherein: In step S1, the detection conditions include: the starting temperature of the chromatographic column oven is below 60°C, preferably 40-50°C, the chromatographic heating program is below 40°C / min, preferably 10-20°C / min; the ionization voltage of the EI source is 50-70eV, preferably 70eV, the ionization current is 10-70μA, the ratio of the intensity of the fragment ion 67 and the fragment ion 71 generated by the ionization of n-hexadecane is 0.2-0.4, preferably 0.25-0.35, and the mass number scanning range is 30-1000, preferably 50-500.

6. The method according to claim 1, wherein: In step S2, the mass fractions of components of different carbon numbers in the non-polar component are calculated using formula (1): M S-Cn =A S-Cn / (A S + A A )× 100 % (1) In formula (1), M S-Cn is the mass fraction of the non-polar component with carbon number n in the hydrocarbon sample to be tested; A S-Cn is the FID chromatogram area of ​​the non-polar component with carbon number n in the hydrocarbon sample to be tested; A S is the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested; A A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

7. The method according to claim 1, wherein: In step S2, the mass fractions of components of different carbon numbers in the polar component are calculated using formula (2): M A-Cn =A A-Cn / (A S + A A )× 100 % (2) In formula (2), M A-Cn is the mass fraction of the polar component with carbon number n in the hydrocarbon sample to be tested; A A-Cn is the FID chromatogram area of ​​the polar component with carbon number n in the hydrocarbon sample to be tested; A S is the total area of ​​the FID chromatogram of the non-polar components in the hydrocarbon sample to be tested; A A is the total area of ​​the FID chromatogram of the polar components in the hydrocarbon sample to be tested.

8. The method according to claim 1, wherein: In step S2, the mass fraction of each type of hydrocarbon in different carbon number array components in the non-polar component is calculated using the SH / T 0606 method or the SH / T 0659 method; The mass fraction of each type of hydrocarbon in different carbon number components in the polar component is calculated using the SH / T 0606 method or the GB / T 18340.4 method.

9. The method according to claim 1, wherein: The distillation range of the hydrocarbon sample to be tested is 10-600°C, preferably 120-540°C.

10. The method according to claim 1, wherein: The hydrocarbon sample to be tested is one or more of straight run oil, catalytic cracking oil, alkylation oil, extraction oil, cracking refined oil, hydrocracking oil, isomerization oil, biomass oil and plastic oil.

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