CN109100413A - System and method for analyzing carbon and hydrogen isotopes oil-free valve of mineral fluid inclusion - Google Patents
System and method for analyzing carbon and hydrogen isotopes oil-free valve of mineral fluid inclusion Download PDFInfo
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- CN109100413A CN109100413A CN201811068229.3A CN201811068229A CN109100413A CN 109100413 A CN109100413 A CN 109100413A CN 201811068229 A CN201811068229 A CN 201811068229A CN 109100413 A CN109100413 A CN 109100413A
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- 238000000034 method Methods 0.000 title claims abstract description 102
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 87
- 239000011707 mineral Substances 0.000 title claims abstract description 87
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000012530 fluid Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 115
- 238000004880 explosion Methods 0.000 claims abstract description 73
- 238000004458 analytical method Methods 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000012360 testing method Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000007710 freezing Methods 0.000 claims description 36
- 230000008014 freezing Effects 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 34
- 238000006722 reduction reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 21
- 238000005086 pumping Methods 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- 238000001819 mass spectrum Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000004519 grease Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 2
- 235000010755 mineral Nutrition 0.000 description 81
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 description 37
- 239000010453 quartz Substances 0.000 description 36
- 239000003921 oil Substances 0.000 description 31
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 25
- 239000005751 Copper oxide Substances 0.000 description 23
- 229910000431 copper oxide Inorganic materials 0.000 description 23
- 238000005422 blasting Methods 0.000 description 20
- 238000011068 loading method Methods 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000190070 Sarracenia purpurea Species 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- COUNCWOLUGAQQG-UHFFFAOYSA-N copper;hydrogen peroxide Chemical compound [Cu].OO COUNCWOLUGAQQG-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002307 isotope ratio mass spectrometry Methods 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical group [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a carbon and hydrogen isotope oil-free valve analysis system for a mineral fluid inclusion, and belongs to the technical field of analysis and detection. The analysis system provided by the invention comprises a gas taking system, a conversion and purification system, a reduction hydrogen production and collection system and a vacuum control system. The analysis system provided by the invention adopts the thermal explosion gas extraction system and the crushing gas extraction system which are connected in parallel, so that the system can freely select a thermal explosion method or a crushing method according to mineral samples and the research requirement; moreover, valves of the whole system are oil-free valves, so that the influence and interference of vacuum grease in the oil-containing valves on analysis results are avoided; meanwhile, the analysis system has the advantages of strong repeatability, simple steps, high analysis and test precision and more stable test data than the test data of an oil valve system.
Description
Technical field
The present invention relates to the technical field of analysis detection, in particular to a kind of mineral fluid inclusions carbon, hydrogen isotope without
Oil valve door analysis system and method.
Background technique
Fluid when mineral formation is represented due to mineral fluid inclusions ingredient, so Fluid Inclusion Compositions contain its master
Diagenesis when mineral originally form or the information at mine, its ingredient (including Element and isotope composition) research is always the earth
The emphasis of the disciplinary studies such as science, environmental science.
Mineral fluid inclusions Stable Isotopic Analysis has two class methods at present: one is the offline of traditional two-way sample introduction
Analytic approach, another kind are the on-line analysis methods of continuous flow sample introduction.Off-line test method are as follows: first with various methods (explosion, pressure
It is broken and grind) gas and liquid in released mineral inclusion enclave collects then by separation, purification and redox reaction
Gas can be tested (for example, H2And CO2Gas), finally using gas isotope than mass spectrograph (IRMS, Isotope Ratio
Mass Spectrometry) entered with the mode of two-way sample introduction (duel inlet) and carries out analysis test.Continuous flow on-line analysis
Method is EA (elemental analyser)-IRMS (isotope ratio mass spectrum) joint technology.This method is exactly to utilize elemental analyser (instrument
Model: Flash 2000HT) high temperature (temperature is at 1400 DEG C or so) cracking inclusion enclave in water generate H2, then pass through chromatographic column
After isolating and purifying and mass spectrum is directly entered with the sample introduction mode of continuous flow (continuous flow) to be tested.Relative to rear
The advantages of person, traditional off-line test analysis method is: 1) analysis precision is high；2) a variety of isotopes can be analyzed；3) reduce benefit
Problem is cleared up with the mineral residue of continuous flow on-line analysis, can disposably analyze many samples.
Off-line test analysis for mineral fluid inclusions isotope two-way sample introduction, presently mainly uses two class sides
Method: thermal explosion method and crush method (or grinding method).Thermal explosion method makes mineral inclusion burst and discharge gas that is, by the method for heating
The method of body.Crush method is exactly to make the method for inclusion enclave rupture release gas using additional mechanical-physical pressure.Thermal explosion method is answered
With than wide, but it is only applicable to the mineral for being not easy to thermally decompose.Crush method is applied less at present, essentially consists in identical sample
The gas that amount specific heat is produced is slightly few, and crushes device and make cumbersome, higher cost.The most important advantage of crush method is that it is not only fitted
For being not easy to thermally decompose mineral, and for cannot apply thermal explosion method easily thermally decompose mineral (such as sulfide, it is pyrite, female
Pyrite, mispickel etc.) it is also suitable.
Mineral inclusion isotope two-way off-line analysis method mostly uses greatly oil valve door at present, there is the vacuum oil in oil valve door
Rouge will affect the accuracy of inclusion enclave isotope analysis.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of mineral fluid inclusions carbon, the oil-free valve analysis of hydrogen isotope
System and method.The present invention uses oil-free valve, improves the accuracy of isotope quantitative analysis in mineral fluid.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of mineral fluid inclusions carbon, the oil-free valve analysis system of hydrogen isotope, including take gas system
System, conversion and purification system, reduction hydrogen manufacturing and collection system and vacuum-control(led) system；
The air-taking system includes that thermal explosion air-taking system being sequentially communicated, being connected with parallel way and crushing take gas system
System, the 15th valve and third cold-trap；The thermal explosion air-taking system includes the thermal explosion device being sequentially communicated, the 18th valve and
17 valves；The crushing air-taking system includes the crushing device and the 16th valve being sequentially communicated；The thermal explosion air-taking system
In the 17th valve, the 16th valve in the crushing system simultaneously be connected to the 15th valve；
The conversion and purification system include the parallel system being sequentially communicated, the 8th valve, the second cold-trap；The taken in conjunction
System include with parallel way setting the first access formed by the 14th valve and the 12nd valve and by the 13rd valve,
The alternate path that copper oxide furnace and the 11st valve are formed；9th valve is set between the 8th valve and parallel system；Institute
State the 9th valve and CO2Sample collection tube connection；The 11st valve and the 12nd valve of 8th valve and parallel system
It is connected to simultaneously；
Pass through third cold-trap and the 16th valve and the between the air-taking system and the conversion and purification system
17 valves are connected to simultaneously；
The reduction hydrogen manufacturing and collection system include the 7th valve, reacting furnace, the first cold-trap, the 5th valve being sequentially communicated
Door, the 4th valve and H2Sample collection tube；6th valve is set between the 7th valve and reacting furnace；
Pass through the second cold-trap and the 7th valve between the conversion and purification system and reduction hydrogen manufacturing and the collection system
Connection；
The vacuum-control(led) system includes low vacuum extract system and fine pumping system；The fine pumping system
Pass through the first valve and the control of the second valve respectively with low vacuum extract system；The fine pumping system and low vacuum pumping
System accesses pipeline by third valve, the tenth valve and the 19th valve；Third valve setting in the 4th valve and
Between 5th valve；Tenth valve is arranged between the 9th valve and the parallel system；19th valve
It is arranged between the 18th valve and thermal explosion air-taking system；First vacuum meter is connected on third valve and the 4th valve
And on the 5th pipeline between valve；Second vacuum meter is connected on the 9th and the 11st pipeline between valve；The third
Vacuum meter is arranged between the 15th valve and the 16th valve, and the third vacuum meter is connect with the 17th valve；
First valve to the 19th valve is oil-free valve.
Preferably, the 6th valve is connect with standard sample injector.
The present invention also provides the analysis system described in above-mentioned technical proposal to mineral fluid inclusions carbon, hydrogen isotope into
The method of row analysis, comprising the following steps:
(1) after mineral samplers being packed into thermal explosion device or crushing device, vacuumize process is carried out to system；
(2) it after vacuumize process, carries out taking solid/liquid/gas reactions, obtains micro-molecular gas；The micro-molecular gas is in third
Freezing collection is carried out in cold-trap；
(3) micro-molecular gas that carrying out the first heating to third cold-trap collects third cold-trap releases, and by simultaneously
Connection system, obtains comprising CO2And H2The mixed gas of O, the mixed gas are transferred in the second cold-trap；Second cold-trap is carried out
Freezing liquid replacement, makes the CO in the second cold-trap2It releases, collects in CO2It is to be determined in sample collection tube；
(4)CO2After collection, the second heating is carried out to the second cold-trap, makes the H in the second cold-trap2O is released, and is led to
It crosses reacting furnace and carries out reduction reaction, the H that will be obtained2H is transferred to by the first cold-trap2It is to be determined in sample collection tube；
(5) by the H of collection2And CO2Carry out mass spectrum two-way off-line test.
Preferably, the refrigerant of third cold-trap is liquid nitrogen in the step (2)；The freezing examination of second cold-trap in step (3)
Agent is first liquid nitrogen, after replace with the mixture of dry ice and alcohol.
Preferably, the step (3) specifically:
After micro-molecular gas freezing is collected, the 7th valve, the 9th valve, the tenth valve and the 15th valve are closed；
And open the 11st valve, the 13rd valve and the 8th valve and open, and the 12nd valve and the 14th valve is kept to close, it will
The freezing reagent of third cold-trap replaces with hot water, makes micro-molecular gas by parallel system, obtains comprising CO2And H2The gaseous mixture of O
Mixed gas is transferred in the second cold-trap by body；
After mixed gas transfer, the 11st valve is closed, the liquid nitrogen in the second cold-trap is filled it up with, then opens the
Ten valves, the second valve；When vacuum degree be 10Pa when, close the second valve, open simultaneously the first valve, by the second cold-trap not
The gas that reagent freezes is frozen to take away；The tenth valve is turned off, replacing the freezing reagent in the second cold-trap is dry ice and alcohol
Mixture, open simultaneously the 9th valve, make the CO in the second cold-trap2It releases, and is collected into and connect with the 9th valve
CO2It is to be determined in sample collection tube.
Preferably, the temperature of the hot water is 40~60 DEG C.
Preferably, the freezing reagent in second cold-trap replaces with dry ice crude alcohol mixture.
Preferably, the CO2Acquisition time be 5min.
Preferably, the step (4) specifically:
Work as CO2After collection, the 7th valve, the 11st valve and the 12nd valve is kept to close, opens the tenth valve,
Second valve takes out low vacuum；It is then shut off the second valve, opens the first valve pumping high vacuum, pump and do not freezed in the second cold-trap
Gas；Then it keeps the 5th valve, the 6th valve and the 8th valve to close, opens the 7th valve, the freezing of the second cold-trap is tried
Agent replaces with hot water, by the H in the second cold-trap2O is released, and carries out reduction hydrogen production reaction by reacting furnace；Restore hydrogen manufacturing
After reaction, third valve and the 4th valve are closed, then the liquid nitrogen cup on the first cold-trap housing opens the 5th valve, note
The reading of lower first vacuum meter, as generation H2Amount；Then the 4th valve is opened, the 7th valve is closed, H2It collects to series connection
H after the 4th valve2It is to be measured in sample collection tube.Preferably, the temperature of the reduction reaction is 830~860 DEG C, the time
For 6min.
The present invention provides a kind of mineral fluid inclusions carbon, the oil-free valve analysis system of hydrogen isotope, including take gas system
System, conversion and purification system, reduction hydrogen manufacturing and collection system, vacuum-control(led) system.System provided by the invention is used with simultaneously
The thermal explosion air-taking system and crushing air-taking system that connection mode connects, make the system be applicable not only to be not easily decomposed mineral, Er Qieshi
Mineral for easily thermally decomposing, and unrestricted choice thermal explosion method or crush method can be needed with what is studied according to sample；Moreover,
The valve of whole system is oil-free valve, avoids influence and interference of the vacuum grease to analysis result in oil valve door；Together
When, system repeatability of the invention is strong, and it is high to analyze measuring accuracy.
The present invention provides a kind of methods for carrying out the analysis of fluid inclusion carbon-hydrogen isotopes using above-mentioned analysis system.This
Invention collects to obtain CO using above system2And H2Afterwards, then mass spectrum two-way off-line test is carried out.Method and step provided by the invention
Simply, analysis precision is high, reproducible.Embodiment the result shows that, using method of the invention to same quartz specimen carry out five
Secondary test, the average value of test result is -74 ‰, compared with utilizing and having 5 test results (- 75.2 ‰) of oil valve door system,
All in the error range of permission, the feasibility of oil-free valve system analysis method is confirmed, and oil-free valve system is tested
As a result standard deviation is smaller, as a result than there is oil valve door system more stable.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of mineral fluid inclusions carbon of the invention, the oil-free valve analysis system of hydrogen isotope；
In Fig. 1,1-1 is fine pumping system, and 2-1 is low vacuum extract system, 4-1 H2Sample collection tube, 5-1 are
First cold-trap, 6-1 are standard sample injector, and 7-1 is reacting furnace, and 8-1 is the second cold-trap, 9-1 CO2Sample collection tube, 13-1 are
Copper oxide furnace, 15-1 are third cold-trap, and 16-1 is crushing device, and 18-1 is thermal explosion device；
1 is the first valve, and 2 be the second valve, and 3 be third valve, and 4 be the 4th valve, and 5 be the 5th valve, and 6 be the 6th valve
Door, 7 be the 7th valve, and 8 be the 8th valve, and 9 be the 9th valve, and 10 be the tenth valve, and 11 be the 11st valve, and 12 be the 12nd
Valve, 13 be the 13rd valve, and 14 be the 14th valve, and 15 be the 15th valve, and 16 be the 16th valve, and 17 be the 17th valve
Door, 18 be the 18th valve, and 19 be the 19th valve；
I is the first vacuum meter, and II is the second vacuum meter, and III is third vacuum meter.
Specific embodiment
The present invention provides a kind of mineral fluid inclusions carbon, the oil-free valve analysis system of hydrogen isotope, structure such as Fig. 1 institutes
Show.In Fig. 1,1-1 is fine pumping system, and 2-1 is low vacuum extract system, 4-1 H2Sample collection tube, 5-1 first
Cold-trap, 6-1 are standard sample injector, and 7-1 is reacting furnace, and 8-1 is the second cold-trap, 9-1 CO2Sample collection tube, 13-1 are oxidation
Copper furnace, 15-1 are third cold-trap, and 16-1 is crushing device, and 18-1 is thermal explosion device；
1 is the first valve, and 2 be the second valve, and 3 be third valve, and 4 be the 4th valve, and 5 be the 5th valve, and 6 be the 6th valve
Door, 7 be the 7th valve, and 8 be the 8th valve, and 9 be the 9th valve, and 10 be the tenth valve, and 11 be the 11st valve, and 12 be the 12nd
Valve, 13 be the 13rd valve, and 14 be the 14th valve, and 15 be the 15th valve, and 16 be the 16th valve, and 17 be the 17th valve
Door, 18 be the 18th valve, and 19 be the 19th valve；
I is the first vacuum meter, and II is the second vacuum meter, and III is third vacuum meter.
The present invention provides a kind of mineral fluid inclusions carbon, the oil-free valve analysis system of hydrogen isotope, including take gas system
System, conversion and purification system, reduction hydrogen manufacturing and collection system, vacuum-control(led) system.
Mineral fluid inclusions carbon provided by the invention, the oil-free valve analysis system of hydrogen isotope, including air-taking system.?
In the present invention, the air-taking system includes that thermal explosion air-taking system being sequentially communicated, being connected with parallel way and crushing take gas system
System, the 15th valve and third cold-trap；The thermal explosion air-taking system includes the thermal explosion device being sequentially communicated, the 18th valve and
17 valves；The crushing air-taking system includes the crushing device and the 16th valve being sequentially communicated；The thermal explosion air-taking system
In the 17th valve, the 16th valve in the crushing system simultaneously be connected to the 15th valve.
In the present invention, the thermal explosion device includes the blasting cartridge inside high temperature furnace and high temperature furnace.The present invention is carrying out heat
It is quick-fried when taking gas, there is choosing that sample is placed in blasting cartridge, by high temperature boiler clothing on blasting cartridge, using high temperature furnace to the sample in blasting cartridge
Product are heated, and thermal explosion gas is generated.In the present invention, the blasting cartridge in the thermal explosion device is connected to the 18th valve, with
The thermal explosion gas for generating blasting cartridge enters system by the 18th valve.In the present invention, the blasting cartridge is preferably provided with one
A piston takes the gas to be when not needing thermal explosion, with piston by blasting cartridge and isolation of system.In the present invention, the temperature of the high temperature furnace
Degree is preferably by variable silicon transformer control.In the present invention, the material of the blasting cartridge is preferably quartz glass；The present invention is to institute
The size for stating blasting cartridge does not have particular/special requirement, uses the blasting cartridge of size known to those skilled in the art.
In the present invention, the material of the crushing device is preferably stainless steel.In the present invention, the shape of the crushing device
Shape is preferably cylindrical body, and the crushing device includes crushing chamber.In the present invention, the crushing chamber outer surface is covered with heating tape,
The temperature that crushing takes gas is obtained by controlling the heating tape.In the present invention, the inside of the crushing chamber, which is one, to turn
Dynamic objective table is loaded with the small column bucket that 12 internal diameters are 2cm, has a handle that can rotate loading outside big cylindrical body crushing chamber
Platform, entire cylindrical body crushing chamber are fixed in a hydraulic system, and it is hydraulic which has the foot pedal being connected on ground to control
Size, mineral samplers (< 10g) are put into small column bucket, and the position of cask is controlled by handle, are controlled using foot pedal hydraulic
Handle rolls the sample in specified small column, ruptures mineral inclusion, by the ingredient in mineral inclusion with gaseous state
Form releases.
The present invention does not have particular/special requirement to the shape design of the third cold-trap, using well known to those skilled in the art cold
Trap.
In the present invention, with the thermal explosion air-taking system of parallel way connection and crushing air-taking system in use, can root
It is selected according to the property of mineral sample, two kinds of air-taking systems are arranged in an analysis system present invention, simplify operation
Process.
In the present invention, the air-taking system can be such that carbon, protium in sample discharges in the form of micro-molecular gas
Out, it and collects in third cold-trap.
Mineral fluid inclusions carbon provided by the invention, the oil-free valve analysis system of hydrogen isotope, including conversion and purifying
System.In the present invention, the conversion and purification system include the parallel system being sequentially communicated, the 8th valve, the second cold-trap；Institute
Stating parallel system includes with the first access of parallel way setting formed by the 14th valve and the 12nd valve and by the
The alternate path that 13 valves, copper oxide furnace and the 11st valve are formed；Is arranged between 8th valve and parallel system
Nine valves；9th valve and CO2Sample collection tube connection；The 11st valve and of 8th valve and parallel system
12 valves are connected to simultaneously.In the present invention, first access and alternate path are selected according to actual needs；When
When needing to be reacted through copper dioxide furnace, alternate path is turned on, simultaneously closes off the first access；If you do not need to copper oxide
Furnace operates then opposite.
In the present invention, the structure of second cold-trap is preferably consistent with third cold-trap, and details are not described herein.The present invention couple
The CO2Collecting pipe does not have particular/special requirement, uses CO well known to those skilled in the art2Sample collection tube.
In the present invention, the material of the copper oxide furnace is preferably quartz glass；In a specific embodiment of the present invention, institute
It states copper oxide furnace and preferably includes air inlet pipe and an air outlet pipe, the air inlet pipe protrudes into copper oxide furnace bottom, and escape pipe is located at copper oxide
Furnace roof portion, to ensure going on smoothly for reaction in furnace.In the present invention, copper oxide is filled in the copper oxide furnace；The present invention
There is no particular/special requirement to the specific loadings of the copper oxide, it can be according to the access times of system and the amount of mineral samplers come really
Determine the loadings of copper oxide.
In the present invention, pass through third cold-trap and the described tenth between the air-taking system and the conversion and purification system
Six valves and the 17th valve are connected to simultaneously.
In the present invention, micro-molecular gas can be completely converted into CO with purification system by the conversion2And H2O gaseous mixture
Body；Simultaneously by CO2It collects.
Mineral fluid inclusions carbon provided by the invention, the oil-free valve analysis system of hydrogen isotope, including reduction hydrogen manufacturing with
Collection system.In the present invention, the reduction hydrogen manufacturing and collection system include the 7th valve, the reacting furnace, first being sequentially communicated
Cold-trap, the 5th valve, the 4th valve and H2Sample collection tube；6th valve is set between the 7th valve and reacting furnace.
In the present invention, preferably it is additionally provided with standard sample injector on the 6th valve, the standard sample injector is can be with
The L-type test tube of rotation, the L-type test tube have the hollow screw lid of rubber gasket, in preparation standard H2When, using standard into
Sample device injects standard water into system.
In the present invention, the reacting furnace is preferably chromium powder furnace.In the present invention, the material of the chromium powder furnace is preferably stone
English glass；The structure of the chromium powder furnace is preferably consistent with copper oxide furnace, and details are not described herein；Chromium is filled in the chromium powder furnace
Powder；In an embodiment of the present invention, when chromium powder loadings are 120g, 2000, sample of 2g or more can be tested.
In the present invention, the structure of first cold-trap is preferably consistent with third cold-trap, and details are not described herein.The present invention couple
The H2Sample collection tube does not have particular/special requirement, uses H well known to those skilled in the art2Sample collection tube.In the present invention
In, the H2Active carbon is filled in sample collection tube, preferably to realize to H2Collection.
In the present invention, pass through the second cold-trap between the conversion and purification system and reduction hydrogen manufacturing and the collection system
It is connected to the 7th valve.
In the present invention, the reduction hydrogen manufacturing and the effect of collection system are to be to the air-taking system, conversion and purifying
The H of system2O is restored, and collects H2。
Mineral fluid inclusions carbon provided by the invention, the oil-free valve analysis system of hydrogen isotope, including vacuum control system
System.In the present invention, the vacuum-control(led) system includes low vacuum extract system and fine pumping system；The high vacuum is taken out
Gas system and low vacuum extract system pass through the first valve and the control of the second valve respectively；The fine pumping system and low true
Empty pump gas system accesses pipeline by third valve, the tenth valve and the 19th valve；The third valve is arranged the described 4th
Between valve and the 5th valve；Tenth valve is arranged between the 9th valve and the parallel system；Described tenth
Nine valves are arranged between the 18th valve and thermal explosion air-taking system；First vacuum meter is connected on third valve and described the
On pipeline between four valves and the 5th valve；Second vacuum meter is connected on the 9th and the 11st pipeline between valve；Institute
It states third vacuum meter to be arranged between the 15th valve and the 16th valve, and the third vacuum meter and the 17th valve
Connection.
In the present invention, the low extract system that vacuumizes is preferably low vacuum mechanical pump；The low vacuum mechanical system
Operating pressure range be 105~10-2Pa。
In the present invention, the fine pumping system preferably includes concatenated fore pump and high vacuum metal diffusion pump.
In the present invention, the operating pressure range of the high vacuum mechanical system is 10-2~10-6Pa。
In the present invention, first valve to the 19th valve is oil-free valve.In the present invention, the no oil valve
Door is preferably two-way valve.The present invention does not have special restriction to the source of the oil-free valve, using those skilled in the art
Well known two lead to oil-free valve.System provided by the invention is all made of oil-free valve, has avoided grease pair in oil valve door
The influence of testing result.
In the present invention, the vacuum-control(led) system is capable of the vacuum degree of accurate detection system, reaches strict control vacuum
The purpose of degree, and then improve and take tolerance, collecting amount etc., reach and improves detection efficiency purpose.
The present invention also provides analysis systems described in utilization above-mentioned technical proposal to mineral fluid inclusions carbon, the same position of hydrogen
The method that element is analyzed, comprising the following steps:
(1) after mineral samplers being packed into thermal explosion device or crushing device, vacuumize process is carried out to system；
(2) it after vacuumize process, carries out taking solid/liquid/gas reactions, obtains micro-molecular gas；The micro-molecular gas is in third
Freezing collection is carried out in cold-trap；
(3) micro-molecular gas that carrying out the first heating to third cold-trap collects third cold-trap releases, and by simultaneously
Connection system, obtains comprising CO2And H2The mixed gas of O, the mixed gas are transferred in the second cold-trap；Second cold-trap is carried out
Freezing liquid replacement, makes the CO in the second cold-trap2It releases, collects in CO2It is to be determined in sample collection tube；
(4)CO2After collection, the second heating is carried out to the second cold-trap, makes the H in the second cold-trap2O is released, and is led to
It crosses reacting furnace and carries out reduction reaction, the H that will be obtained2It is transferred in the first cold-trap；Again by the H in the first cold-trap2It is transferred to H2Sample
It is to be determined in collecting pipe；
(5) by the H of collection2And CO2Carry out mass spectrum two-way off-line test.
Analysis method provided by the invention, first by mineral samplers be packed into thermal explosion device or crushing device after, to system into
Row vacuumize process.
In the present invention, for needing to carry out for the mineral samplers for taking gas using crushing system, system vacuumize process
Concrete operations process preferably include: by mineral samplers be packed into stainless steel cask, and by small cylinder by mark be put into crushing dress
It sets on the corresponding position of objective table, in addition disposable copper gasket, in crushing chamber lid, and tightens sealing；Meanwhile closing the first valve
Door, the piston that blasting cartridge is furnished with blasting cartridge beyond the Great Wall open other all valves, using low vacuum extract system, to system into
Row takes out low vacuum；When the reading of three vacuum meters is respectively less than 10Pa；It closes the second valve, open the first valve, and keep it
The state of his valve is as the state for taking out low vacuum.
In the present invention, the granularity of the mineral samplers is preferably 40~60 mesh, more preferably 50 mesh, the mineral samplers
Loadings be preferably 2~3g.In the present invention, the mineral samplers are preferably through drying process.In the present invention, described dry
The baking oven that dry processing is preferably put into 105 DEG C toasts 3~12 hours, for being easy to the mineral of the moisture absorption, such as halite, needs to toast 6
~12 hours.
In the present invention, for the mineral samplers for needing to take gas using thermal explosion system, the vacuumize process of system has
Body are as follows: mineral samplers are fitted into blasting cartridge, take away the piston on blasting cartridge；The first valve, the 16th valve are closed, it is opened
Its all valve carries out pumping low vacuum to system using low vacuum extract system；When the reading of three vacuum meters is respectively less than 10Pa
When；It closes the second valve, open the first valve, and keep the state of other valves as the state for taking out low vacuum.
In the present invention, the granularity of the mineral samplers is preferably 40~60 mesh, more preferably 50 mesh；The mineral samplers
Loadings be preferably 3~5g, more preferably 4g.In a specific embodiment of the present invention, preferably true according to mineral samplers type
Determine the loadings of mineral samplers, e.g., for the mineral samplers that magmatic hydrotherm is formed, mineral samplers loadings are preferably 3g, for
Epithermal and sedimentogenic mineral samplers, mineral samplers loadings are preferably 5g；When only needing the hydrogen isotope to mineral
When being tested, then mineral samplers loadings halve on the basis of the above, i.e. the mineral samplers loadings of magmatic hydrotherm formation are excellent
It is selected as 1.5g, epithermal and sedimentogenic mineral samplers loadings are preferably 2.5g.
After system vacuumize process, the present invention carries out taking solid/liquid/gas reactions, obtains micro-molecular gas；The micro-molecular gas
Freezing collection is carried out in third cold-trap.In the present invention, according to the property of mineral samplers, selection needs to take the device of gas.
In the present invention, for needing to carry out taking the specific of solid/liquid/gas reactions for the mineral samplers for taking gas using crushing system
Operation preferably includes: when vacuum meter reading is 0Pa, and copper oxide furnace assigned temperature, close the 13rd valve, the 14th valve
With the 17th valve, it is connected to crushing device only with third vacuum meter, third cold-trap；Third is set to freezing reagent cup is equipped with again
On cold-trap, starts crushing and take gas, obtain micro-molecular gas；The micro-molecular gas carries out freezing collection in third cold-trap.
In the present invention, it is preferably 100~110 DEG C that the crushing, which takes the temperature of gas, and pressure is preferably 20MPa, the oxygen
The set temperature for changing copper furnace is preferably 600~650 DEG C；The temperature that the freezing is collected is preferably -196 DEG C；The freezing is collected
Temperature is preferably reached by the cooling third cold-trap of liquid nitrogen.
In the present invention, it is preferably 1~2 time that the crushing, which takes the number of gas,.
It in the present invention, include taking the specific behaviour of solid/liquid/gas reactions for body for needing to take the mineral of gas using thermal explosion system
Preferably include: when vacuum meter reading is 0Pa, high temperature furnace reaches thermal expousure temperature and copper oxide furnace reaches assigned temperature,
Close the 13rd valve, the 14th valve, the 16th valve and the 19th valve, make thermal explosion device only with third vacuum meter,
The connection of three cold-traps；Again on the glass holder to third cold-trap equipped with freezing reagent, and high temperature furnace is set on blasting cartridge, starts thermal explosion
Reaction, obtains micro-molecular gas；The micro-molecular gas carries out freezing collection in third cold-trap.
In the present invention, the temperature of the thermal expousure is preferably 500~650 DEG C, and the time is preferably 20min.The present invention
It is preferred that the actual temp of thermal expousure is determined according to mineral samplers species, such as high temperature mineral (garnet and magnetic iron ore
Deng), the temperature of thermal expousure is preferably 650 DEG C；For quartz, the temperature of thermal expousure is preferably 500 DEG C.In the present invention,
During thermal expousure, mineral samplers burst, and release micro-molecular gas.
After micro-molecular gas freezing is collected, the present invention, which carries out the first heating to third cold-trap, collects third cold-trap
Micro-molecular gas releases, and by parallel system, obtains comprising CO2And H2The mixed gas of O, the mixed gas transfer
Into the second cold-trap；Freezing liquid replacement is carried out to the second cold-trap, makes the CO in the second cold-trap2It releases, collects in sample cell
In, it is to be determined.
When in the micro-molecular gas include CnH2n+2、H2Further reaction is needed with gases such as CO, CO could be formed2With
H2When O, needs small analysis gas carrying out redox reaction through copper dioxide furnace, obtain comprising CO2And H2The mixed gas of O.
In the present invention, the temperature of the redox reaction is preferably 600~650 DEG C.In the present invention, when including in copper oxide furnace
CnH2n+2When with CO gas, the reaction equation in copper oxide furnace is shown below:
CnH2n+2+ 4CuO=xCO2+yH2O+zCu；
CO+CuO=CO2+Cu。
In the present invention, for the mineral containing transition-metal ions, such as magnetic iron ore, garnet, Fe therein2+And/or Mn2 +It is reacted at high temperature with the water in inclusion enclave and generates H2, H2It reacts in copper oxide furnace and generates H2O, to prevent these H2Ease
It loses and causes isotope fractionation.Specific reaction equation are as follows:
H2+ CuO=H2O+Cu。
In the present invention, when micro-molecular gas needs further reaction, the micro-molecular gas passes through the tool of the first access
Body operating procedure are as follows: close the 7th valve, the 9th valve, the tenth valve and the 15th valve；And open the 11st valve, the tenth
Three valves and the 8th valve, and the 12nd valve and the 14th valve is kept to close, the freezing reagent of third cold-trap is replaced with
Hot water makes micro-molecular gas by copper oxide furnace, obtains comprising CO2And H2Mixed gas is transferred to second by the mixed gas of O
In cold-trap.In the present invention, the temperature of the hot water is preferably 40~60 DEG C.In the present invention, the mixed gas shifts
Time is preferably 5min.
When the micro-molecular gas has been CO2And H2When O, when not needing further progress reaction, alternate path is opened
The 14th valve and the 12nd valve are opened, and the first path blockade i.e. the 13rd valve and the 11st valve is kept to close.
In the present invention, when micro-molecular gas does not need further to react, the micro-molecular gas is by alternate path
Concrete operation step preferably includes: after micro-molecular gas freezing is collected, closing the 7th valve, the 9th valve, the tenth valve
With the 15th valve；And the 12nd valve and the 14th valve and the 8th valve are opened, and keep the 11st valve and the 13rd
Valve is closed, and the freezing reagent of third cold-trap is replaced with hot water, micro-molecular gas is made to be directly over the 12nd valve and the tenth
Four valves are obtained comprising CO2And H2Mixed gas is transferred in the second cold-trap by the mixed gas of O.In the present invention, described
Freezing reagent in three cold-traps and the second cold-trap is preferably liquid nitrogen.In the present invention, the temperature of the hot water is preferably 40~60
℃.In the present invention, the time of the mixed gas transfer is preferably 5min.
No matter which kind of mode is used, after mixed gas is transferred to the second cold-trap, the present invention carries out the second cold-trap
Freezing liquid replacement, makes the CO in the second cold-trap2It releases, collects in sample cell, it is to be determined.In the present invention, replacement the
When freezing reagent in two cold-traps, the freezing reagent replaced is preferably dry ice crude alcohol mixture.
Concrete operation step after mixed gas is transferred to the second cold-trap are as follows: after mixed gas transfer,
It keeps the 11st valve and the 12nd valve to close, the liquid nitrogen in the second cold-trap is filled it up with, then open the tenth valve, the second valve
Door is 10Pa to vacuum degree；The second valve is closed, the first valve is opened simultaneously, is freezed reagent is not frozen in the second cold-trap
Gas take away；The tenth valve is turned off, the mixture that the freezing reagent in the second cold-trap is dry ice and alcohol is replaced, beats simultaneously
The 9th valve is opened, the CO in the second cold-trap is made2It releases, and is collected into the CO connecting with the 9th valve2In sample collection tube,
It is to be determined.
CO2After collection, secondary temperature elevation is carried out to the second cold-trap, releases the water in the second cold-trap, and pass through
Reacting furnace carries out reduction reaction, obtained H2H is transferred to by the first cold-trap2It is to be determined in sample cell.
In the present invention, the temperature of the secondary temperature elevation is preferably 40~60 DEG C, and more preferably 45~55 DEG C, most preferably
50℃.In the present invention, the reacting furnace preferably includes chromium powder furnace.In the present invention, the temperature of reduction reaction be preferably 830~
860 DEG C, more preferably 840~855 DEG C, most preferably 845~850 DEG C.In the present invention, the time of the reduction reaction is preferred
For 6min.In the present invention, the specific reaction equation of the reduction reaction is as follows:
2Cr+3H2O=Cr2O3+3H2↑。
In the present invention, the freezing reagent of first cold-trap is preferably liquid nitrogen.
In the present invention, CO2Concrete operations process after collection preferably includes: working as CO2After collection, the is kept
Seven valves, the 11st valve and the 12nd valve are closed, and the tenth valve is opened, and the second valve takes out low vacuum；It is then shut off second
Valve opens the first valve pumping high vacuum, pumps the gas not freezed in the second cold-trap；Then the 5th valve, the 6th valve are kept
Door and the 8th valve are closed, and open the 7th valve, the freezing reagent of the second cold-trap is replaced with hot water, will be in the second cold-trap
H2O is released, and carries out reduction hydrogen production reaction by reacting furnace；After restoring hydrogen production reaction, third valve and the are closed
Then four valves, the liquid nitrogen cup on the first cold-trap housing open the 5th valve, write down the reading of the first vacuum meter, as generate
H2Amount；Then the 4th valve is opened, the 7th valve is closed, H2It collects to being connected on the H after the 4th valve2Sample collection tube
In, it is to be measured.
It is collected into CO2And H2Afterwards, the present invention is by the H of collection2And CO2Carry out mass spectrum two-way off-line test.
The present invention does not have particular/special requirement to the specific method of the mass spectrum two-way off-line test, uses those skilled in the art
Well known method.
In the present invention, the carbon of the mineral samplers, hydrogen isotope test result are according to standard H2Test result conversion
It obtains.Present invention preferably uses above systems to produce standard H2, then using mass spectrum two-way off-line test to standard H2It is surveyed
Examination.
In the present invention, the standard H2Produce and preferably inject standard water in chromium powder furnace, collect reaction and obtain
H2, as standard H2.In the present invention, the standard water is preferably national standard water, specific such as QYTB1 (seawater) and QYTB2
(Xi Zangshui).
In the present invention, the standard H2Produce and preferably include following steps:
(a) vacuumize process is carried out to system；
(b) standard water injected system is entered standard water in reacting furnace with gaseous state and is restored by standard sample injector
Reaction；
(c) after the completion of reduction reaction, by the standard H of generation2It collects in H2In collecting pipe.
In the present invention, the mode of the vacuumize process of the step (a) preferably with system described in above-mentioned technical proposal
Unanimously, details are not described herein for step (1) in the method analyzed mineral fluid inclusions carbon, hydrogen isotope.
In the present invention, the reduction reaction temperature in the step (b) and time preferably with water described in above scheme also
Former hydrogen manufacturing is consistent, and details are not described herein；The injection rate of the standard water is preferably 2 μ L.
In the present invention, the step (b) specifically: when the first low vacuum table and the second low vacuum meter reading are 0Pa, and
When reacting furnace reaches reduction reaction temperature, close the 5th valve and the 7th valve, open the 6th valve, make reacting furnace with it is other every
From, and be connected to standard sample injector；Then standard syringe is used, 2 μ L of standard water is taken, injects reduction reaction system, standard water exists
In the case where heating tape or external heat source, enter reacting furnace in a gaseous form, redox reaction occurs.
In the present invention, H is collected in the step (c)2Mode preferably with the H of above scheme2Collection mode is consistent,
This is repeated no more.
In the present invention, the mineral samplers inclusion enclave carbon isotope test result is according to standard carbon dioxide test result
Conversion obtains.Standard carbon dioxide gas is to be reacted to be made with anhydrous phosphoric acid by standard GB/T W04405 and GBW04406, so
Its result is measured using mass spectrum two-way off-line test afterwards.
Thermal explosion air-taking system and crushing air-taking system are connected in parallel by system provided by the invention, those skilled in the art
It can according to need and selected, simplify experimental implementation；The application of oil-free valve simultaneously, also improves isotope analysis result
Accuracy.
A kind of mineral fluid inclusions carbon provided by the invention, the oil-free valve of hydrogen isotope are analyzed below with reference to embodiment
System and method are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Using oil-free valve analysis system of the invention and existing there is oil valve door analysis system to same magmatic hydrotherm mine
Quartz mineral sample carries out 5 thermal explosion method test comparisons in bed ore, and mineral samplers are labeled as 15ND01, each test condition
And operating method is consistent, difference be only that valve difference, test method the following steps are included:
(1) standard H is prepared2
1) preparation.Open the prime mechanical pump and metal diffusion pump of low vacuum mechanical pump, high vacuum；Open copper oxide
Furnace, high temperature furnace and reacting furnace；Opening the second valve makes entire reaction unit connection low vacuum extract system, and open system remaining
Valve；When three vacuum meter readings are less than 10Pa, turn off the second valve, opens the first valve, make entire reaction unit
It is connect with fine pumping system.
2) hydrogen manufacturing is restored.When left and right low vacuum meter reading is 0Pa, and reacting furnace is up to 850 DEG C, the 5th valve and the are closed
Seven valves open the 8th valve, reacting furnace are isolated with other, and be connected to standard sample injector；Then it is infused with special standard
Emitter takes 2 μ L of standard, injects standard sample injector；Standard water is in the case where heating tape or external heat source are heated, in a gaseous form
Into reacting furnace, control generates H2The oxygen reduction reaction reaction time be 6min.
3) H is collected2.At the end of reduction reaction 6 minutes, third valve and the 4th valve are closed, the first cold-trap is put on
Then liquid nitrogen cup opens the 5th valve, writes down the reading of the first vacuum meter, as generation H2Amount；Then the 4th valve is opened,
H2The H equipped with active carbon after being collected into the 4th valve2In sample collection tube, acquisition time is 3 minutes.
(2) standard CO is prepared2
It is reacted and is made with anhydrous phosphoric acid using standard GB/T W04405 and GBW04406, preparation process is conventional method,
It is not belonging to present patent application.
(3) the producing of mineral samplers gas (including H2And CO2)
1) preparation.Mineral samplers are fitted into blasting cartridge, the piston on blasting cartridge is taken away；Close the first valve,
16 valves open other all valves using low vacuum extract system and carry out pumping low vacuum to system；When three vacuum meters
Reading when being respectively less than 10Pa；It closes the second valve, open the first valve, and keep the state of other valves and smoke low vacuum
State is the same.
2) thermal explosion takes gas.When vacuum meter reading is 0Pa, high temperature furnace reaches 500 DEG C and copper oxide furnace reaches 600 DEG C, closes
The 13rd valve, the 14th valve and the 19th valve are closed, is connected to thermal explosion device only with third vacuum meter, third cold-trap；Again
On liquid nitrogen glass holder to third cold-trap, and high temperature furnace is set on blasting cartridge, starts thermal explosion, and keep explosion 20 minutes, obtained
Small analysis organic gas.
3) purification for gas and CO2Collection.At the end of explosion 20 minutes, close the door the 7th valve, the tenth valve, the 15th
Valve, the second cold-trap on liquid nitrogen glass holder；And it opens the 11st valve and the 13rd valve and keeps the 12nd valve and the tenth
Four valves are closed, and the liquid nitrogen cup on third cold-trap is being changed the hot water cup that temperature is 40~60 DEG C, is being made small in third cold-trap
Molecular gas releases, and by copper oxide furnace, is transferred in the second cold-trap, controls time 5min；
At the end of previous step 5 minutes, the 11st valve and the 12nd valve are closed, the liquid nitrogen cup outside the second cold-trap is added
Full liquid nitrogen, then opens the tenth valve, the gas not freezed by liquid nitrogen in the second cold-trap is taken away；The tenth valve is turned off,
The liquid nitrogen cup of second cold-trap changes dry ice crude alcohol mixture cup into, allows CO in the second cold-trap2It releases, and is collected into and is connected on
The 9th subsequent CO of valve2In sample collection tube, CO is collected2Time be 5min.
4) hydrogen manufacturing is restored.As collection CO2After, then the tenth valve is opened, it pumps do not freezed in the second cold-trap again
Gas；It is then shut off the 5th valve, the 6th valve, the 8th valve, the dry ice crude alcohol mixture cup for removing the second cold-trap is changed
Hot water cup, in this way the H in the second cold-trap2O is input in a gaseous form in chromium powder furnace, brings it about the reaction of reduction hydrogen manufacturing,
The control reaction time is 6min.
5)H2It collects.With collection standard H above2The step of it is consistent.
The standard H of coming is collected to above2, standard CO2, sample H2And backpack body CO2, carry out mass spectrometric measurement.Test method
It is the off-line test mode of the two-way sample introduction used.The result of test is the isotopic ratio of sample or standard to reference gas, so
The value (value of opposite international standard) of mineral inclusion carbon-hydrogen isotopes is calculated separately out according still further to following formula (1) and (2) afterwards.
Formula (1)；
In formula (1):
δ13CSA-RE--- δ of the sample with respect to reference gas13C value；
δ13CST-RE--- δ of the working stamndard with respect to reference gas13C value；
δ13CST-V-PDB--- δ of the working stamndard with respect to international standard V-PDB13C value.
Formula (2)；
In formula (2):
δDSA-RE--- δ D value of the sample with respect to reference gas；
δDST-RE--- δ D value of the working stamndard with respect to reference gas；
δDST-VSMOW--- δ D value of the working stamndard with respect to international standard V-SMOW.
Gained test result is listed in Table 1 below.
Table 1: same mineral samplers two kinds of different analysis systems, five thermal explosion method Measurement results tables
| Sample number | Sample type | Sample size/g | Test result/‰ | Using method |
| 15ND01 | Quartz | 2.5 | -76 | There is oil valve door thermal explosion method |
| 15ND01 | Quartz | 2.5 | -73 | There is oil valve door thermal explosion method |
| 15ND01 | Quartz | 2.5 | -78 | There is oil valve door thermal explosion method |
| 15ND01 | Quartz | 2.5 | -74 | There is oil valve door thermal explosion method |
| 15ND01 | Quartz | 2.5 | -75 | There is oil valve door thermal explosion method |
| 15ND01 | Quartz | 2.5 | -74 | Oil-free valve thermal explosion method |
| 15ND01 | Quartz | 2.5 | -77 | Oil-free valve thermal explosion method |
| 15ND01 | Quartz | 2.5 | -72 | Oil-free valve thermal explosion method |
| 15ND01 | Quartz | 2.5 | -75 | Oil-free valve thermal explosion method |
| 15ND01 | Quartz | 2.5 | -72 | Oil-free valve thermal explosion method |
As it can be seen from table 1 test result of the thermal explosion method of oil-free valve analysis system to same mineral samplers are as follows: average
Value is -74.0 ‰；Standard deviation is 1.90 ‰；There is the thermal explosion method of oil valve door analysis system to the test result of same mineral samplers
Are as follows: average value is -75.2 ‰, and standard variance is 1.92 ‰.As it can be seen that the analysis result of oil-free valve system and having oil valve door system
Analysis result be not much different, in allowed limits, illustrate oil-free valve system analysis method be it is stable, it is feasible.
And the standard deviation 1.90 ‰ of oil-free valve system is better than the standard deviation (1.92 ‰) for having oil valve door system, this explanation is oil-free
Valve system testing and analysis data is more stable.
Embodiment 2
Using oil-free valve analysis system and there are the two methods (thermal explosion method and crush method) of oil valve door analysis system respectively
Analysis test comparison is carried out to the same gangue mineral sample (quartz) of same quartz vein gold ore；Quartz mineral sample is marked respectively
It is denoted as 15YE21,15YE22,15YE23,15YE24,15YE25.
There are oil valve door system thermal explosion method, oil-free valve system thermal explosion method same as Example 1；Difference is only that valve not
Together.There is the difference of oil valve door system crush method, oil-free valve system crush method and embodiment 1 to be only that, it, will when pumped vacuum systems
The piston of blasting cartridge beyond the Great Wall, makes vacuum system carry out vacuum pumping to crushing air-taking system；Crushing takes jia bombardier rapid are as follows: works as vacuum
When meter reading is 0Pa, and copper oxide furnace reaches 600 DEG C, closes the 13rd valve and the 14th valve, makes to crush device only with the
Three vacuum meters, the connection of third cold-trap；Again on liquid nitrogen glass holder to third cold-trap；Then the rotating handle handle for rotating objective table is equipped with
The cask for crushing mineral samplers is adjusted to the underface of hydraulic handle, and the pressure for adjusting hydraulic press is 20MPa, and foot is stepped on control and stepped on
Plate rolls the mineral samplers in cask twice.
Two kinds of 2: two kinds of analysis systems of table take gas method Measurement results contrast table
| Sample number | Sample type | Sample size/g | Test result/‰ | Using method |
| 15YE21 | Quartz | 2.5 | -85 | Oil-free valve thermal explosion method |
| 15YE21 | Quartz | 2.5 | -82 | Oil-free valve crush method |
| 15YE22 | Quartz | 2.5 | -80 | Oil-free valve thermal explosion method |
| 15YE22 | Quartz | 2.5 | -78 | Oil-free valve crush method |
| 15YE23 | Quartz | 2.5 | -86 | Oil-free valve thermal explosion method |
| 15YE23 | Quartz | 2.5 | -84 | Oil-free valve crush method |
| 15YE24 | Quartz | 2.5 | -93 | Oil-free valve thermal explosion method |
| 15YE24 | Quartz | 2.5 | -91 | Oil-free valve crush method |
| 15YE25 | Quartz | 2.5 | -90 | Oil-free valve thermal explosion method |
| 15YE25 | Quartz | 2.5 | -89 | Oil-free valve crush method |
| 15YE21 | Quartz | 2.5 | -84 | There is oil valve door thermal explosion method |
| 15YE21 | Quartz | 2.5 | -83 | There is oil valve door crush method |
| 15YE22 | Quartz | 2.5 | -81 | There is oil valve door thermal explosion method |
| 15YE22 | Quartz | 2.5 | -80 | There is oil valve door crush method |
| 15YE23 | Quartz | 2.5 | -87 | There is oil valve door thermal explosion method |
| 15YE23 | Quartz | 2.5 | -85 | There is oil valve door crush method |
| 15YE24 | Quartz | 2.5 | -92 | There is oil valve door thermal explosion method |
| 15YE24 | Quartz | 2.5 | -89 | There is oil valve door crush method |
| 15YE25 | Quartz | 2.5 | -91 | There is oil valve door thermal explosion method |
| 15YE25 | Quartz | 2.5 | -89 | There is oil valve door crush method |
From table 2 it can be seen that for identical mineral samplers and the identical test result for taking gas method but different valve systems,
Its difference also all in the range of 3 ‰, illustrates that oil-free valve system is a kind of feasible analysis system.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. the oil-free valve analysis system of a kind of mineral fluid inclusions carbon, hydrogen isotope, including air-taking system, conversion and purifying system
System, reduction hydrogen manufacturing and collection system and vacuum-control(led) system；
The air-taking system include be sequentially communicated, with the thermal explosion air-taking system of parallel way connection and crushing air-taking system, the
15 valves and third cold-trap；The thermal explosion air-taking system includes the thermal explosion device being sequentially communicated, the 18th valve and the 17th
Valve；The crushing air-taking system includes the crushing device and the 16th valve being sequentially communicated；In the thermal explosion air-taking system
The 16th valve in 17th valve, the crushing system is connected to the 15th valve simultaneously；
The conversion and purification system include the parallel system being sequentially communicated, the 8th valve, the second cold-trap；The parallel system packet
It includes with the first access of parallel way setting formed by the 14th valve and the 12nd valve and by the 13rd valve, oxidation
The alternate path that copper furnace and the 11st valve are formed；9th valve is set between the 8th valve and parallel system；Described
Nine valves and CO2Sample collection tube connection；The 11st valve and the 12nd valve of 8th valve and parallel system are simultaneously
Connection；
Pass through third cold-trap and the 16th valve and the 17th between the air-taking system and the conversion and purification system
Valve is connected to simultaneously；
The reduction hydrogen manufacturing and collection system include the 7th valve being sequentially communicated, reacting furnace, the first cold-trap, the 5th valve, the
Four valves and H2Sample collection tube；6th valve is set between the 7th valve and reacting furnace；
The conversion is connected to by the second cold-trap with the 7th valve between purification system and reduction hydrogen manufacturing and the collection system；
The vacuum-control(led) system includes low vacuum extract system and fine pumping system；The fine pumping system and low
Vacuum-pumping system passes through the first valve and the control of the second valve respectively；The fine pumping system and low vacuum pumping system are logical
Cross third valve, the tenth valve and the 19th valve access pipeline；The third valve is arranged in the 4th valve and the 5th
Between valve；Tenth valve is arranged between the 9th valve and the parallel system；The 19th valve setting
Between the 18th valve and thermal explosion air-taking system；First vacuum meter is connected on third valve and the 4th valve and the
On pipeline between five valves；Second vacuum meter is connected on the 9th and the 11st pipeline between valve；The third vacuum
Table is arranged between the 15th valve and the 16th valve, and the third vacuum meter is connect with the 17th valve；
First valve to the 19th valve is oil-free valve.
2. analysis system according to claim 1, which is characterized in that the 6th valve is connect with standard sample injector.
3. a kind of analyze mineral fluid inclusions carbon, hydrogen isotope using analysis system described in as claimed in claim 1 or 22
Method, comprising the following steps:
(1) after mineral samplers being packed into thermal explosion device or crushing device, vacuumize process is carried out to system；
(2) it after vacuumize process, carries out taking solid/liquid/gas reactions, obtains micro-molecular gas；The micro-molecular gas is in third cold-trap
In carry out freezing collection；
(3) micro-molecular gas that carrying out the first heating to third cold-trap collects third cold-trap releases, and passes through taken in conjunction
System is obtained comprising CO2And H2The mixed gas of O, the mixed gas are transferred in the second cold-trap；Second cold-trap is freezed
Liquid replacement, makes the CO in the second cold-trap2It releases, collects in CO2It is to be determined in sample collection tube；
(4)CO2After collection, the second heating is carried out to the second cold-trap, makes the H in the second cold-trap2O is released, and by anti-
Furnace is answered to carry out reduction reaction, the H that will be obtained2H is transferred to by the first cold-trap2It is to be determined in sample collection tube；
(5) by the H of collection2And CO2Carry out mass spectrum two-way off-line test.
4. according to the method described in claim 3, it is characterized in that, third cold-trap is liquid nitrogen in the step (2)；Step (3)
In the freezing reagent of the second cold-trap be first liquid nitrogen, after replace with the mixture of dry ice and alcohol.
5. according to right to go 3 described in method, which is characterized in that the step (3) specifically:
After micro-molecular gas freezing is collected, the 7th valve, the 9th valve, the tenth valve and the 15th valve are closed；And it beats
It opens the 11st valve, the 13rd valve and the 8th valve to open, and the 12nd valve and the 14th valve is kept to close, by third
The freezing reagent of cold-trap replaces with hot water, makes micro-molecular gas by parallel system, obtains comprising CO2And H2The mixed gas of O,
Mixed gas is transferred in the second cold-trap；
After mixed gas transfer, the 11st valve is closed, the liquid nitrogen in the second cold-trap is filled it up with, then opens the tenth valve
Door, the second valve；When vacuum degree is 10Pa, the second valve is closed, the first valve is opened simultaneously, it will be not cold in the second cold-trap
Freeze the gas that reagent freezes to take away；Turn off the tenth valve, replacing the freezing reagent in the second cold-trap is the mixed of dry ice and alcohol
Object is closed, the 9th valve is opened simultaneously, makes the CO in the second cold-trap2It releases, and is collected into the CO connecting with the 9th valve2Sample
It is to be determined in product collecting pipe.
6. according to the method described in claim 5, it is characterized in that, the temperature of the hot water is 40~60 DEG C.
7. according to the method described in claim 5, it is characterized in that, the freezing reagent in second cold-trap replaces with dry ice wine
Smart mixture.
8. according to the method described in claim 5, it is characterized in that, the CO2Acquisition time be 5min.
9. the method according to claim 3 or 5, which is characterized in that the step (4) specifically:
Work as CO2After collection, the 7th valve, the 11st valve and the 12nd valve is kept to close, the tenth valve of opening, second
Valve takes out low vacuum；It is then shut off the second valve, the first valve pumping high vacuum is opened, pumps the gas not freezed in the second cold-trap
Body；Then it keeps the 5th valve, the 6th valve and the 8th valve to close, the 7th valve is opened, by the freezing reagent of the second cold-trap
Hot water is replaced with, by the H in the second cold-trap2O is released, and carries out reduction hydrogen production reaction by reacting furnace；It is anti-to restore hydrogen manufacturing
After answering, third valve and the 4th valve are closed, then the liquid nitrogen cup on the first cold-trap housing is opened the 5th valve, write down
The reading of first vacuum meter, as generation H2Amount；Then the 4th valve is opened, the 7th valve is closed, H2It collects to being connected on
H after 4th valve2It is to be measured in sample collection tube.
10. according to the method described in claim 9, it is characterized in that, the temperature of the reduction reaction be 830~860 DEG C, the time
For 6min.
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