Method for distinguishing atmosphere, coal type gas, oil type gas and biogas by adopting nitrogen family

Abstract

The invention relates to a method for distinguishing atmosphere, coal type gas, oil type gas and biogas by adopting nitrogen family. The method comprises the following steps: (1) respectively collecting an atmosphere sample, a coal type gas sample, an oil type gas sample and a biogas sample; (2) obtaining a color-mass spectrum of each sample by adopting a gas chromatography-mass spectrometry technology, respectively obtaining mass numbers and abundance of nitrogen groups in all the samples by adopting a mass selection detector MSD, and respectively establishing a mass number abundance table of N2 in each sample; (3) respectively establishing a mass number abundance reproduction summary table of each sample N2; (4) establishing a mass number molecule percentage concentration induction table of atmosphere, coal type gas, oil type gas and biogas; and (5) performing the step (2) on an unknown sample to obtain the mass number of the nitrogen family in the unknown sample, and comparing the mass number with the known mass number molecular percentage concentration induction table of the nitrogen family to preliminarily determine the type of the unknown sample. The difference of atmosphere, coal type gas, oil type gas and biogas can be digitally distinguished.

Description

Technical Field

[0001] The present invention relates to the technical fields of natural gas, geology, meteorology, petroleum, nuclear science, human medicine, animal and plant research, and in particular to a method for distinguishing between atmospheric gas, coal-type gas, oil-type gas and biogas by using nitrogen groups. Background Art

[0002] Natural gas types, schemes and methods for classifying natural gas resources into different types according to different research and use purposes. According to components, it is divided into dry gas and wet gas; hydrocarbon gas and non-hydrocarbon gas. According to genesis, it is divided into organic gas (organic source) and inorganic gas (inorganic source). According to the state of occurrence, it is divided into free gas, dissolved gas, adsorbed gas, and solid gas hydrate. According to the parent material type, it is divided into humic gas (coal-type gas), saprophytic gas (oil-type gas), and humic saprophytic gas (terrestrial organic gas). According to the evolution stage of organic matter, it is divided into biogas, bio-thermal catalytic transition zone gas, pyrolysis gas (thermal catalytic, thermal cracking gas), high-temperature thermal cracking gas, etc.

[0003] Although there are methods for distinguishing between atmosphere, coal-type gas, oil-type gas, and biogas using argon and oxygen groups, there is currently no method for distinguishing between atmosphere, coal-type gas, oil-type gas, and biogas using nitrogen group. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for distinguishing atmosphere, coal-type gas, oil-type gas and biogas by using nitrogen family.

[0005] In order to solve the above problems, the present invention discloses a method for distinguishing atmosphere, coal-type gas, oil-type gas and biogas by using nitrogen family, comprising the following steps:

[0006] ⑴ Collect air samples, coal-type gas samples, oil-type gas samples, and biogas samples respectively;

[0007] (2) Gas chromatography-mass spectrometry was used to obtain the chromatograms of atmospheric samples, coal-type gas samples, oil-type gas samples, and biogas samples, and the mass number and abundance of nitrogen groups in all samples were obtained by mass selective detector (MSD). Each sample was tested 10 times to establish the N 2 Mass number abundance table;

[0008] ⑶ Calculate the N in each sample 2 The mass abundance values ​​of each sample N are compared. 2 The peaks with 10 repetitions of mass number were retained, and N 2 Summary table of mass abundance recurrence;

[0009] ⑷ According to each sample N 2 The mass abundance of atmospheric, coal-type gas, oil-type gas, and biogas N 2The percentage of the mass number molecules 14, 15, 16, 28, 29, 30 in common is used to establish a summary table of the percentage concentration of mass number molecules of atmosphere, coal-type gas, oil-type gas, and biogas;

[0010] ⑸ Use gas chromatography-mass spectrometry to obtain a chromatogram-mass spectrum for the unknown sample, and use a mass selective detector MSD to obtain the mass number of the nitrogen group in the unknown sample, and then compare it with the molecular percentage concentration summary table of the mass number of the known nitrogen group, so as to preliminarily determine whether the unknown sample is an atmospheric sample, a coal-type gas sample, an oil-type gas sample, or a biogas sample.

[0011] In the step (4), the mass number molecule percentage concentration summary table is replaced by a mass number molecule summary table, which is based on the N of each sample. 2 The mass abundance reproducibility summary table is obtained.

[0012] The determination of the unknown sample in step (5) is replaced by the following method: a gas chromatography-mass spectrometry technique is used to obtain a chromatogram-mass spectrum of the unknown sample, and a mass selective detector MSD is used to obtain the mass number of the nitrogen group in the unknown sample, and then compared with the molecular summary table of the mass number of the known nitrogen group, so as to preliminarily determine whether the unknown sample is an atmospheric sample, a coal-type gas sample, an oil-type gas sample, or a biogas sample.

[0013] The conditions of the gas chromatography-mass spectrometry technology are as follows: the chromatographic column is a molecular sieve column with an outer diameter of 3 mm and a column length of 1.0 to 2.0 m; the carrier gas is H 2 ; The column temperature is constant at 40℃; the injection port temperature is 130℃; the column flow rate is 30-40mL / min; the MSD detector temperature is 250℃; the injection volume is 0.2mL; the injection method is a manual syringe.

[0014] The conditions of the mass selective detector MSD are as follows: the transmission line temperature is 250° C.; the ion source temperature is 250° C.; the ionization mode is EI; the ionization energy is 70 eV; and the mass number scanning range is 2-150.

[0015] Compared with the prior art, the present invention has the following advantages:

[0016] 1. The present invention uses a chromatography-mass spectrometer to measure and compare the mass number, mass percentage concentration and mass abundance ratio to calculate nitrogen (N 2 ) group mass number molecules can be analyzed and compared to digitally distinguish the differences between atmospheric gas, coal-type gas, oil-type gas, and biogas.

[0017] 2. The mass number-abundance ratio method of the present invention is used to analyze the nitrogen (N) in the atmosphere, coal-type gas, oil-type gas, and biogas in terms of mass number molecular distribution. 2 ) plays the role of digital model fingerprint comparison.

[0018] 3. The mass number abundance percentage concentration method of the present invention has the function of comparing the digital model values ​​of the atmosphere, coal-type gas, oil-type gas and biogas in terms of mass number abundance percentage concentration.

[0019] 4. By adopting the method of the present invention, a digital fingerprint library of atmosphere, coal-type gas, oil-type gas and biogas can be established for mutual comparison. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0021] Figure 1 This is the GC-MSD analysis of Lanzhou atmosphere chromatogram-mass spectrogram in the present invention (Note: the red lines in the figure represent mass spectrum scanning points).

[0022] Figure 2 This is the gas chromatograph-mass spectrum of the 2# coal type analyzed by GC-MSD in the present invention (Note: the red lines in the figure represent mass spectrum scanning points).

[0023] Figure 3 This is the gas chromatograph-mass spectrum of the Yingdong 9# oil type analyzed by GC-MSD in the present invention (Note: the red lines in the figure represent mass spectrometry scanning points).

[0024] Figure 4 This is the GC-MSD analysis of H2 biogas - mass spectrum in the present invention (Note: the red lines in the figure represent mass spectrum scanning points). DETAILED DESCRIPTION

[0025] In the following examples, the instruments are: TRACE GC ULTRA gas chromatograph, MSD detector and the matching chromatographic and mass spectrometric workstation (Thermo Corporation, USA).

[0026] The conditions for gas chromatography-mass spectrometry technology are: the chromatographic column is a molecular sieve column with an outer diameter of 3 mm and a column length of 1.0 to 2.0 m; the carrier gas is H 2 ; The column temperature is constant at 40℃; the injection port temperature is 130℃; the column flow rate is 30-40mL / min; the MSD detector temperature is 250℃; the injection volume is 0.2mL; the injection method is a manual syringe.

[0027] The conditions of the mass selective detector MSD are as follows: the transmission line temperature is 250°C; the ion source temperature is 250°C; the ionization mode is EI; the ionization energy is 70 eV; and the mass number scanning range is 2-150.

[0028] Samples: Lanzhou outdoor atmosphere; Yingdong 9# oil-type gas; Se H2 biogas; Jiantan 2# coal-type gas.

[0029] A method for distinguishing atmosphere, coal-type gas, oil-type gas, and biogas using nitrogen family, comprising the following steps:

[0030] ⑴ Collect atmospheric samples, coal-type gas samples, oil-type gas samples, and biogas samples respectively.

[0031] (2) Gas chromatography-mass spectrometry was used to obtain the chromatograms of atmospheric samples, coal-type gas samples, oil-type gas samples, and biogas samples, and the mass number and abundance of nitrogen groups in all samples were obtained by mass selective detector (MSD). Each sample was tested 10 times to establish the N 2 The experimental results are shown in the table of mass abundance. Figures 1 to 4 , Tables 1 to 4.

[0032] Table 1 MSD analysis of N in 10 Lanzhou atmospheric samples 2 Mass abundance table

[0033]

[0034] Table 2 MSD analysis of N in 10 sharp probe 2# coal type gas samples 2 Mass abundance table

[0035]

[0036] Table 3 MSD analysis of N in 10 Yingdong 9# oil-type gas samples 2 Mass abundance table

[0037]

[0038]

[0039]

[0040] ⑶ Calculate the N in each sample 2 The mass abundance values ​​of each sample N are compared. 2 The peaks with 10 repetitions of mass number were retained, and N 2 The results are shown in Tables 5 to 8.

[0041] Table 5 MSD analysis of N in 10 Lanzhou atmospheric samples 2 Summary table of mass abundance reproducibility

[0042]

[0043] Table 6 MSD analysis of N in 10 sharp probe 2# coal type gas samples 2 Summary table of mass abundance reproducibility

[0044]

[0045] Table 7 MSD analysis of N in 10 Yingdong 9# oil-type gas samples 2 Summary table of mass abundance reproducibility

[0046]

[0047] Table 8 MSD analysis of N in 10 H2 biogas samples 2 Summary table of mass abundance reproducibility

[0048]

[0049] ⑷Mass number method:

[0050] According to each sample N 2 The mass number abundance recurrence summary table of the atmosphere, coal-type gas, oil-type gas, and biogas mass number molecular summary table is established, see Table 9.

[0051] Table 9 Summary of mass number molecules of atmosphere, coal-type gas, oil-type gas and biogas

[0052]

[0053] From Table 9, we can see that atmospheric, coal-type gas, oil-type gas, biogas N 2 The distribution of molecules with different mass numbers is different.

[0054] Percent concentration method:

[0055] According to each sample N 2 The mass abundance of atmospheric, coal-type gas, oil-type gas, and biogas N 2 The percentage of the common mass number molecules 14, 15, 16, 28, 29, 30 is used to establish the percentage concentration summary of the mass number molecules of atmosphere, coal-type gas, oil-type gas, and biogas, see Table 10.

[0056] Table 10 Nitrogen (N) in atmosphere, coal-type gas, oil-type gas and biogas 2 ) Group mass number molecular percentage concentration summary table

[0057]

[0058] From Table 10, we can see that nitrogen (N 2 ) The mass numbers 14, 28, and 29 percent concentrations show a trend.

[0059] The atmospheric, coal-type gas, oil-type gas, and biogas N in Tables 5 to 8 2 The abundance values ​​of the common mass number molecules 14, 15, 16, 28, 29, and 30 are respectively calculated as mass number abundance ratios, see Tables 11 to 14.

[0060] Table 11 MSD analysis of N in 10 Lanzhou air samples 2 Mass number abundance ratio table

[0061]

[0062] Table 12 MSD analysis of N in 10 sharp probe 2# coal type gas samples 2 Mass number abundance ratio table

[0063]

[0064] Table 13 MSD analysis of N in 10 Yingdong 9# oil-type gas samples 2 Mass number abundance ratio table

[0065]

[0066] Table 14MSD analysis of N in 10 H2 biogas samples 2 Mass number abundance ratio table

[0067]

[0068] The mass abundance ratios of the average values ​​in Tables 11 to 14 are summarized in Table 15.

[0069] Table 15 N of atmospheric gas, coal gas, oil gas and biogas 2 Mass number abundance ratio comparison table

[0070]

[0071] From Table 15, we can see that atmospheric, coal-type gas, oil-type gas, biogas N 2 There are large differences in the abundance ratios of some mass numbers, for example 28 N 2 / 14 N 2 , 29 N 2 / 14 N 2 , 29 N 2 / 15 N 2 wait.

[0072] ⑸ Use gas chromatography-mass spectrometry to obtain the chromatogram-mass spectrum of the unknown sample, and use the mass selective detector MSD to obtain the mass number of the nitrogen group in the unknown sample, and then compare it with the mass number molecule summary table or mass number molecule percentage concentration summary table of the known nitrogen group, so as to preliminarily determine whether the unknown sample is an atmospheric sample, a coal-type gas sample, an oil-type gas sample, or a biogas sample.

Claims

1. A method for distinguishing atmospheric gas, coal-type gas, oil-type gas, and biogas using nitrogen family, comprising the following steps: ⑴ Collect air samples, coal-type gas samples, oil-type gas samples, and biogas samples respectively; (2) For atmospheric samples, coal-type gas samples, oil-type gas samples, and biogas samples, gas chromatography-mass spectrometry was used to obtain the chromatograms of each sample, and the mass number and abundance of the nitrogen group in all samples were obtained by mass selective detector MSD. Each sample was tested 10 times, and the mass number abundance table of N2 in each sample was established; (3) Compare the mass abundance values ​​of N2 in each sample respectively, retain the mass values ​​of N2 peaks in each sample that have 10 repetitions, and establish a summary table of the repetition of mass abundance of N2 in each sample; (4) According to the mass number abundance recurrence summary table of each sample N2, the percentage of mass number molecules 14, 15, 16, 28, 29, 30 in the atmosphere, coal-type gas, oil-type gas, and biogas is established; ⑸ Use gas chromatography-mass spectrometry to obtain a chromatogram-mass spectrum for the unknown sample, and use a mass selective detector MSD to obtain the mass number of the nitrogen group in the unknown sample, and then compare it with the molecular percentage concentration summary table of the mass number of the known nitrogen group, so as to preliminarily determine whether the unknown sample is an atmospheric sample, a coal-type gas sample, an oil-type gas sample, or a biogas sample.

2. A method for distinguishing atmospheric gas, coal-type gas, oil-type gas, and biogas using nitrogen family as claimed in claim 1, characterized in that: The mass number molecule percentage concentration summary table in step (4) is replaced by a mass number molecule summary table, which is obtained based on the mass number abundance recurrence summary table of each sample N2.

3. The method of using nitrogen family to distinguish between atmospheric gas, coal-type gas, oil-type gas and biogas according to claim 1, characterized in that: The determination of the unknown sample in step (5) is replaced by the following method: a gas chromatography-mass spectrometry technique is used to obtain a chromatogram-mass spectrum of the unknown sample, and a mass selective detector MSD is used to obtain the mass number of the nitrogen group in the unknown sample, and then compared with the molecular summary table of the mass number of the known nitrogen group, so as to preliminarily determine whether the unknown sample is an atmospheric sample, a coal-type gas sample, an oil-type gas sample, or a biogas sample.

4. The method of using nitrogen family to distinguish between atmospheric gas, coal-type gas, oil-type gas and biogas according to claim 1, characterized in that: The conditions of the gas chromatography-mass spectrometry technology are: the chromatographic column is a molecular sieve column with an outer diameter of 3 mm and a column length of 1.0~2.0 m; the carrier gas is H2; the column temperature is a constant 40°C; the injection port temperature is 130°C; the column flow rate is 30~40 mL / min; the MSD detector temperature is 250°C; the injection volume is 0.2 mL; and the injection method is a manual syringe.

5. The method of using nitrogen family to distinguish between atmospheric gas, coal-type gas, oil-type gas and biogas according to claim 1, characterized in that: The conditions of the mass selective detector MSD are as follows: the transmission line temperature is 250° C.; the ion source temperature is 250° C.; the ionization mode is EI; the ionization energy is 70 eV; and the mass number scanning range is 2-150.

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