CN105548416A - Hydrogen isotope analysis method of light hydrocarbon monomer hydrocarbon in natural gas and light hydrocarbon enrichment apparatus - Google Patents
Hydrogen isotope analysis method of light hydrocarbon monomer hydrocarbon in natural gas and light hydrocarbon enrichment apparatus Download PDFInfo
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- CN105548416A CN105548416A CN201510962416.6A CN201510962416A CN105548416A CN 105548416 A CN105548416 A CN 105548416A CN 201510962416 A CN201510962416 A CN 201510962416A CN 105548416 A CN105548416 A CN 105548416A
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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
- 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
Abstract
The present invention provides a hydrogen isotope analysis method of a light hydrocarbon monomer hydrocarbon in natural gas and a light hydrocarbon enrichment apparatus. The apparatus comprises a natural gas sample cylinder, a light hydrocarbon collection bottle, a water removal purification pipe, a light hydrocarbon enrichment tube and a temperature control box; the natural gas sample cylinder and the water removal purification pipe are in communication, a connecting pipe of the natural gas sample cylinder and the water removal purification pipe is provided with a gas-pressure meter and a first needle valve; the water removal purification pipe is in communication with one end of the light hydrocarbon enrichment tube, a connecting pipe of the water removal purification pipe and the light hydrocarbon enrichment tube is provided with a tee joint, and the tee joint is in communication with the light hydrocarbon collection bottle; the other end of the light hydrocarbon enrichment tube and a gas flowmeter are in communication, a connecting pipe of the light hydrocarbon enrichment tube and the gas flowmeter is provided with a second needle valve; the other end of the light hydrocarbon enrichment tube is provided with a third needle valve; and the temperature control box is arranged outside the light hydrocarbon enrichment tube. The hydrogen isotope analysis method of the light hydrocarbon monomer hydrocarbon in the natural gas is completed by use of the light hydrocarbon enrichment apparatus. The hydrogen isotope analysis method of the light hydrocarbon monomer hydrocarbon in the natural gas and the light hydrocarbon enrichment apparatus have the advantages of simple structure, easy and fast operation, high analysis data accuracy and good repeatability.
Description
Technical field
The present invention relates to a kind of light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method and rock gas lighter hydrocarbons enriching apparatus, belong to petroleum geology exploration field.
Background technology
Rock gas is a kind of high-quality, efficient, clean low-carbon energy.China's natural gas aboundresources, but discovery degree is low, and development potentiality is larger.Development natural gas exploration and development gordian technique, accelerates Gas Industry development, for adjustment China energy structure, uplift the people's living standard, promote energy-saving and emission-reduction, reply climate change has important strategic importance.
In rock gas, each gas composition and carbon thereof, hydrogen isotope data play an important role in Natural Gas Origin, source and degree of ripeness research thereof.But because gas component is fairly simple, the principal ingredient of deep layer, highly-matured gas and biogas is only methane, the Geochemical Characteristics of gaseous component in simple dependence rock gas, special in the natural gas province with mixed sources, qualitative sentence to know and degree of ripeness is determined to be difficult to obtain reliable result, assist the Geochemical Characteristics research carrying out association lighter hydrocarbons in rock gas then can provide information and evidence more accurately.
Accompanying natural gas lighter hydrocarbons are important component parts of rock gas gas reservoir, containing abundant geochemical information, are applied to mainly its component and the individual carbon isotope data of petroleum exploration domain at present.Light hydrocarbon component in mensuration rock gas and individual carbon isotope generally adopt the method for chromatographic column front end liquid nitrogen frozen to carry out enrichment method.Rock gas injects from injection port, and light hydrocarbon component is wherein frozen enrichment in chromatographic column front end, and after removing cold-trap, each light hydrocarbon component is separated in the chromatography column and enters detecting device or isotope mass spectrometer successively, thus obtains corresponding light hydrocarbon component or carbon isotopic data.
Petroleum gas hydrogen isotope is great for oil and gas geochemistry Research Significance, and the analysis of oil gas detailed hydrocarbon hydrogen isotope and application thereof are forward position and the difficult point of research at present.But the mensuration of rock gas light hydrocarbon component/individual carbon isotope can't be used for measuring light hydrocarbon monomer hydrogen isotope, this is because
1h and
2relative mass difference ratio between D
12c and
13c is large, and in identical change procedure, the fractionation of hydrogen isotope is more obvious.In the freezing of post front end, cold-trap withdraws rear each light hydrocarbon compounds can produce obvious hydrogen isotope fractionation from solid-state becoming in the process of gaseous state, and this will cause analysis result to occur deviation.
In order to solve the isotope assay problem of low concentration component in rock gas, the people such as Henning devise a set of gas sample and sampling system for measuring C
1-C
5alkane hydro carbon isotope, but this system does not have concentration effect, is not too applicable to the hydrogen isotope analysis of light hydrocarbon monomer.Publication number is the Chinese patent application of CN103048412A and CN103048394A, preenrichment chromatogram-mass spectrometric analysis for isotope the system of design can be used for the hydrogen isotope analysis of low abundance hydrogen in rock gas, but have employed online input mode owing to have employed 5A molecular sieve as adsorbent, hydrogen isotope fractionation effect and the dead volume excessive chromatographic peak broadening caused and the problem such as overlapping may be produced when carrying out lighter hydrocarbons enrichment and analyzing.Therefore it is very necessary for developing new rock gas light hydrocarbon monomer hydrocarbon hydrogen isotope analysis method.
Summary of the invention
In order to solve the problems of the technologies described above, the object of the present invention is to provide a kind of easy to operate, quick, analyze the light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method that data accuracy is high and reproducible, and meet the structure simple rock gas lighter hydrocarbons enriching apparatus of above-mentioned analytical approach requirement.
In order to realize above-mentioned technical purpose, the present invention provide firstly a kind of rock gas lighter hydrocarbons (C
5-12) enriching apparatus, this rock gas lighter hydrocarbons enriching apparatus comprises: rock gas sample steel cylinder, the purification pipe that dewaters, lighter hydrocarbons receiving flask, lighter hydrocarbons enrichment pipe and temperature-controlled box;
Wherein, described rock gas sample steel cylinder is communicated with the purification pipe that dewaters, and described rock gas sample steel cylinder is provided with rain glass, the first needle-valve with the connecting line of the purification pipe that dewaters;
The described purification pipe that dewaters is communicated with one end of lighter hydrocarbons enrichment pipe, described in the dewater connecting line of purification pipe and lighter hydrocarbons enrichment pipe threeway is set, described threeway is communicated with lighter hydrocarbons receiving flask;
The other end of described lighter hydrocarbons enrichment pipe is communicated with gas meter, and the connecting line of described lighter hydrocarbons enrichment pipe and gas meter is provided with the second needle-valve;
The other end of described lighter hydrocarbons enrichment pipe is provided with the 3rd needle-valve;
The outer setting of described lighter hydrocarbons enrichment pipe has temperature-controlled box.
In above-mentioned rock gas lighter hydrocarbons enriching apparatus provided by the invention, preferably, described lighter hydrocarbons enrichment pipe is hollow stainless-steel tube.
In above-mentioned rock gas lighter hydrocarbons enriching apparatus provided by the invention, preferably, in described lighter hydrocarbons enrichment pipe, be filled with activated charcoal or molecular sieve adsorption material.
According to the specific embodiment of the present invention, can filling 5A molecular sieve in lighter hydrocarbons enrichment pipe, but be not limited to 5A molecular sieve.Even if filling 5A molecular sieve, because above-mentioned rock gas lighter hydrocarbons enriching apparatus of the present invention is off-line enriching apparatus, the lighter hydrocarbons of enrichment finally by solvent at low temperatures wash-out collect in lighter hydrocarbons receiving flask, airtight lighter hydrocarbons receiving flask guarantees that light hydrocarbon component avoids volatilization to scatter and disappear, not only can auto injection analysis, also there will not be obvious fractionation effect, and the problem that dead volume is excessive.
In above-mentioned rock gas lighter hydrocarbons enriching apparatus provided by the invention, the rain glass on the connecting line that rock gas sample steel cylinder is communicated with the purification pipe that dewaters is near natural gas steel cylinder side, and the first needle-valve is near dewatering purification pipe side.
Present invention also offers a kind of light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method, it utilizes above-mentioned rock gas lighter hydrocarbons enriching apparatus to complete, and this light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method comprises the following steps:
In the described purification pipe that dewaters, load water suction filler, the first needle-valve, the second needle-valve, the 3rd needle-valve are all in closed condition, and described threeway is communicated with lighter hydrocarbons enrichment pipe with the purification pipe that dewaters, and disconnects with lighter hydrocarbons receiving flask;
Refrigerant is injected in described temperature-controlled box, when the temperature of temperature-controlled box drops to temperature required, open the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder, make the rock gas in rock gas sample steel cylinder flow through lighter hydrocarbons enrichment pipe with the speed of 1mL/min-4mL/min;
After being enriched to the light hydrocarbon component meeting test request, close the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder, described threeway is communicated with lighter hydrocarbons enrichment pipe with lighter hydrocarbons receiving flask, and disconnects with the purification pipe that dewaters;
The temperature of adjustment temperature-controlled box is-50 DEG C to-60 DEG C, eluant, eluent is injected by the 3rd needle-valve, the light hydrocarbon component of enrichment is eluted in lighter hydrocarbons receiving flask through lighter hydrocarbons enrichment pipe by eluant, eluent, detailed hydrocarbon is obtained through chromatograph analysis, after pyrolysis furnace, carry out isotope analysis, complete the analysis to light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope.Here the light hydrocarbon component meeting test request refers to that the carbon number reaching certain enriching quantity is the component of 5-12.Concrete enriching quantity is that those skilled in the art are rule of thumb confirmable.
In light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention, preferably, when carrying out chromatograph analysis, chromatographic condition is: chromatography capillary post is PONA post, the specification of chromatography capillary post is 50m × 0.2mm × 0.5 μm, flow rate of carrier gas is 0.8mL/min-1.5mL/min (being more preferably 1.5mL/min), injector temperature is 280 DEG C-300 DEG C (being more preferably 280 DEG C), post case initial temperature 30 DEG C-35 DEG C (being more preferably 30 DEG C), with the ramp to 70 DEG C of 1 DEG C/min-5 DEG C/min (being more preferably 1.5 DEG C/min) after constant temperature 10min-30min (being more preferably 15min), again with the ramp to 130 DEG C of 2 DEG C/min-10 DEG C/min (being more preferably 2.5 DEG C/min), then constant temperature is kept until all chromatographic peaks have gone out with the ramp to 280 DEG C-300 DEG C (being more preferably 280 DEG C) of 3 DEG C/min-10 DEG C/min (being more preferably 3.5 DEG C/min).
In light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention, preferably, when carrying out isotope analysis, isotope mass spectrometry condition is: Pintsch process furnace temperature 1420 DEG C-1450 DEG C (being more preferably 1450 DEG C), ion gun vacuum tightness 2.1 × 10
-6mBar-2.6 × 10
-6mBar (is more preferably 2.6 × 10
-6mBar), ion source voltage 9.51kV-10kV (being more preferably 9.51kV), the H of isotope instrument
3 +factor values <1.0 × 10
-5and keep stable.
In light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention, preferably, described eluant, eluent comprises carbon disulphide or methylene chloride.
In light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention, preferably, the refrigerant of employing comprises liquid nitrogen, dry ice or other cold-producing medium; More preferably, the refrigerant of employing comprises liquid nitrogen or dry ice.Wherein, when selecting liquid nitrogen to be cold-producing medium, the whole low boiling point hydrocarbon component (C comprising methane can be collected
1+); And when selecting dry ice as cold-producing medium, the low boiling point hydrocarbon component (C of carbon number higher than heptane can be collected
7+).
In light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention, preferably, the water suction filler of employing comprises magnesium perchlorate, calcium oxide or Bibulous Silica Gel.
In above-mentioned light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method of the present invention, refrigerant is injected in temperature-controlled box, that opens in the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder when in temperature-controlled box, temperature drops to temperature required is temperature required, different according to the difference of refrigerant injected, those skilled in the art can determine as required.Such as: when liquid nitrogen is refrigerant, temperature is-195 DEG C, chilling temperature during ethanol solid-liquid two-phase coexistent is-114 DEG C, and when dry ice is refrigerant, temperature is-80 DEG C.
The light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method utilizing above-mentioned rock gas lighter hydrocarbons enriching apparatus to complete provided by the invention, specifically comprises the following steps:
At the water suction filler that in purification pipe, loading has activated that dewaters, the airtight connection of each parts of rock gas lighter hydrocarbons enriching apparatus, first needle-valve, the second needle-valve and the 3rd needle-valve are all in closed condition, and threeway is communicated with lighter hydrocarbons enrichment pipe with the purification pipe that dewaters, and disconnects with lighter hydrocarbons receiving flask;
Refrigerant is injected in temperature-controlled box, when in temperature-controlled box, temperature drops to temperature required, the valve of slow unlatching first needle-valve, the second needle-valve and rock gas sample steel cylinder, the rock gas in rock gas sample steel cylinder is made to flow through lighter hydrocarbons enrichment pipe with the speed of 1mL/min-4mL/min, higher boiling light hydrocarbon component in rock gas meets the enrichment of condensation knot at lighter hydrocarbons enrichment pipe place, lower boiling gas composition is then discharged from flowmeter;
After being enriched to the light hydrocarbon component meeting test request, close the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder, threeway is communicated with lighter hydrocarbons enrichment pipe with lighter hydrocarbons receiving flask, and purification pipe disconnects with dewatering;
The temperature of temperature-controlled box is adjusted to-50 DEG C to-60 DEG C, and inject eluant, eluent by the 3rd needle-valve, the light hydrocarbon component of enrichment is eluted in lighter hydrocarbons receiving flask through lighter hydrocarbons enrichment pipe by eluant, eluent, and sealing is preserved.From lighter hydrocarbons receiving flask, get the sample of appropriate volume by automatic sampler when carrying out light hydrocarbon analysis and inject chromatography column feed materials mouth, the each component of lighter hydrocarbons is separated into detailed hydrocarbon in chromatographic capillary chromatographic column, the gas that isotope instrument detects is converted into subsequently in pyrolysis furnace, finally obtain each light hydrocarbon component detailed hydrocarbon hydrogen isotope value in rock gas by the software kit of isotope instrument, complete the analysis to light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope; Wherein,
Chromatographic running parameter is set as follows: chromatography capillary post is PONA post, the specification of chromatography capillary post is 50m × 0.2mm × 0.5 μm, flow rate of carrier gas is 0.8mL/min-1.5mL/min (being preferably 1.5mL/min), injector temperature is 280 DEG C-300 DEG C (being preferably 280 DEG C), post case initial temperature 30 DEG C-35 DEG C (being preferably 30 DEG C), with the ramp to 70 DEG C of 1 DEG C/min-5 DEG C/min (being preferably 1.5 DEG C/min) after constant temperature 10min-30min (be preferably 15min), again with the ramp to 130 DEG C of 2 DEG C/min-10 DEG C/min (being preferably 2.5 DEG C/min), then constant temperature is kept until all chromatographic peaks have gone out with the ramp 280 DEG C-300 DEG C of 3 DEG C/min-10 DEG C/min (being preferably 3.5 DEG C/min) (being preferably 280 DEG C),
The running parameter of isotope mass spectrometry is set as follows: Pintsch process furnace temperature 1420 DEG C-1450 DEG C (being preferably 1450 DEG C), ion gun vacuum tightness 2.1 × 10
-6mBar-2.6 × 10
-6mBar (is preferably 2.6 × 10
-6mBar), ion source voltage 9.51kV-10kV (being preferably 9.51kV), the H of isotope instrument
3 +factor values <1.0 × 10
-5and keep stable.
The accuracy of the rock gas light hydrocarbon monomer hydrocarbon hydrogen isotope value utilizing light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method provided by the invention to obtain is high and reproducible.
Rock gas lighter hydrocarbons enriching apparatus processing and fabricating of the present invention is simple, easy to use, and lighter hydrocarbons concentration effect is obvious, and main enrichment means cost is lower, can reuse according to demand or single use.
The lighter hydrocarbons of rock gas lighter hydrocarbons enriching apparatus of the present invention enrichment are analyzed by chromatogram automatic sampler auto injection, and analysis operation is simple.
The rock gas sample utilizing rock gas lighter hydrocarbons enriching apparatus of the present invention to collect can be used for multiple Natural Gas Analysis project, such as chromatographic quantitative analysis and isotope analysis.
Accompanying drawing explanation
Fig. 1 is the rock gas lighter hydrocarbons enriching apparatus structural representation in embodiment 1.
Fig. 2 is lighter hydrocarbons concentration effect chromatogram in the rock gas sample in embodiment 1.
Fig. 3 is lighter hydrocarbons concentration effect chromatogram in the rock gas sample in embodiment 1.
Main Reference symbol description
A rock gas sample steel cylinder B rain glass C1 first needle-valve C2 second needle-valve C3 the 3rd needle-valve D dewaters the threeway F lighter hydrocarbons receiving flask G lighter hydrocarbons enrichment pipe H temperature-controlled box I gas meter that purification pipe E can be communicated with between two
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
The present embodiment provide firstly a kind of rock gas lighter hydrocarbons enriching apparatus, and as shown in Figure 1, it comprises the structural representation of this rock gas lighter hydrocarbons enriching apparatus: rock gas sample steel cylinder A, the purification pipe D that dewaters, lighter hydrocarbons receiving flask F, lighter hydrocarbons enrichment pipe G and temperature-controlled box H;
Wherein, rock gas sample steel cylinder A is communicated with the purification pipe D that dewaters, and the connecting line of the two is provided with rain glass B, the first needle-valve C1; Rain glass B is near natural gas steel cylinder A, and the first needle-valve C1 is near dewatering purification pipe D;
The purification pipe D that dewaters is communicated with one end of lighter hydrocarbons enrichment pipe G, and the connecting line of the two is provided with the threeway E that can be communicated with between two;
The other end of lighter hydrocarbons enrichment pipe G is communicated with gas meter I, the connecting line of the two is provided with the second needle-valve C2;
The other end of lighter hydrocarbons enrichment pipe G is provided with the 3rd needle-valve C3;
The outer setting of lighter hydrocarbons enrichment pipe G has temperature-controlled box H;
Lighter hydrocarbons enrichment pipe G is the hollow stainless-steel tube being filled with activated charcoal or molecular sieve adsorption material.
The present embodiment additionally provides the light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method utilizing above-mentioned rock gas lighter hydrocarbons enriching apparatus to complete, and specifically comprises the following steps:
At the water suction filler that in purification pipe D, loading has activated that dewaters, by the airtight connection of each parts of rock gas lighter hydrocarbons enriching apparatus, first needle-valve C1, the second needle-valve C2, the 3rd needle-valve C3 are all in closed condition, the threeway E that can be communicated with between two is communicated with the purification pipe D and lighter hydrocarbons enrichment pipe G that dewaters, and disconnects with lighter hydrocarbons receiving flask F;
Liquid nitrogen is injected in temperature-controlled box H, when in temperature-controlled box H, temperature drops to temperature required, the valve of slow unlatching first needle-valve C1, the second needle-valve C2 and rock gas sample steel cylinder A, the rock gas in rock gas sample steel cylinder A is made to flow through lighter hydrocarbons enrichment pipe G with the speed of 1mL/min-4mL/min, higher boiling light hydrocarbon component in rock gas meets the enrichment of condensation knot at lighter hydrocarbons enrichment pipe G place, lower boiling gas composition is then discharged from gas meter I;
The valve of the first needle-valve C1, the second needle-valve C2, the 3rd needle-valve C3 and rock gas sample steel cylinder A is closed after being enriched to the light hydrocarbon component meeting test request, the threeway E that can be communicated with between two is communicated with lighter hydrocarbons enrichment pipe G with lighter hydrocarbons receiving flask F, and purification pipe D disconnects with dewatering;
The temperature of temperature-controlled box H is adjusted to-60 DEG C, eluant, eluent is injected by the 3rd needle-valve C3, the light hydrocarbon component of enrichment is eluted in lighter hydrocarbons receiving flask F through lighter hydrocarbons enrichment pipe G by eluant, eluent, sealing is preserved, from lighter hydrocarbons receiving flask F, get the sample of appropriate volume by automatic sampler when carrying out light hydrocarbon analysis and inject chromatography column feed materials mouth, the each component of lighter hydrocarbons is separated into detailed hydrocarbon in chromatographic capillary chromatographic column, the gas that isotope instrument detects is converted into subsequently in pyrolysis furnace, finally obtain each light hydrocarbon component detailed hydrocarbon hydrogen isotope value in rock gas by the software kit of isotope instrument, complete the analysis to light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope, wherein,
Setting chromatographic condition of work is: chromatography capillary post is PONA post (50m × 0.2mm × 0.5 μm), flow rate of carrier gas is 1.5mL/min, injector temperature is 280 DEG C, post case initial temperature 30 DEG C, 70 DEG C are raised to 1.5 DEG C/min after constant temperature 15min, be raised to 130 DEG C with 2.5 DEG C/min again, be then raised to 280 DEG C with 3.5 DEG C/min and keep constant temperature until all chromatographic peaks have gone out;
The condition of work of setting isotope mass spectrometry is: Pintsch process furnace temperature 1450 DEG C, ion gun vacuum tightness 2.6 × 10
- 6mBar, ion source voltage 9.51kV, the H of isotope instrument
3 +factor values <1.0 × 10
-5and keep stable;
Wherein, as shown in Figures 2 and 3, the corresponding compound title of each chromatographic peak is in table 1 (only having marked the lighter hydrocarbons peak number that component concentration is larger) for rock gas lighter hydrocarbons concentration effect chromatogram.
Table 1
Above embodiment illustrates, rock gas lighter hydrocarbons enriching apparatus provided by the invention can be used for multiple Natural Gas Analysis project, such as chromatographic quantitative analysis and isotope analysis; The accuracy of light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method is high and reproducible.
Claims (10)
1. a rock gas lighter hydrocarbons enriching apparatus, is characterized in that, this rock gas lighter hydrocarbons enriching apparatus comprises: rock gas sample steel cylinder, the purification pipe that dewaters, lighter hydrocarbons receiving flask, lighter hydrocarbons enrichment pipe and temperature-controlled box;
Wherein, described rock gas sample steel cylinder is communicated with the purification pipe that dewaters, and described rock gas sample steel cylinder is provided with rain glass, the first needle-valve with the connecting line of the purification pipe that dewaters;
The described purification pipe that dewaters is communicated with one end of lighter hydrocarbons enrichment pipe, described in the dewater connecting line of purification pipe and lighter hydrocarbons enrichment pipe be provided with threeway, described threeway is communicated with described lighter hydrocarbons receiving flask;
The other end of described lighter hydrocarbons enrichment pipe is communicated with gas meter, and the connecting line of described lighter hydrocarbons enrichment pipe and gas meter is provided with the second needle-valve;
The other end of described lighter hydrocarbons enrichment pipe is provided with the 3rd needle-valve;
The outer setting of described lighter hydrocarbons enrichment pipe has temperature-controlled box.
2. rock gas lighter hydrocarbons enriching apparatus according to claim 1, is characterized in that, described lighter hydrocarbons enrichment pipe is hollow stainless-steel tube.
3. rock gas lighter hydrocarbons enriching apparatus according to claim 1 and 2, is characterized in that, is filled with activated charcoal or molecular sieve adsorption material in described lighter hydrocarbons enrichment pipe.
4. a light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method, it utilizes the rock gas lighter hydrocarbons enriching apparatus described in any one of claim 1-3 to complete, and it is characterized in that, this light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method comprises the following steps:
In the described purification pipe that dewaters, load water suction filler, the first needle-valve, the second needle-valve, the 3rd needle-valve are all in closed condition, and described threeway is communicated with lighter hydrocarbons enrichment pipe with the purification pipe that dewaters, and disconnects with lighter hydrocarbons receiving flask;
Refrigerant is injected in described temperature-controlled box, when the temperature of temperature-controlled box drops to temperature required, open the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder, make the rock gas in rock gas sample steel cylinder flow through lighter hydrocarbons enrichment pipe with the speed of 1mL/min-4mL/min;
After being enriched to the light hydrocarbon component meeting test request, closing the valve of the first needle-valve, the second needle-valve and rock gas sample steel cylinder, threeway is communicated with lighter hydrocarbons enrichment pipe with lighter hydrocarbons receiving flask, and disconnect with the purification pipe that dewaters;
The temperature of adjustment temperature-controlled box is-50 DEG C to-60 DEG C, eluant, eluent is injected by the 3rd needle-valve, the light hydrocarbon component of enrichment is eluted in lighter hydrocarbons receiving flask through lighter hydrocarbons enrichment pipe by eluant, eluent, detailed hydrocarbon is obtained through chromatograph analysis, after pyrolysis furnace, carry out isotope analysis, complete the analysis to light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope.
5. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 4, it is characterized in that, when carrying out chromatograph analysis, chromatographic condition is: chromatography capillary post is PONA post, the specification of chromatography capillary post is 50m × 0.2mm × 0.5 μm, flow rate of carrier gas is 0.8mL/min-1.5mL/min, injector temperature is 280 DEG C-300 DEG C, post case initial temperature 30 DEG C-35 DEG C, with the ramp to 70 DEG C of 1 DEG C/min-5 DEG C/min after constant temperature 10min-30min, again with the ramp to 130 DEG C of 2 DEG C/min-10 DEG C/min, then constant temperature is kept until all chromatographic peaks have gone out with the ramp to 280 of 3 DEG C/min-10 DEG C/min DEG C-300 DEG C.
6. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 4, it is characterized in that, when carrying out isotope analysis, isotope mass spectrometry condition is: Pintsch process furnace temperature 1420 DEG C-1450 DEG C, ion gun vacuum tightness 2.1 × 10
- 6mBar-2.6 × 10
-6mBar, ion source voltage 9.51kV-10kV, the H of isotope instrument
3 +factor values <1.0 × 10
-5and keep stable.
7. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 4, it is characterized in that, described eluant, eluent comprises carbon disulphide or methylene chloride.
8. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 4, it is characterized in that, described refrigerant comprises liquid nitrogen, dry ice or other cold-producing medium.
9. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 8, it is characterized in that, described refrigerant comprises liquid nitrogen or dry ice.
10. light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method according to claim 4, it is characterized in that, described water suction filler comprises magnesium perchlorate, calcium oxide or Bibulous Silica Gel.
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