CN204630990U - A kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection - Google Patents
A kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection Download PDFInfo
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- CN204630990U CN204630990U CN201520170297.6U CN201520170297U CN204630990U CN 204630990 U CN204630990 U CN 204630990U CN 201520170297 U CN201520170297 U CN 201520170297U CN 204630990 U CN204630990 U CN 204630990U
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The utility model provides a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection.This device comprises the first injector, the one or eight logical valve, chemical trap, the two or eight logical valve, the second injector, the first cold-trap, the second cold-trap, the first helium pressure regulator valve, the second helium pressure regulator valve, the 3rd helium pressure regulator valve.The on-line preconcentration that in the rock gas detected for stable isotope of the present utility model, trace hydro carbons enriching apparatus can realize trace hydro carbons in rock gas, be connected with gas chromatograph, stable isotope mass spectrometer, the Stable Isotopic Analysis of different hydrocarbons component can be realized; And this device is simple to operate, quick, accurate, widely applicable, have good repeatability.
Description
Technical field
The utility model relates to a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, belongs to analytical chemistry field.
Background technology
The element composition of rock gas is relatively single, and its carbon, the meaning of hydrogen isotope composition research to its tracer study seem particularly important, and the stable isotope research of rock gas has become the necessary means of Gas Source Correlation research.But, in the rock gas sample that part is special, because various geologic agent causes the content of hydrocarbon gas component very low, the mass spectrographic detectability requirement of stable isotope can not be met, be difficult to the stable isotope information obtaining these components, limit the application of stable isotope technology in oil-gas exploration.To analyze the stable isotope of this trace hydro carbons, first must carry out effective enrichment to it.
At present, two kinds are mainly contained to the enrichment of the low concentration hydro carbons of above several types and detection technique both at home and abroad:
1) off-line preenrichment-stable isotope detection technique.This technology is used for analyzing the isotopic method of single gas composition (Craig, 1957).Concrete steps are: rock gas is isolated CH in gas chromatograph (GC)
4, C
2h
6, C
3h
8etc. single component; Be CO by burning in methane and homolog thereof one by one excessive oxygen at high temperature
2and H
2o; The CO of each component generation is collected one by one with glass tube
2or H
2o; When carrying out carbon isotope test, CO will be contained
2glass tube connects with isotope mass spectrometer (IRMS), carries out carbon isotope test.When carrying out hydrogen isotope test, H will be contained
2the glass tube of O is at high temperature prepared into H by zinc, uranium or cadmium reducing process
2, the sample bottle contained after reduction is connected with isotope mass spectrometer (IRMS), carries out hydrogen isotope test.This technology is since nineteen fifty, and its Basic Design does not significantly change, and its important advantage is that carbon isotope measuring accuracy is up to 0.01 ‰.But this technology is not high due to complex operation, efficiency, is not used in routine analysis, but still is frequently used to and tests (McCauley, 1999) as the accuracy of standard to such new technology.
2) online cold-trap enrichment-stable isotope detection technique.This kind of technology is applied in the isotope analysis of the micro-hydrocarbon gas such as geology inclusion, air, moral purity, deep-sea hydrothermal.The stable isotope research that these devices are low concentration hydro carbons provides basic means, due to the difference of enrichment object, the part such as sample introduction, enrichment cold-trap in online cold-trap enriching apparatus be there are differences, and enriching apparatus differs from one another, but the aspect such as accuracy, practicality still comes with some shortcomings.
The scholars such as Tsunogai (Tsunogai, et al., 1998,2000) in methane and deep-sea hydrothermal during the stable carbon isotope research of methane, devise roughly similar online methane-rich system in air.This device is made up of 3 cold-traps, 2 chromatographic columns, 1 six-way valve.This device manual operational unit is many, complex operation, cold-trap control temperature difficulty; Tang Junhong etc. (2006) use for reference the thinking of the scholars such as Tsunogai, its component is simplified, only adopt 1 cold-trap, but its manually-operated gate parts are still more, complicated operation, and only have one-level cold-trap to carry out enrichment to hydro carbons such as the methane in gas, this will continue to enter by directly causing the gas sample in chromatogram, cause the peak hangover of target components obviously, the poor accuracy of data measured.
The another kind of similar enriching apparatus of the scholars such as Rice (Rice, et al., 2001) design and use.This device is made up of 2 six-way valves and 2 cold-traps.By " six-way valve " to methane preenrichment, " cold-trap " is assembled again to methane, multi-position valve handoff technique achieves carbon to methane in air, hydrogen isotope analysis, but this device has its shortcoming: 1, owing to employing quantity tube, limit sample size, limitation is existed to the analysis of other similar samples; 2, this device has " six-way valve " and " cold-trap " two cold-trap end members simultaneously, be used separately as first enrichment and again enrichment optimize peak shape, but design existing defects, this is the hydro carbons owing to flowing out from " six-way valve ", if do not lived by " cold-trap " complete enrichment, what hydro carbons that then have trace, that be not frozen in can continue flows to chromatographic column, causes in chromatographic column and can there is high background value, directly cause the accuracy of detected value to be deteriorated.
Allen and Stephanie (Allen, Stephanie 2003) uses the carbon isotope composition of volatile component in preenrichment device stable connection isotope mass spectrometry research air.This enriching apparatus by sample pot, vacuum diaphragm pump, electromagnetic flow control device, 2 dewater and CO
2trap, two-stage low temperature enrichment unit form, and be connected to chromatogram-combustion furnace-stable isotope mass spectrum detect by a gas six-way valve.Its mode adopting vacuum diaphragm pump to vacuumize impels sample gas through preenrichment cold-trap, and this can cause in enrichment cold-trap and form certain negative pressure, and this enrichment for the low molecular hydrocarbon of high volatility is totally unfavorable.In addition, although its manual components relatively other devices had and significantly simplified, but still seem too loaded down with trivial details.Above-mentioned several enriching apparatus parts are many, and need manual operation more, are difficult to the accurate control realizing each action, and the comparability of different group test result can be caused thus poor, and this is also one of maximum shortcoming of said apparatus.
(the Cao Yacheng such as Cao Yacheng, 2008) PreCon utilizing Thermofisher company of the U.S. to produce connects GC/C-IRMS and measures the Methane Carbon Isotope in air, it can carry out stable carbon isotope mensuration to the methane in air well, but do not consider the heavy hydrocarbon in gas sample due to its design concept, it can not carry out enrichment to the ethane in gas sample, hydrocarbon gas more than propane, is also just difficult to realize the Stable Isotopic Analysis to these components.
At present, key issue how to build a set of simple to operate, quick, widely applicable, trace hydrocarbon component enriching apparatus with good repeatability.
Utility model content
For solving the problems of the technologies described above, the purpose of this utility model is to provide a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection.
For achieving the above object, the utility model provides a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, and this device comprises the logical valve 102 of the first injector the 101, the 1, chemical trap the 103, the 28 logical valve 104, second injector 105, first cold-trap 106, second cold-trap 107, first helium pressure regulator valve 108, second helium pressure regulator valve 109, the 3rd helium pressure regulator valve 110;
Described first injector 101 is connected by the 6th port 6 of pipeline with the one or eight logical valve 102, and the two ends of chemical trap 103 lead to valve 102 respectively by pipeline five-port 5 with the one or eight is connected with the two or eight the 7th port G leading to valve 104;
The two ends of described first cold-trap 106 are connected with the 8th port H with the two or eight the 3rd port C leading to valve 104 respectively by pipeline;
By pipeline, the first port A of valve 104 logical with the two or eight, the 8th port 8 of the one or eight logical valve 102 are connected respectively at the two ends of described second cold-trap 107;
The five-port E of the described 28 logical valve 104 is connected by the 3rd port 3 of pipeline with the one or eight logical valve 102;
Described second injector 105 is connected by the second port B of pipeline with the two or eight logical valve 104;
Described first helium pressure regulator valve 108 is connected with the first injector 101 by pipeline;
Described second helium pressure regulator valve 109, the 3rd helium pressure regulator valve 110 are connected with the one or eight the 4th port 4, second port 2 leading to valve 102 respectively by pipeline;
Wherein the one or eight logical the first port one described in valve 102 is arranged clockwise to the 8th port 8;
Wherein the two or eight logical the first port A described in valve 104 is arranged counterclockwise to the 8th port H.
According to device described in the utility model, described eight logical valves are this area conventional equipment, such as are that port becomes eight of circular arrangement logical valves.
According to device described in the utility model, above-mentioned first helium pressure regulator valve 108 is connected with the first injector 101 by pipeline, and it can provide the helium flow of constant voltage for the first injector 101, and the flow velocity controlling helium is 5-10mL/min;
Above-mentioned second helium pressure regulator valve 109 is connected by the 4th port 4 of pipeline with the one or eight logical valve 102, and it can provide the helium flow of constant voltage for the first eight logical valves 102, and the flow velocity of control helium is 1-2mL/min;
Above-mentioned 3rd helium pressure regulator valve 110 is connected by second port 2 of pipeline with the one or eight logical valve 102, and it can provide the helium flow of constant voltage for the second eight logical valves 104, and the flow velocity of control helium is 1-2mL/min.
According to device described in the utility model, preferably, described pipeline is quartz capillary.
According to device described in the utility model, preferably,
When this device is in preenrichment state, the logical valve 104 of the one or eight logical valve the 102 and the 28 is all in " loading " state, and now, five-port 5 and the 6th port 6 of the one or eight logical valve 102 are connected; 7th port G and the 8th port H of the two or eight logical valve 104 are connected, 3rd port C and the 4th port D is connected, and forms the state that the first injector the 101, the 1 leads to valve 102, logical valve 104, first cold-trap 106 of chemical trap the 103, the 28 is connected successively thus;
When this device is in secondary enrichment, the one or eight logical valve 102 is in " loading " state, and the two or eight logical valve 104 is in " sample introduction " state, and now, the 7th port 7 and the 8th port 8 of the one or eight logical valve 102 are connected; Second port B and the 3rd port C of the two or eight logical valve 104 are connected, first port A and the 8th port H is connected, and forms the state that the logical valve 102 of the second injector the 105, the 28 logical valve 104, first cold-trap 106, second cold-trap the 107, the 1 is connected successively thus;
After secondary enrichment terminates, the hydro carbons of enrichment will enter chromatographic column 111 and the stable isotope mass spectrometer 112 of gas chromatograph successively, now, two or eight logical valve 104 is in " loading " state, one or eight logical valve 102 is in " sample introduction " state, and the first port one and the 8th port 8 of the one or eight logical valve 102 are connected; First port A and the second port B of the two or eight logical valve 104 are connected, one or eight logical first port one of valve 102 is connected with the chromatographic column 111 of gas chromatograph, forms the logical state that valve 104, second cold-trap the 107, the 1 leads to valve 102, the chromatographic column 111 of gas chromatograph is connected successively of the second injector the 105, the 28 thus.
According to device described in the utility model, preferably, described first cold-trap 106 is the cold-trap of stainless steel pipeline filling 80-100 order 5A molecular sieve.
According to device described in the utility model, preferably, the internal diameter of described stainless steel pipeline is 0.8-1.2mm, is more preferably 1mm.
According to device described in the utility model, preferably, described second cold-trap 107 is the cold-trap of stainless steel pipeline filling 80-100 order 5A molecular sieve.
According to device described in the utility model, preferably, the internal diameter of described stainless steel pipeline is 0.4-0.6mm, is more preferably 0.5mm.
According to device described in the utility model, preferably, described chemical trap 103 is quartz glass tube chemistry trap, and by the glass wool shutoff of its two ends.
According to device described in the utility model, preferably, described chemical trap 103 is the chemical trap that in quartz glass tube, subsection filling has calcium oxide and magnesium perchlorate or NaOH and magnesium perchlorate.
According to device described in the utility model, preferably, the internal diameter of described quartz glass tube is 3-6mm.
According to device described in the utility model, the part in above-mentioned first injector 101 rock gas that to be these detect for stable isotope in trace hydro carbons enriching apparatus, its former injection port with gas chromatograph, i.e. the effect difference of the second injector 105; The effect of the first injector 101 is the rock gases being injected proper volume by syringe, and the helium for purging is injected in the effect of the second injector 105.In view of the first injector is different from the effect that the second injector plays, therefore, the service condition of the two is also incomplete same.The utility model is that make enriching apparatus of the present utility model variant in performance relative to existing equipment, the utility model self does not improve the first injector 101 because newly increased the first injector 101 in this enriching apparatus.
According to device described in the utility model, above-mentioned first cold-trap 106, second cold-trap 107 is the cold-trap of this area routine, the utility model does not improve the structure of this cold-trap, just due to different from the enrichment object of cold-trap of the prior art, and then the filler loaded in cold-trap is different, the filler of filling in the first cold-trap 106, second cold-trap 107 of the present utility model is 80-100 object 5A molecular sieve.
According to device described in the utility model, the working temperature of above-mentioned first cold-trap 106, second cold-trap 107 is 77 ± 10K; By the first cold-trap 106, second cold-trap 107 is placed in liquid nitrogen, remain on 77 ± 10K to make the working temperature of the first cold-trap 106, second cold-trap 107.
According to device described in the utility model, above-mentioned chemical trap 103 is the chemical trap of this area routine, and the utility model does not improve the structure of this chemical trap, and in the utility model, the effect of chemical trap 103 absorbs the CO in rock gas
2, H
2the components such as O.
Of the present utility model for stable isotope detect rock gas in trace hydro carbons enriching apparatus be connected between the injection port of gas chromatograph and the chromatographic column 111 of gas chromatograph.Above-mentioned second injector 105 is the original injection port of gas chromatograph, and the one or eight logical first port one of valve 102 is connected with the chromatographic column 111 of gas chromatograph.
According to device described in the utility model, the logical valve 104 of the above-mentioned 1 logical valve the 102, the 28 is equipped with drain, and other gases such as helium can pass through drain discharger; In preferred embodiment of the present utility model, the 7th port 7 of the one or eight logical valve 102 is drain, and the 4th port D, the 6th port F of the two or eight logical valve 104 are drain.
According to device described in the utility model, the logical valve 104 of above-mentioned 1 logical valve the 102, the 28 is that the routine eight of this area leads to valve, the utility model does not improve the logical valve 104 of the above-mentioned 1 logical valve the 102, the 28, eight ports of the above-mentioned 1 logical valve 102 are labeled as port one-8 respectively, and the position of the first port one, the second port 2, the 3rd port 3, the 4th port 4, five-port 5, the 6th port 6, the 7th port 7, the 8th port 8 carries out arranging according to the order of 1-8; Eight ports of the two or eight logical valve 104 are labeled as port A-H respectively, and the position of the first port A, the second port B, the 3rd port C, the 4th port D, five-port E, the 6th port F, the 7th port G, the 8th port H carries out arranging according to the order of A-H.
According to device described in the utility model, this device can be used for stable isotope and detects, and in preferred embodiment of the present utility model, aforementioned stable isotope comprises the isotope of carbon, hydrogen.
To adopt in the above-mentioned rock gas detected for stable isotope trace hydro carbons enriching apparatus to trace hydro carbons carry out enrichment and stable carbon isotope detect time, can carry out as follows:
1, the preenrichment of trace hydrocarbon gas:
Adjust the logical valve 104 of the one or eight logical valve the 102 and the 28 and be all in " loading " state, now the logical valve 102 of the first injector the 101, the 1, logical valve 104, first cold-trap 106 of chemical trap the 103, the 28 are connected successively;
First cold-trap 106 is placed in liquid nitrogen, and cooling more than 30s, makes the temperature of the first cold-trap 106 remain on 77K;
With syringe, the rock gas of proper volume (this volume is different with the difference of enrich target component concentration, and sample size is generally 10 microlitre-5 milliliters) is injected the first injector 101, the CO in rock gas
2, H
2the components such as O are adsorbed when chemical trap 103, hydrocarbon component enrichment in the first cold-trap 106, and other gases are discharged through the 4th port D of the two or eight logical valve 104, and the time of above-mentioned preenrichment is about 120s;
Now, second cold-trap 107 is not placed in liquid nitrogen, the logical valve 102 of second injector the 105, the 28 logical valve 104, second cold-trap the 107, the 1 is connected successively, helium in second injector 105 will flow continuously through the second cold-trap 107, and the 7th port 7 on the one or eight logical valve 102 is discharged, and can reach and rush the object of sweeping to remaining hydro carbons in the second cold-trap 107.
2, the secondary enrichment of trace hydrocarbon gas:
In Pre-enrichment, the second cold-trap 107 is put into liquid nitrogen by 30s in advance, makes the temperature of the second cold-trap 107 remain on 77K;
Adjust the two or eight logical valve 104 and be in " sample introduction " state, the one or eight logical valve 102 is still in " loading " state.Now, the logical valve 102 of the second injector the 105, the 28 logical valve 104, first cold-trap 106, second cold-trap the 107, the 1 is connected successively;
Proposed from liquid nitrogen by first cold-trap 106, at room temperature, in the first cold-trap 106, the hydrocarbon gas of enrichment discharges, and enters enrichment in the second cold-trap 107, and unnecessary helium is discharged by the 7th port 7 on the one or eight logical valve 102.The time of secondary enrichment is about 120s.
In this process, the helium flow in the first injector 101 continues to flow into chemical trap 103, and discharges from the 6th port F the two or eight logical valve 104, to reach the object of rinsing rock gas residual in chemical trap.
3, chromatogram-stable isotope mass spectrophotometry
After secondary enrichment terminates, by the hydro carbons of enrichment enter gas chromatography-stable isotope mass spectrum be used in conjunction instrument time, the logical valve 104 of adjustment the two or eight is in " loadings " state, and the one or eight leads to valve 102 is in " sample introduction " state, now, the first port one of the one or eight logical valve 102 and the 8th port 8 are connected; First port A and the second port B of the two or eight logical valve 104 are connected, one or eight logical first port one of valve 102 is connected with the chromatographic column 111 of gas chromatograph, forms the logical state that valve 104, second cold-trap the 107, the 1 leads to valve 102, the chromatographic column 111 of gas chromatograph is connected successively of the second injector the 105, the 28 thus.
Second cold-trap 107 is proposed from liquid nitrogen, at room temperature, by the helium flow in the second injector 105, the hydro carbons of enrichment in the second cold-trap 107 is brought into the chromatographic column 111 of gas chromatograph.Hydrocarbon component after being separated, entering oxidation tube successively and is oxidized, product C O in the chromatographic column 111 of gas chromatograph
2enter stable isotope mass spectrometer to analyze, obtain the carbon isotope value of hydrocarbon component.
Now, second helium pressure regulator valve 109, chemical trap 103, two or eight logical valve 104, first cold-trap 106 is connected successively, the helium flow that second helium pressure regulator valve 109 provides flows through logical valve 104, first cold-trap 106 of chemical trap the 103, the 28 successively, the 4th port D on the two or eight logical valve 104 discharges, to reach the object of rinsing gas component residual in chemical trap 103, first cold-trap 106.
After detection completes, the first cold-trap 106 is reentered in liquid nitrogen, and adjusts the logical valve 104 of the one or eight logical valve the 102 and the 28 and be all in " loading " state, to carry out the analysis of next sample.
Above process can set gradually action through stable isotope mass spectrometer workstation, realizes automatically controlling, thus guarantees the repeatability of analytic process.
The utility model provides a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, and it is arranged between the injection port of gas chromatograph and the chromatographic column of gas chromatograph, and increases a special injector newly.By the water in chemical trap removing rock gas sample and CO
2, eluting gas carries out first enrichment in the liquid nitrogen cold trap being filled with 5A molecular sieve, is changed by pneumatic valve, the product of first enrichment is filled with enrichment again in the liquid nitrogen cold trap of 5A molecular sieve at another, makes hydrocarbon component more concentrated, contributes to optimizing peak shape.Subsequently, at ambient temperature, discharged by the product of secondary enrichment, bring enriched product into chromatographic column by the helium in the original injection port of chromatograph, hydrocarbon component, after chromatographic column is separated, is oxidized, product C O successively
2enter stable isotope mass spectrometer to analyze, obtain the carbon isotope value of hydrocarbon component.
Compared with prior art, the utility model has the advantage of:
1, the utility model devises independent injection port for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, has broken away from the restriction of the original injection port of chromatograph.Not only can trace hydrocarbon component in enrichment conventional gas, and to the more special gaseous sample of sampling ratio (as: usually containing more CO in the gas in geology inclusion, air, moral purity, deep-sea hydrothermal
2, H
2o, O
2, N
2) in the hydrocarbon gas of microscratch amount also can effectively enrichment.
2, the utility model adopts two-stage to be filled with the cold-trap of 5A molecular sieve for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, and the temperature of its work is controlled by liquid nitrogen, bioaccumulation efficiency is high, greatly can reduce the injection rate IR of sample on the one hand; On the other hand, the internal diameter slightly large (1mm) of preenrichment cold-trap, substantially reduces the time needed for enrichment.Hydro carbons enrichment again in secondary enrichment cold-trap of preenrichment, the internal diameter of secondary enrichment cold-trap is 0.5mm, close to the diameter (0.32mm) of chromatographic column, hydro carbons component when entering chromatographic column can be made more concentrated, reduce the appearance of tailed peak, make detection data more accurate.
3, the utility model adopts two eight logical valves for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, switched by pneumatic valve, both two cold-traps had been met to the demand of hydrocarbon gas enrichment, guarantee that again the void gas component flowing out cold-trap is discharged by drain in time, avoid the pollution to pipeline.Meanwhile, in the process of Vavle switching, with helium, the parts and pipeline that have played effect are purged in time, effectively prevent the pollution to next sample.
4, the utility model is used for the action of each assembly in trace hydro carbons enriching apparatus in the rock gas of stable isotope detection by conputer controlled, and avoid manually operated difference to cause the difference detecting data, Data Detection precision is high, good comparability.
5, the utility model is good for the compatibility of trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, be not limited to and be connected with gas chromatograph, stable isotope mass spectrometer, it can also connect by checkout equipment different from other, realizes the detection analysis of disparity items.As connected on gas chromatograph, the light hydrocarbon component (C to trace in rock gas can be realized
5-C
8) analyze.
Of the present utility model for stable isotope detect rock gas in trace hydro carbons enriching apparatus simple to operate, quick, accurate, widely applicable, there is good repeatability.Device of the present utility model can realize, to the on-line preconcentration of trace hydro carbons in rock gas, being connected, can realizing the Stable Isotopic Analysis of different hydrocarbons component with gas chromatograph, stable isotope mass spectrometer.
Accompanying drawing explanation
In Fig. 1 rock gas that to be the utility model detect for stable isotope, trace hydro carbons enriching apparatus is in the schematic diagram of preenrichment state;
In Fig. 2 rock gas that to be the utility model detect for stable isotope, trace hydro carbons enriching apparatus is in the schematic diagram of secondary enrichment state;
Fig. 3 is the schematic diagram that the hydro carbons of trace hydro carbons enriching apparatus enrichment in the rock gas detected for stable isotope through the utility model enters Spectrometry state;
Fig. 4 is that in stake 202 rock gas after embodiment 2 is diluted, the ethane of trace and propane, after the enrichment of this enriching apparatus, are oxidized successively, product C O after the chromatographic column of gas chromatograph is separated again
2enter stable isotope mass spectrometer to carry out analyzing the analysis of spectra obtained;
Fig. 5 is that in stake 202 rock gas after embodiment 2 is diluted, the ethane of trace and propane, without enrichment, are directly oxidized successively, product C O after the chromatographic column of gas chromatograph is separated again
2enter stable isotope mass spectrometer to carry out analyzing the analysis of spectra obtained;
Fig. 6 is that in stake 202 rock gas of the not diluted of embodiment 2, ethane and propane, without enrichment, are directly oxidized successively, product C O after the chromatographic column of gas chromatograph is separated again
2enter stable isotope mass spectrometer to carry out analyzing the analysis of spectra obtained.
Main Reference label declaration:
The logical valve of 101 first injector 102 the or eight
The logical valve of 103 chemical trap 104 the two or eight
105 second injector 106 first cold-traps
107 second cold-trap 108 first helium pressure regulator valves
109 second helium pressure regulator valve 110 the 3rd helium pressure regulator valves
Chromatographic column 112 stable isotope mass spectrometer (IRMS) of 111 gas chromatographs
Eight ports of the one or eight logical valve 102 are respectively the first port one, the second port 2, the 3rd port 3, the 4th port 4, five-port 5, the 6th port 6, the 7th port 7, the 8th port 8;
Eight ports of the two or eight logical valve 104 are respectively the first port A, the second port B, the 3rd port C, the 4th port D, five-port E, the 6th port F, the 7th port G, the 8th port H.
Embodiment
In order to there be understanding clearly to technical characteristic of the present utility model, object and beneficial effect, referring now to Figure of description, following detailed description is carried out to the technical solution of the utility model, but can not be interpreted as to of the present utility model can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection, this device comprises the logical valve 102 of the first injector the 101, the 1, chemical trap the 103, the 28 logical valve 104, second injector 105, first cold-trap 106, second cold-trap 107, first helium pressure regulator valve 108, second helium pressure regulator valve 109, the 3rd helium pressure regulator valve 110;
Described first injector 101 is connected by the 6th port 6 of quartz capillary with the one or eight logical valve 102, and the two ends of chemical trap 103 lead to valve 102 respectively by quartz capillary five-port 5 with the one or eight is connected with the two or eight the 7th port G leading to valve 104;
The two ends of described first cold-trap 106 are connected with the 8th port H with the two or eight the 3rd port C leading to valve 104 respectively by quartz capillary;
By quartz capillary, the first port A of valve 104 logical with the two or eight, the 8th port 8 of the one or eight logical valve 102 are connected respectively at the two ends of described second cold-trap 107;
The five-port E of the described 28 logical valve 104 is connected by the 3rd port 3 of quartz capillary with the one or eight logical valve 102;
Described second injector 105 is connected by the second port B of quartz capillary with the two or eight logical valve 104;
Described first helium pressure regulator valve 108 is connected with the first injector 101 by quartz capillary; It can provide the helium flow of constant voltage for the first injector 101, and to control its flow velocity be 5-10mL/min;
Described second helium pressure regulator valve 109, the 3rd helium pressure regulator valve 110 are connected with the one or eight the 4th port 4, second port 2 leading to valve 102 respectively by quartz capillary, second helium pressure regulator valve 109, the 3rd helium pressure regulator valve 110 are respectively the helium flow that the logical valve 104 of the one or eight logical valve the 102, the 28 provides constant voltage, and control its flow velocity and be 1-2mL/min.
The logical valve 104 of above-mentioned 1 logical valve the 102, the 28 is equipped with drain, and other gases such as helium can pass through drain discharger; 7th port 7 of the one or eight logical valve 102 is drain in the present embodiment, and the 4th port D, the 6th port F of the two or eight logical valve 104 are drain.
Above-mentioned first cold-trap 106 adopts internal diameter be the stainless steel pipeline of 1mm and fill 80-100 object 5A molecular sieve formation;
Above-mentioned second cold-trap 107 adopts internal diameter be the stainless steel pipeline of 0.5mm and fill 80-100 object 5A molecular sieve formation;
Above-mentioned chemical trap 103 adopts internal diameter to be the quartz glass tube of 6mm, fills calcium oxide (CaO) and magnesium perchlorate (Mg (ClO in quartz glass tube
4)
2), and glass wool shutoff is used at two ends;
The working temperature of above-mentioned first cold-trap 106, second cold-trap 107 is 77 ± 10K.
When this device is in preenrichment state, the logical valve 104 of the one or eight logical valve the 102 and the 28 is all in " loading " state, and now, five-port 5 and the 6th port 6 of the one or eight logical valve 102 are connected; 7th port G and the 8th port H of the two or eight logical valve 104 are connected, 3rd port C and the 4th port D is connected, form the state that the first injector the 101, the 1 leads to valve 102, logical valve 104, first cold-trap 106 of chemical trap the 103, the 28 is connected successively thus, its constitutional diagram as shown in Figure 1;
When this device is in secondary enrichment, the one or eight logical valve 102 is in " loading " state, and the two or eight logical valve 104 is in " sample introduction " state, and now, the 7th port 7 and the 8th port 8 of the one or eight logical valve 102 are connected; Second port B and the 3rd port C of the two or eight logical valve 104 are connected, first port A and the 8th port H is connected, form the state that the logical valve 102 of the second injector the 105, the 28 logical valve 104, first cold-trap 106, second cold-trap the 107, the 1 is connected successively thus, its constitutional diagram as shown in Figure 2;
After secondary enrichment terminates, the hydro carbons of enrichment will enter chromatographic column 111 and the stable isotope mass spectrometer 112 of gas chromatograph, now, two or eight logical valve 104 is in " loading " state, one or eight logical valve 102 is in " sample introduction " state, now, the first port one of the one or eight logical valve 102 and the 8th port 8 are connected; First port A and the second port B of the two or eight logical valve 104 are connected, one or eight logical first port one of valve 102 is connected with the chromatographic column 111 of gas chromatograph, form the logical valve 102 of logical valve 104, second cold-trap of the second injector the 105, the 28 the 107, the 1 thus, state that the chromatographic column 111 of gas chromatograph, stable isotope mass spectrometer 112 are connected successively, its constitutional diagram is as shown in Figure 3.
Embodiment 2
The present embodiment carries out on-line preconcentration-stable carbon isotope to the ethane in stake 202 rock gas after dilution and propane components and detects, it adopts realizing for trace hydro carbons enriching apparatus in the rock gas of stable isotope detection of embodiment 1, and this detection method comprises the following steps:
In stake 202 rock gas in the present embodiment, the volume content of ethane is 11.23%, and the volume content of propane is 7.32%, and use helium to dilute stake 202 rock gas, after dilution, in rock gas, the volume content of ethane is about 0.04%.
1, the preenrichment of trace hydrocarbon gas:
Adjust the logical valve 104 of the one or eight logical valve the 102 and the 28 and be all in " loading " state, now the logical valve 102 of the first injector the 101, the 1, logical valve 104, first cold-trap 106 of chemical trap the 103, the 28 are connected successively;
First cold-trap 106 is placed in liquid nitrogen, and cooling more than 30s, makes the temperature of the first cold-trap 106 remain on 77K;
With syringe, stake 202 rock gas after 180 microlitre dilutions is injected the first injector 101, the CO in rock gas
2, H
2the components such as O are adsorbed when chemical trap 103, hydrocarbon component enrichment in the first cold-trap 106, and other gases are discharged through the 4th port D of the two or eight logical valve 104, and the time of above-mentioned preenrichment is about 120s;
Now, second cold-trap 107 is not placed in liquid nitrogen, the logical valve 102 of second injector the 105, the 28 logical valve 104, second cold-trap the 107, the 1 is connected successively, helium in second injector 105 will flow continuously through the second cold-trap 107, and the 7th port 7 on the one or eight logical valve 102 is discharged, and can reach and rush the object of sweeping to remaining hydro carbons in the second cold-trap 107.
2, the secondary enrichment of trace hydrocarbon gas:
In Pre-enrichment, the second cold-trap 107 is put into liquid nitrogen by 30s in advance, makes the temperature of the second cold-trap 107 remain on 77K;
Adjust the two or eight logical valve 104 and be in " sample introduction " state, the one or eight logical valve 102 is still in " loading " state.Now, the logical valve 102 of the second injector the 105, the 28 logical valve 104, first cold-trap 106, second cold-trap the 107, the 1 is connected successively;
Proposed from liquid nitrogen by first cold-trap 106, at room temperature, in the first cold-trap 106, the hydrocarbon gas of enrichment discharges, and enters enrichment in the second cold-trap 107, and unnecessary helium is discharged by the 7th port 7 on the one or eight logical valve 102, and the time of secondary enrichment is about 120s.
In this process, the helium flow in the first injector 101 continues to flow into chemical trap 103, and discharges from the 6th port F the two or eight logical valve 104, to reach the object of rinsing rock gas residual in chemical trap.
3, chromatogram-stable isotope mass spectrophotometry
After secondary enrichment terminates, by the hydro carbons of enrichment enter gas chromatography-stable isotope mass spectrum be used in conjunction instrument time, the logical valve 104 of adjustment the two or eight is in " loadings " state, and the one or eight leads to valve 102 is in " sample introduction " state, now, the first port one of the one or eight logical valve 102 and the 8th port 8 are connected; First port A and the second port B of the two or eight logical valve 104 are connected, one or eight logical first port one of valve 102 is connected with the chromatographic column 111 of gas chromatograph, forms the state that logical valve 104, second cold-trap the 107, the 1 of the second injector the 105, the 28 leads to valve 102, the chromatographic column 111 of gas chromatograph, stable isotope mass spectrometer 112 are connected successively thus.
Second cold-trap 107 is proposed from liquid nitrogen, at room temperature, by the helium flow in the second injector 105, the hydro carbons of enrichment in the second cold-trap 107 is brought into the chromatographic column 111 of gas chromatograph.Hydrocarbon component after being separated, entering oxidation tube successively and is oxidized, product C O in the chromatographic column 111 of gas chromatograph
2enter stable isotope mass spectrometer 112 to analyze, collected by stable isotope mass spectrometer 112
12c
16o
16o,
13c
16o
16o,
12c
18o
16the gas chromatogram of O and ratio thereof, process the data obtained, and obtains the carbon isotope ratio of ethane and propane components, as shown in table 1.Meanwhile, in the rock gas after dilution, the ethane of trace and propane are after the enrichment of this enriching apparatus, are oxidized successively, product C O after the chromatographic column 111 of gas chromatograph is separated again
2enter stable isotope mass spectrometer 112 and carry out analyzing the analysis of spectra that obtains as shown in Figure 4.
Now, second helium pressure regulator valve 109, chemical trap 103, two or eight logical valve 104, first cold-trap 106 is connected successively, the helium flow that second helium pressure regulator valve 109 provides flows through chemical trap 103 successively, two or eight logical valve 104, first cold-trap 106, the 4th port D on the two or eight logical valve 104 discharges, to reach the object of rinsing gas component residual in chemical trap 103, first cold-trap 106.
After detection completes, the first cold-trap 106 is reentered in liquid nitrogen, and adjusts the logical valve 104 of the one or eight logical valve the 102 and the 28 and be all in " loading " state, to carry out the analysis of next sample.
Embodiment 3
The present embodiment carries out stable carbon isotope detection to the ethane in stake 202 rock gas after dilution and propane components, its do not adopt embodiment 1 for stable isotope detect rock gas in trace hydro carbons enriching apparatus carry out enrichment, its detection method is identical with the method in embodiment 2, difference part is that the sample size of stake 202 rock gas after diluting is 2000 microlitres, in stake 202 rock gas after dilution, the ethane of trace and propane are without enrichment, directly be oxidized successively again after the chromatographic column 111 of gas chromatograph is separated, product C O
2enter stable isotope mass spectrometer 112 and carry out analyzing the analysis of spectra that obtains as shown in Figure 5, test result is as shown in table 1.
Embodiment 4
The present embodiment carries out stable carbon isotope detection to the ethane in stake 202 rock gas and propane components, its do not adopt embodiment 1 for stable isotope detect rock gas in trace hydro carbons enriching apparatus carry out enrichment, its detection method is identical with the method in embodiment 2, difference part is that the sample size of stake 202 rock gas is 6 microlitres, in stake 202 rock gases, the ethane of trace and propane are without enrichment, directly be oxidized successively again after the chromatographic column 111 of gas chromatograph is separated, product C O
2enter stable isotope mass spectrometer 112 and carry out analyzing the analysis of spectra that obtains as shown in Figure 6, test result is as shown in table 1.
Above process can set gradually action through stable isotope mass spectrometer workstation, realizes automatically controlling, thus guarantees the repeatability of analytic process.
In Fig. 4,5,6, peak 1, peak 2, peak 3 are the peak of Standard Gases (gas) the CO2 gas of stable isotope mass spectrometer work; Peak 4 is the peak of ethane component; Peak 5 is the peak of propane components; Peak 6 is the peak of isobutane component; Peak 7 is the peak of normal butane.The utility model chooses 4-peak, peak 7 as a comparison, investigates the performance of enriching apparatus of the present utility model.
Experimental data as can be seen from table 1, if the stake after dilution 202 rock gas does not use the enriching apparatus of the utility model embodiment 1 to carry out enrichment, and directly use routine inspection method to detect, its measured value and standard value (stake 202 rock gas) differ greatly, ethane carbon isotope measured value differs 3.7 ‰, much larger than systematic error 0.5 ‰ with standard value (standard value of ethane carbon isotope is-29.71); And identical stake 202 rock gas sample, through the enriching apparatus of the utility model embodiment 1, the sample size of stake 202 rock gas samples is reduced to 180 microlitres by 2000 microlitres carrying out enrichment without enriching apparatus before, the peak intensity of ethane brings up to 17V (as shown in Figure 4) by about the 3V (as shown in Figure 5) carrying out enrichment without enriching apparatus, and this can absolutely prove that enriching apparatus bioaccumulation efficiency of the present utility model is high.In addition, stake 202 rock gas sample is after enriching apparatus enrichment of the present utility model, and the carbon isotope measured value of each component such as ethane, propane differs very little with standard value, illustrate that obvious carbon isotope fractionation does not occur enrichment process; In the utility model, with stake 202 rock gas of not diluted without enrichment, be directly oxidized successively again after the chromatographic column 111 of gas chromatograph is separated, product C O
2enter stable isotope mass spectrometer 112 and carry out analyzing the data of acquisition as standard value, therefore, the standard value of ethane, propane, isobutane, normal butane carbon isotope is respectively-29.71 ,-28.72 ,-27.78 ,-27.26.
In sum, can think of the present utility model for trace hydro carbons enriching apparatus enrichment superior performance in the rock gas of stable isotope detection.
Table 1
Claims (9)
1. one kind for stable isotope detect rock gas in trace hydro carbons enriching apparatus, it is characterized in that, this device comprises the first injector (101), the one or eight logical valve (102), chemical trap (103), the two or eight logical valve (104), the second injector (105), the first cold-trap (106), the second cold-trap (107), the first helium pressure regulator valve (108), the second helium pressure regulator valve (109), the 3rd helium pressure regulator valve (110);
Described first injector (101) is connected by the 6th port (6) of pipeline with the one or eight logical valve (102), and the two ends of chemical trap (103) lead to valve (102) respectively by pipeline five-port (5) with the one or eight is connected with the two or eight the 7th port (G) leading to valve (104);
The two ends of described first cold-trap (106) are connected with the 8th port (H) with the two or eight the 3rd port (C) leading to valve (104) respectively by pipeline;
By pipeline, first port (A) of valve (104) logical with the two or eight, the 8th port (8) of the one or eight logical valve (102) are connected respectively at the two ends of described second cold-trap (107);
The five-port (E) of the described 28 logical valve (104) is connected by the 3rd port (3) of pipeline with the one or eight logical valve (102);
Described second injector (105) is connected by second port (B) of pipeline with the two or eight logical valve (104);
Described first helium pressure regulator valve (108) is connected with the first injector (101) by pipeline;
The 4th port (4) of valve (102) logical with the or eight, the second port (2) are connected respectively by pipeline for described second helium pressure regulator valve (109), the 3rd helium pressure regulator valve (110);
Wherein the one or eight logical the first port (1) described in valve (102) is arranged clockwise to the 8th port (8);
Wherein the two or eight logical the first port (A) described in valve (104) is arranged counterclockwise to the 8th port (H).
2. device according to claim 1, is characterized in that, described pipeline is quartz capillary.
3. device according to claim 1, is characterized in that,
When this device is in preenrichment state, one or eight logical valve (102) and the two or eight logical valve (104) are all in " loading " state, now, the five-port (5) of the one or eight logical valve (102) is connected with the 6th port (6); 7th port (G) of the two or eight logical valve (104) is connected with the 8th port (H), 3rd port (C) and the 4th port (D) are connected, and form the first injector (101) thus, state that the one or eight logical valve (102), chemical trap (103), the two or eight logical valve (104), the first cold-trap (106) are connected successively;
When this device is in secondary enrichment, one or eight logical valve (102) is in " loading " state, two or eight logical valve (104) is in " sample introduction " state, now, the 7th port (7) of the one or eight logical valve (102) is connected with the 8th port (8); Second port (B) of the two or eight logical valve (104) is connected with the 3rd port (C), first port (A) and the 8th port (H) are connected, and form the second injector (105) thus, state that the two or eight logical valve (104), the first cold-trap (106), the second cold-trap (107), the one or eight logical valve (102) are connected successively;
After secondary enrichment terminates, the hydro carbons of enrichment will enter chromatographic column (111) and the stable isotope mass spectrometer (112) of gas chromatograph successively, now, two or eight logical valve (104) is in " loading " state, one or eight logical valve (102) is in " sample introduction " state, and first port (1) of the one or eight logical valve (102) is connected with the 8th port (8); First port (A) of the two or eight logical valve (104) is connected with the second port (B), one or eight logical first port (1) of valve (102) is connected with the chromatographic column (111) of gas chromatograph, forms the second injector (105), the two or eight thus and leads to valve (104), the second cold-trap (107), the or eight leads to valve (102), the chromatographic column (111) of gas chromatograph is connected successively state.
4. the device according to any one of claim 1-3, is characterized in that, described first cold-trap (106) is the cold-trap of stainless steel pipeline filling 80-100 order 5A molecular sieve.
5. device according to claim 4, is characterized in that, the internal diameter of described stainless steel pipeline is 0.8-1.2mm.
6. the device according to any one of claim 1-3, is characterized in that, described second cold-trap (107) is the cold-trap of stainless steel pipeline filling 80-100 order 5A molecular sieve.
7. device according to claim 6, is characterized in that, the internal diameter of described stainless steel pipeline is 0.4-0.6mm.
8. the device according to any one of claim 1-3, is characterized in that, described chemical trap (103) is quartz glass tube chemistry trap, and by the glass wool shutoff of its two ends.
9. device according to claim 8, is characterized in that, the internal diameter of described quartz glass tube is 3-6mm.
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| CN117269383B (en) * | 2023-09-05 | 2024-06-18 | 中国科学院深海科学与工程研究所 | Multi-type low Wen Duobu purging and concentrating device and purging and concentrating method thereof |
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