CN113804769A - Light hydrocarbon carbon isotope enrichment analytical equipment in natural gas - Google Patents
Light hydrocarbon carbon isotope enrichment analytical equipment in natural gas Download PDFInfo
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- CN113804769A CN113804769A CN202010545608.8A CN202010545608A CN113804769A CN 113804769 A CN113804769 A CN 113804769A CN 202010545608 A CN202010545608 A CN 202010545608A CN 113804769 A CN113804769 A CN 113804769A
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 56
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 55
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 55
- 239000003345 natural gas Substances 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012360 testing method Methods 0.000 claims abstract description 18
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- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010201 enrichment analysis Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G—PHYSICS
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- 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
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- G01N2030/8868—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 elemental analysis, e.g. isotope dilution analysis
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Abstract
The utility model provides a light hydrocarbon carbon isotope enrichment analytical equipment in natural gas, includes the preparation chromatogram, nitrogen source and main line are connected to the preparation chromatogram, and vacuum system, bubble system and test system connect respectively on the main line, vacuum system includes vacuometer and vacuum pump, the bubble system includes the bubble meter, test system is including the cold hydrazine one that connects gradually, cold hydrazine two, cold hydrazine three and isotope analysis test system. The invention carries out on-line isotope detection on the enriched and separated light hydrocarbon, prevents the fractionation of carbon isotopes in multiple sampling and sample injection, and ensures the accuracy of analysis and test.
Description
Technical Field
The invention relates to an isotope enrichment analysis device, in particular to an enrichment analysis device for light hydrocarbon carbon isotopes in natural gas.
Background
The carbon isotopes with different components in the natural gas can accurately identify the cause type of the natural gas and evaluate the maturity of the natural gas, and most of the prior applications are mainly C1～C5Investigation of component carbon isotopes, however C1～C5The component molecules have limited kinds and simple structure, and the carbon isotope provides relatively limited information, except C in moisture1～C5Component (d) C6～C8The light hydrocarbon of the component has high visibility and complex molecular structure, and the research on the characteristics of the carbon isotopes of the series monomers has important significance for exploring and researching the cause of natural gas, identifying the type of gas and comparing gas sources.
Because the content of light hydrocarbon in the natural gas is often small, the C in the natural gas is accurately analyzed6～C8The difficulty of light hydrocarbon isotopes of the components is high, and people adopt the on-line separation of carbon isotopesThe analytical technique, however, because the sample volume that gets into in the detector is less in the actual analysis, often can produce the fluctuation of data, when light hydrocarbon content was extremely low, often because the content is less than the detection line, and unable detection, consequently, develop novel enrichment device of light hydrocarbon component in the natural gas and method, received everybody's extensive attention.
In conventional chromatographic separation processes, separation of various gas components in natural gas can be achieved by adjusting the chromatographic conditions, however, where C is5Gas-like component and C6The time interval of the retention time of the gas-like component is limited, so that the enriched C is easily caused in the enrichment process6～C8The component contains a certain amount of C5Component (b) due to part C5Freezing point of component and part C6The freezing points of the components are similar, so that C cannot be achieved in the subsequent cold trap5Component (A) and (C)6Complete separation of the components. The influence is relatively small when the component analysis of light hydrocarbon is carried out, however, when the carbon isotope analysis of the light hydrocarbon component is carried out, because the retention time of the adjacent light hydrocarbon components is relatively small and even can not be completely separated, the subsequent test influence on the light hydrocarbon carbon isotope is influenced.
In the enrichment of isotopes, various cold hydrazines are often used. A cold trap is a device that prevents vapor or liquid from entering the measurement instrument from the system, or from entering the system from the measurement instrument. It provides a very low temperature surface on which molecules can condense and increase the vacuum by one to two orders of magnitude. However, improper use of cold traps can reduce the accuracy of the instrument, cause damage to the instrument or system, and create a physical incident. For example, many mixtures of fats used in cold traps are toxic and can also be handled improperly to cause an explosion. The rate of cold trap evaporation is affected not only by the energy intake, but also by the pump speed of the vacuum pump. The larger sample evaporation surface area is the bottleneck affecting the efficiency of the vacuum pump, not the sample volume and quantity. It is more efficient to use a cold trap rather than a larger vacuum pump. Due to the use of the cold trap, on one hand, the condensation of water vapor is facilitated, and on the other hand, the evaporation density of the organic solvent is improved, so that the condensation is easier.
Cold trap processing is a cooling device used to collect substances within a certain melting point range. A U-shaped tube is placed in the refrigerant, when gas passes through the U-shaped tube, substances with high melting points are changed into liquid, and substances with low melting points pass through the U-shaped tube to play a role in separation. However, the use of cold hydrazine alone often fails to achieve satisfactory results due to the complex components in natural gas. The data of various experiments are often not accurate enough, and the experiment efficiency is low
In view of the above, a system for preparing a sample by carbon isotopes, which is a reasonable and effective improvement on the missing light hydrocarbon components in natural gas, is designed, and a brand new sample preparation method is introduced.
Disclosure of Invention
The invention aims to solve the problem of inaccurate carbon isotope analysis of light hydrocarbon components in natural gas, and provides a system and a method for enriching light hydrocarbon components in natural gas.
In order to realize the aim, the invention provides a system and a method for enriching, analyzing and testing light hydrocarbon components in natural gas, which adopt a preparative chromatogram, and can effectively realize C in light hydrocarbon by adjusting the chromatographic condition of the preparative chromatogram1～C5Component (A) and (C)6～C8Complete separation of the components. The invention adopts chromatographic separation and multi-cold trap enrichment coupling separation mode, different from conventional chromatographic separation for completely separating different components, and the chromatographic separation condition set by the invention aims at realizing C5Component (A) and (C)6The time intervals of the retention times of the components are expanded as much as possible to achieve complete separation thereof.
When all C are6～C8When the components are completely enriched, multiple cold traps are adopted for separation, so that light hydrocarbon components (C) with different carbon numbers are realized6And C7 +Separation of components) can effectively ensure the separation effect of light hydrocarbon components with different carbon numbers;
the chromatographic conditions are optimized, and finally, the accurate test of carbon isotopes of different light hydrocarbon components is realized.
The specific implementation method comprises the following steps:
the utility model provides a light hydrocarbon carbon isotope enrichment analytical equipment in natural gas, includes the preparation chromatogram, nitrogen source and main line are connected to the preparation chromatogram, and vacuum system, bubble system and test system connect respectively on the main line, vacuum system includes vacuometer and vacuum pump, the bubble system includes the bubble meter, test system is including the cold hydrazine one that connects gradually, cold hydrazine two, cold hydrazine three and isotope analysis test system.
Preferably, valves are respectively arranged between the nitrogen source and the preparative chromatography, between the main pipeline and the preparative chromatography, between the vacuum system and the main pipeline, between the bubble meter and the main pipeline, between the first cold hydrazine and the second cold hydrazine, between the second cold hydrazine and the third cold hydrazine, and between the third cold hydrazine and the isotope test system.
Preferably, the valve is a vacuum valve.
Preferably, the first cold hydrazine, the second cold hydrazine and the third cold hydrazine are different cold hydrazines.
Preferably, the cold hydrazine at least comprises a liquid nitrogen cold trap, a dry ice cold trap and an alcohol cold hydrazine.
The invention has the following beneficial effects:
adopts a preparative chromatographic separation method to optimize chromatographic conditions to ensure C in the chromatogram5Component (A) and (C)6The retention time interval of the components is more than 7min, and the C is realized6～C8Component (A) and (C)1～C5Complete separation of components;
c in light hydrocarbon is purified by adopting a light hydrocarbon purification method6～C8While the components are completely retained, C is further removed1～C5Small amounts of moisture in the components and natural gas;
by adopting multi-type cold traps, C is further realized6Component (A) and (C)7Separating the above components;
the enrichment separation light hydrocarbon is subjected to on-line isotope detection, so that fractionation of carbon isotopes in multiple sampling and sample introduction is prevented, and the accuracy of analysis and test is ensured.
Drawings
Fig. 1 is a schematic structural diagram of a carbon isotope enrichment analysis system according to the present invention.
The reference numbers are as follows:
1. preparing a chromatogram; 2. a vacuum valve; 3. helium gas; 4. a vacuum valve; 5. a vacuum valve; 6. a vacuum gauge; 7: a vacuum pump; 8. a vacuum valve; 9. a bubble meter; 10. a vacuum valve; 11. a first cold trap; 12. a vacuum valve; 13. a second cold trap; 14. a vacuum valve; 15. a third cold trap; 16. a vacuum valve; 17. isotope analysis test system
Detailed Description
The detailed description and technical contents of the present invention are described below with reference to the accompanying drawings, which are provided for reference and illustration purposes only and are not intended to limit the present invention.
As shown in fig. 1, the device for enriching and analyzing carbon isotopes of light hydrocarbon component monomer hydrocarbon in natural gas comprises a light hydrocarbon enrichment system and an analysis and detection system, wherein the light hydrocarbon enrichment system comprises a chromatograph, a vacuum valve, a vacuum pump, a helium gas circuit, a cold trap, a bubble meter and a vacuum valve which are connected in sequence; the analytical detection system mainly comprises a chromatograph and an isotope mass spectrometer.
In order to achieve the purpose, the invention adopts the following technical scheme that the carbon isotope detection of the light hydrocarbon component carbon isotope monomer hydrocarbon carbon isotope in the natural gas is divided into five steps:
(1) vacuum detection
Introducing helium into the system, removing impurity gas, starting the vacuum system, and observing the vacuum degree in the sample cell by a vacuum gauge until the vacuum degree reaches 10-2pa。
(2) Chromatographic separation
Injecting natural gas into the preparative chromatography, and optimizing the chromatographic conditions through multiple experiments, wherein the light hydrocarbon C can be obtained by the natural gas through the preparative chromatography6～C8Component (A) and (C)1～C5The components are completely separated, and the chromatographic condition is that (the chromatographic column is a propack Q packed column, the temperature programming condition is that the initial temperature is 40 ℃, and the constant temperature is kept for 1 minuteThen heating to 145 ℃ at a speed of 10 ℃/min, keeping the temperature for 15 minutes, heating to 145 ℃ at a speed of 2 ℃/min, keeping the temperature for 15 minutes, taking helium as carrier gas and setting the flow rate to 13mL/min)
(3) Purification of light hydrocarbons
The light hydrocarbon components obtained by preparative chromatographic separation are further purified and enriched in two cold traps, the separation of water and hydrocarbon gas is realized through the first cold trap, and the separation of C is realized through the second cold trap6～C8And (5) enriching the components until the cold hydrazine III.
(4) Staged release
Based on the temperature difference of different cold traps (such as a first cold trap liquid nitrogen cold trap, a second cold trap alcohol cold trap and a third cold trap dry ice cold trap), firstly, enriched gas is transferred from the liquid nitrogen cold trap to the dry ice cold trap to realize C in light hydrocarbon components6Component (A) and (C)7Separating the above components.
(5) Analytical testing
C to be released6Component (A) and (C)7The components are introduced into an isotope chromatography-mass spectrometry detection system, the separation, reaction and detection of light hydrocarbon component monomer hydrocarbon are carried out through chromatography, so that the carbon isotope analysis of the light hydrocarbon monomer hydrocarbon in the natural gas is realized, and the chromatographic conditions are as follows: al (Al)2O3A capillary column, wherein the programmed temperature rise condition is that the initial temperature is 40 ℃, the temperature is kept for 1 minute, then the temperature is raised to 145 ℃ at the speed of 1.5 ℃/min, the temperature is kept for 20 minutes, then the temperature is raised to 280 ℃ at the speed of 2 ℃/min, the temperature is kept for 15 minutes, the carrier gas is helium gas, and the flow rate is 3mL/min
Compared with the existing light hydrocarbon enrichment and detection method, the method adopts a two-step enrichment method of preparative chromatographic separation and cold trap condensation for the first time, and ensures that the light hydrocarbon C is enriched6～C8Component (A) and (C)1～C5The complete separation of the components prevents the fractionation of light hydrocarbon, and then adopts a plurality of types of cold traps to realize the slow release of light hydrocarbon gas, and finally couples with a mass spectrometer to achieve the light hydrocarbon C6～C8The optimal separation effect of the components finally realizes the enrichment and accurate test of the monomer hydrocarbon of the light hydrocarbon component in the natural gas,
the enrichment and analytical test method of the present system is illustrated by the operation in practical application below:
(1) the vacuum valves 2, 4, 8, 10, 12, 14 and 16 are closed to fill the reaction lines with helium gas, and when continuous bubbles are observed in the bubble gauge 9, the vacuum valves 2, 8 and 16 are opened.
(2) Opening a vacuum valve 5, and vacuumizing the reaction tube;
(3) when the vacuum degree of the sample tube reaches 10-2At Pa, the vacuum valves 5, 10, 12 and 14 are opened;
(4) adjusting the temperature of the cold trap, wherein the cold trap 11 is an alcohol liquid nitrogen cold trap, and the cold trap 13 adopts a liquid nitrogen cold trap;
(5) injecting 5ml of natural gas sample into the preparative chromatograph 1, closing the vacuum valve 8 to make C in the natural gas1～C5The components are discharged, and when the appearance of light hydrocarbon C is observed in the chromatogram6During the component composition, the vacuum valve 8 is opened, the vacuum valves 10 and 12 are closed, and the trace water vapor in the natural gas is removed through the cold trap 11 to remove the light hydrocarbon C in the natural gas6～C8The components remain in the cold trap 13;
(6) the vacuum valve 12 is opened, the vacuum valve 14 is closed, and the temperature of the cold trap 13 is slowly increased;
(7) closing the vacuum valves 2, 4, 10 and 12, and injecting helium gas into the pipeline;
(8) closing the vacuum valve 16 to make C in light hydrocarbon6The components enter a chromatograph and are reacted and detected;
(9) the vacuum valve 14 is disconnected, and the temperature of the cold trap 15 is slowly increased;
(10) closing the vacuum valve 16 to make C in the light hydrocarbon7The above components enter chromatography and isotope mass spectrometry.
While the invention has been described with reference to a number of illustrative embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Therefore, any simple modifications or equivalent substitutions made in accordance with the embodiments of the present invention are within the scope of the claims of the present invention.
Claims (5)
1. The utility model provides a light hydrocarbon carbon isotope enrichment analytical equipment in natural gas, includes preparation chromatogram, its characterized in that: the preparation chromatogram is connected with a nitrogen source and a main pipeline, a vacuum system, a bubble system and a test system are respectively connected on the main pipeline, the vacuum system comprises a vacuum gauge and a vacuum pump, the bubble system comprises a bubble gauge, and the test system comprises a first cold hydrazine, a second cold hydrazine, a third cold hydrazine and an isotope analysis test system which are sequentially connected.
2. The isotopic enrichment analysis device for light hydrocarbon carbon in natural gas as claimed in claim 1, wherein: valves are respectively arranged between the nitrogen source and the preparative chromatograph, between the main pipeline and the preparative chromatograph, between the vacuum system and the main pipeline, between the bubble meter and the main pipeline, between the first cold hydrazine and the second cold hydrazine, between the second cold hydrazine and the third cold hydrazine, and between the third cold hydrazine and the isotope test system.
3. The isotopic enrichment analysis device for light hydrocarbon carbon in natural gas as claimed in claim 2, wherein: the valve is a vacuum valve.
4. The device for isotopically enriching and analyzing light hydrocarbon carbon in natural gas as claimed in claim 2 or 3, wherein: the first cold hydrazine, the second cold hydrazine and the third cold hydrazine are different cold hydrazines.
5. The isotopic enrichment analysis device of light hydrocarbon carbon in natural gas as claimed in claim 4, wherein: the cold hydrazine at least comprises a liquid nitrogen cold trap, a dry ice cold trap and an alcohol cold hydrazine.
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