CN109187838A - Single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water - Google Patents

Single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water Download PDF

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Publication number
CN109187838A
CN109187838A CN201811130365.0A CN201811130365A CN109187838A CN 109187838 A CN109187838 A CN 109187838A CN 201811130365 A CN201811130365 A CN 201811130365A CN 109187838 A CN109187838 A CN 109187838A
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China
Prior art keywords
sulfide
mass number
hydrocarbon
water
carrier gas
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CN201811130365.0A
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Chinese (zh)
Inventor
潘旭
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Lanzhou Center for Oil and Gas Resources of Institute of Geology and Geophysics of CAS
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Lanzhou Center for Oil and Gas Resources of Institute of Geology and Geophysics of CAS
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Priority to CN201811130365.0A priority Critical patent/CN109187838A/en
Publication of CN109187838A publication Critical patent/CN109187838A/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample

Abstract

The present invention relates to hydrocarbon, sulfide signal and mass number Abundances and ratios in a kind of single injected sampling analysis water, comprising the following steps: (1) carrier gas flows into clarifier, and purified carrier gas purity is made to be greater than 99.999%；(2) purified carrier gas enters in the porous polymer bead chromatographic column for having placed sample to be tested, the H after adsorption/desorption acts on, in sample to be tested2O is sent into flame ionisation detector FID, flame photometric detector FPD, mass selective detector MSD and is detected simultaneously through current divider, respectively obtains MSD ion stream chromatogram, spectrogram is looked in FID hydrocarbonylation, FPD sulfide chromatogram, and then obtains H2Hydrocarbon in O, sulfide signal area and16H2O、17H2O、18H2O、19H2O、20H2O、21H2The mass number Abundances of O and 11 are compared with stabilizing water quality amount number abundance ratio.The present invention is simple, easy to operate, can be applied in the fields such as water source, deep-sea, geology, meteorology, petroleum, environmental protection, human medical, animals and plants research.

Description

Single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water
Technical field
The present invention relates to the technologies such as water source, deep-sea, geology, meteorology, human medical, animals and plants research, petroleum, environmental protection necks Hydrocarbon, sulfide signal and mass number Abundances and ratio in domain more particularly to single injected sampling analysis water.
Background technique
Water is one of most common substance on the earth, is the important of all life existence including inorganic chemical, the mankind Resource and the most important component part of organism.It there is no the pertinent literature report for determining hydrocarbon in water, sulfide source at present.
Summary of the invention
Technical problem to be solved by the invention is to provide hydrocarbon, vulcanization in a kind of easy, easy single injected sampling analysis water Object signal and mass number Abundances and ratio.
To solve the above problems, hydrocarbon, sulfide signal and mass number abundance in single injected sampling analysis water of the present invention Value and ratio, comprising the following steps:
(1) carrier gas of the purity greater than 99.99% flows into clarifier under the pressure of 0.40 ~ 0.60 MPa, keeps purified carrier gas pure Degree is greater than 99.999%；
(2) the purified carrier gas is entered by the time programming six-way injection valve being located in color-mass spectrograph through injection port Place sample to be tested porous polymer bead chromatographic column in, 30 ~ 50 DEG C at a temperature of after adsorption/desorption acts on, it is described to H in sample2O is sent into flame ionisation detector FID, flame photometric detector FPD, quality selection detection through current divider simultaneously Device MSD is detected, and respectively obtains MSD ion stream chromatogram, spectrogram is looked in FID hydrocarbonylation, FPD sulfide chromatogram, and then is obtained Obtain H2Hydrocarbon in O, sulfide signal area and16H2O、17H2O、18H2O、19H2O、20H2O、21H2The mass number Abundances of O and17H2O/16H2O、18H2O/16H2O、19H2O/16H2O、21H2O/16H2O、18H2O/17H2O、19H2O/17H2O、21H2O/17H2O、19H2O/18H2O、21H2O/18H2O、21H2O/19H2O、21H2O/20H2O ratio.
The step (1) in carrier gas be hydrogen or helium.
The step (2) in porous polymer bead chromatographic column refer in fill out Porapak, Chromosorb, GDX high polymer The stainless steel tube packed column or internal diameter that any one internal diameter is 1 ~ 5mm in bead and column length is 0.5 ~ 9m are 0.3 ~ 0.6mm and column The capillary column of a length of 10 ~ 90m.
Compared with the prior art, the present invention has the following advantages:
1, using the method for the present invention, it can be seen that water it is long what, that is, in unit water different quality number molecule distribution:16H2O ≈0.43%；17H2O≈11.54%；18H2O≈72.85%；19H2O≈14.94%；20H2O≈0.21%；21H2O≈0.04%。
2, using the method for the present invention, 11 be can get compared with stabilizing water quality amount number abundance ratio:17H2O/16H2O≈27.1、18H2O/16H2O≈171.11、19H2O/16H2O≈35.094、21H2O/16H2O≈0.1、18H2O/17H2O≈6.31、19H2O/17H2O ≈1.3、21H2O/17H2O≈0.0037、19H2O/18H2O≈0.21、21H2O/18H2O≈0.00058、21H2O/19H2O≈0.0028 、21H2O/20H2O≈0.2。
3, by the method for the invention, specify that water can be measured by FID, FPD.
4, using the method for the present invention, the water (H of each sample can be established2O) mass number abundance ratio and hydrocarbon, sulfide area Fingerprint base, for mutually compare.
5, the present invention is simple, easy to operate, can be applied to water source, deep-sea, geology, meteorology, petroleum, environmental protection, human medical, moves In the fields such as plant research.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is MSD ion stream chromatogram of the present invention, spectrogram, FPD sulfide chromatogram are looked in FID hydrocarbonylation.
Fig. 2 is that MSD of the present invention analyzes water quality number scanning 2 ~ 1000amu color-mass spectrogram.
Fig. 3 is that MSD of the present invention analyzes water quality number scanning 2 ~ 100amu color-mass spectrogram.
Specific embodiment
Single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water, comprising the following steps:
(1) carrier gas of the purity greater than 99.99% flows into clarifier under the pressure of 0.40 ~ 0.60 MPa, keeps purified carrier gas pure Degree is greater than 99.999%.
Wherein: carrier gas is hydrogen or helium.
(2) purified carrier gas leads to sample introduction by being located in color-mass spectrograph the time programming six of (GC-FID-FPD-MSD) Valve enters through injection port and has placed in the porous polymer bead chromatographic column of sample to be tested, 30 ~ 50 DEG C at a temperature of through adsorbing H after desorption, in the sample to be tested2O is sent into flame ionisation detector FID, flame photometric detection through current divider simultaneously Device FPD, mass selective detector MSD are detected, and respectively obtain MSD ion stream chromatogram, spectrogram is looked in FID hydrocarbonylation, FPD sulphur Compound chromatogram (referring to Fig. 1), and then obtain H2Hydrocarbon in O, sulfide signal area and16H2O、17H2O、18H2O、19H2O、20H2O 、21H2The mass number Abundances of O and17H2O/16H2O、18H2O/16H2O、19H2O/16H2O、21H2O/16H2O、18H2O/17H2O、19H2O/17H2O、21H2O/17H2O、19H2O/18H2O、21H2O/18H2O、21H2O/19H2O、21H2O/20H2O ratio.
Wherein: porous polymer bead chromatographic column refers to that interior fill out in Porapak, Chromosorb, GDX high polymer bead is appointed The stainless steel tube packed column or internal diameter that a kind of internal diameter of anticipating is 1 ~ 5mm and column length is 0.5 ~ 9m be 0.3 ~ 0.6mm and column length be 10 ~ The capillary column of 90m.
It can be seen that main component is water (H from MSD ion flow graph2O), there are also some air (Air)；Spectrum is looked in FID hydrocarbonylation It can be seen that in figure and contain hydrocarbonylation object in water peak；Contain sulfide signal in FPD sulfide chromatogram in water peak.Illustrate from porous height What the small goalpost of polymers distillated be containing hydrocarbon, sulfide water peak rather than pure water molecule peak, and water be also can by FID, FPD is measured.
Mass number distribution in water
The mass number distribution in water is understood by MSD: setting 2 ~ 1000 amu of scanning range, testing result deduct background, see figure 2, table 1.
1 mass selective detector of table (MSD) analyzes water quality number and scans 2 ~ 1000amu abundance table
The scanning that can be seen that 2 ~ 1000amu of water quality number from Fig. 2, table 1 has table in mass number (Mass) units to three digits It reaches, and mass number of total abundance (Intensity) value up to 99.99% is below 100.Illustrate to evaporate from the small goalpost of porous polymer Water peak out includes numerous mass numbers (Mass) in units to three-figure molecule.
Reproducibility experiment
Water quality number 2 ~ 100amu of scanning range is set, 10 same water sample reproducibility experiments are done, testing result deducts background, See Fig. 3, table 2 ~ 3.
2 MSD of table analyzes 10 water sample mass number scanning 2 ~ 100amu Abundances reproducibility and tests table
3 MSD of table analyzes 10 water sample mass number scanning 2~100amu abundance ratio reproducibility and tests table
The scanning in 2 ~ 100amu of water quality number is found out from Fig. 3, table 2, it can be seen that the molecular distribution of different quality number passes through table 2 In each mass number abundance mutual ratios reproducibility calculate, inductive statistics, relative standard deviation RSD(%)≤5% mass number Abundance ratio is shown in Table 3, determines that workable mass number is shown in Table 4 from table 3.
Table 3 illustrates mass number abundance ratio workable for water:17H2O/16H2O≈27.1、18H2O/16H2O≈171.11、19H2O/16H2O≈35.094、21H2O/16H2O≈0.1、18H2O/17H2O≈6.31、19H2O/17H2O≈1.3、21H2O/17H2O≈ 0.0037、19H2O/18H2O≈0.21、21H2O/18H2O≈0.00058、21H2O/19H2O≈0.0028、21H2O/20H2O≈0.2。
Mass number workable for table 4

Claims (3)

1. single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water, comprising the following steps:
(1) carrier gas of the purity greater than 99.99% flows into clarifier under the pressure of 0.40 ~ 0.60 MPa, keeps purified carrier gas pure Degree is greater than 99.999%；
(2) the purified carrier gas is entered by the time programming six-way injection valve being located in color-mass spectrograph through injection port Place sample to be tested porous polymer bead chromatographic column in, 30 ~ 50 DEG C at a temperature of after adsorption/desorption acts on, it is described to H in sample2O is sent into flame ionisation detector FID, flame photometric detector FPD, quality selection detection through current divider simultaneously Device MSD is detected, and respectively obtains MSD ion stream chromatogram, spectrogram is looked in FID hydrocarbonylation, FPD sulfide chromatogram, and then is obtained Obtain H2Hydrocarbon in O, sulfide signal area and16H2O、17H2O、18H2O、19H2O、20H2O、21H2The mass number Abundances of O and17H2O/16H2O、18H2O/16H2O、19H2O/16H2O、21H2O/16H2O、18H2O/17H2O、19H2O/17H2O、21H2O/17H2O、19H2O/18H2O、21H2O/18H2O、21H2O/19H2O、21H2O/20H2O ratio.
2. hydrocarbon, sulfide signal and mass number Abundances and ratio in single injected sampling analysis water as described in claim 1, special Sign is: the step (1) in carrier gas be hydrogen or helium.
3. hydrocarbon, sulfide signal and mass number Abundances and ratio in single injected sampling analysis water as described in claim 1, special Sign is: the step (2) in porous polymer bead chromatographic column refer in fill out Porapak, Chromosorb, GDX high polymer small The stainless steel tube packed column or internal diameter that any one internal diameter is 1 ~ 5mm in ball and column length is 0.5 ~ 9m are 0.3 ~ 0.6mm and column length For the capillary column of 10 ~ 90m.
CN201811130365.0A 2018-09-27 2018-09-27 Single injected sampling analyzes hydrocarbon, sulfide signal and mass number Abundances and ratio in water Pending CN109187838A (en)

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CN111781284A (en) * 2020-07-08 2020-10-16 中国科学院西北生态环境资源研究院 Method for identifying light water, heavy water and heavy oxygen water by using mass number-abundance ratio method

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Application publication date: 20190111