CN109060932A - Carbon and hydrogen isotope analysis system and method for mineral fluid inclusion - Google Patents
Carbon and hydrogen isotope analysis system and method for mineral fluid inclusion Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 102
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 102
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 60
- 239000011707 mineral Substances 0.000 title claims abstract description 60
- 238000004458 analytical method Methods 0.000 title claims abstract description 34
- 239000012530 fluid Substances 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 95
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000012360 testing method Methods 0.000 claims abstract description 42
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000005751 Copper oxide Substances 0.000 claims abstract description 27
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 27
- 238000004880 explosion Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 44
- 238000005086 pumping Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000006722 reduction reaction Methods 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 31
- 239000001569 carbon dioxide Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- 238000001819 mass spectrum Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 5
- COUNCWOLUGAQQG-UHFFFAOYSA-N copper;hydrogen peroxide Chemical compound [Cu].OO COUNCWOLUGAQQG-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 51
- 229960004424 carbon dioxide Drugs 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000010453 quartz Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000190070 Sarracenia purpurea Species 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007689 inspection Methods 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
- 238000005259 measurement Methods 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
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010430 carbonatite Substances 0.000 description 1
- 238000004587 chromatography analysis 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910052958 orpiment Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
-
- 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
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a hydrocarbon isotope analysis device for most mineral fluid inclusion, which comprises a crushing gas taking system, a conversion and purification system, a reduction hydrogen production and collection system and a vacuum control and detection system. The method has the advantages that the crushing method is used for extracting gas to replace the currently and commonly used thermal explosion gas extraction method, so that the time is saved; the crushing gas extraction system can avoid the reaction of valence-variable ions and water at high temperature in a thermal explosion method, and minerals without valence-variable element ions do not need to pass through a CuO furnace, so that the time is saved again; the device can simultaneously analyze the composition of two kinds of carbon and hydrogen isotopes, and simultaneously simplifies the testing steps without passing through a copper oxide furnace; the crushing gas taking and the chromium powder reduction hydrogen production are designed into two relatively independent and connected units, so that the overall arrangement is convenient; the system provided by the invention only comprises two cold traps, and has simple flow and easy operation.
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 point
Analysis system and method.
Background technique
Since mineral fluid inclusions are the diagenesis or BIFhosted gold deposit of its mineral trap in forming process, fluid inclusion
Ingredient represents physical chemistry information when its host originally forms in forming process, its ingredient (including element and same
Position element composition) research is always the very important research contents of subjects such as geoscience, environmental science, thus becomes current research
Hot spot.
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 the continuous flow sample introduction to grow up in recent years.Traditional off-line test method are as follows:
(burst, crush and grind) gas and liquid in released mineral inclusion enclave first with various methods, then by separation,
Purification and redox reaction, collection can test gas (for example, H2And CO2Gas), finally compare mass spectrum using gas isotope
Instrument (IRMS, Isotope Ratio Mass Spectrometry) enters progress with the mode of two-way sample introduction (duel inlet)
Analysis test.Continuous flow on-line analysis is EA (elemental analyser)-IRMS (isotope ratio mass spectrum) joint technology.This method
Exactly using in elemental analyser (instrument model: Flash 2000HT) high temperature (temperature is at 1400 DEG C or so) cracking inclusion enclave
Water generates hydrogen, then by after chromatography column separating purification and direct with the sample introduction mode of continuous flow (continuous flow)
It is tested into mass spectrum.Relative to the latter, the advantages of traditional off-line test analysis method is: 1) analysis precision is high；2) may be used
Analyze a variety of isotopes；3) reduce and clear up problem using the mineral residue of continuous flow on-line analysis, can disposably divide
Analyse many samples.
For the off-line test analysis method of mineral fluid inclusions isotope two-way sample introduction, thermal explosion is presently mainly used
Method makes mineral inclusion burst and discharges the method for gas that is, by the method for heating.The extensive use of the thermal explosion method is this
Method operation is relatively easy, and the gas relatively other methods that thermal explosion goes out are more, is easier analysis test.But with matter
The raising of spectrum analysis sensitivity, demand sample size are greatly reduced.Using crushing method released mineral fluid inclusion gas into
Row isotope analysis is also possibly realized.It is prior, for the mineral for being easy to thermally decompose, such as sulfide (pyrite, orpiment iron
Mine, mispickel etc.), thermal explosion method is not just available, because the substance meeting contaminated system that the thermal decomposition of these substances generates, influences separation inspection
Survey effect.Though thering is document and patent to mention crush method or grind method at present to take gas or water, do not see the experiment skill that may be implemented also
Art process is applied to mineral fluid inclusions isotope test 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-hydrogen isotopes analysis system and sides
Method, system provided by the invention include crushing air-taking system, can take gas and hydrogen manufacturing two by the independent thermal explosion that is respectively completed simultaneously
Process, and precision is high, high-efficient.
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, hydrogen isotope analysis system, including crush air-taking system, turn
Change and purification system, reduction hydrogen manufacturing and collection system and vacuum control and detection system；
Crushing air-taking system, conversion and the purification system include the crushing device being sequentially connected in series on pipeline, first cold
Trap and carbon dioxide collection pipe are disposed with the 13rd valve, the 12nd valve between the crushing device and the first cold-trap
With the 11st valve, copper oxide furnace is also parallel between the 12nd valve and the 11st valve；First cold-trap and two
The tenth valve is provided between carbonoxide collecting pipe；
The reduction hydrogen manufacturing and collection system include the cold finger being sequentially connected in series on pipeline, chromium powder furnace, the second cold-trap and hydrogen
Gas collecting pipe；The cold finger is connected on pipeline by the 7th valve；The 6th valve is provided between the cold finger and chromium powder furnace；
The 5th valve and third valve are disposed among second cold-trap and Hydrogen collection pipe；
The conversion is connected to purification system and reduction hydrogen manufacturing with collection system by the 9th valve, and the setting of the 9th valve exists
Between carbon dioxide collection pipe and cold finger；
The vacuum-control(led) system includes low vacuum extract system, fine pumping system, the first low vacuum table and second
Low vacuum table；The low vacuum extract system and fine pumping system pass through the 4th valve access pipeline；The high vacuum is taken out
The first valve is additionally provided between gas system and the 4th valve；Is provided between the low vacuum extract system and the 4th valve
Two valves；
4th valve and the 13rd valve are connected to form main vacuum-pumping pipeline；
9th valve is connected to main vacuum-pumping pipeline, and the 8th valve is provided on connecting pipeline；Described first is low
Vacuum meter is arranged between the 9th valve and the 8th valve；
The second low vacuum table is arranged between the 5th valve and third valve, the 5th valve and main vacuum-pumping tube
Road connection；
First valve, the second valve, third valve, the 8th valve and the tenth valve are two two-way valves；4th valve
Door, the 11st valve and the 12nd valve are three two-way valves；5th valve, the 6th valve, the 7th valve, the 9th valve and
13 valves are three triple valves.
Preferably, standard sample injector is additionally provided on the 6th valve.
Preferably, the material of the copper oxide furnace and chromium powder furnace is quartz glass, and the material of the crushing device is stainless
Steel.
The present invention also provides the systems described in above-mentioned technical proposal to divide mineral fluid inclusions carbon, hydrogen isotope
The method of analysis, comprising the following steps:
(1) vacuumize process is carried out to system；
(2) mineral samplers are packed into crushing device, then carry out crushing under vacuum conditions and take gas, the gas of generation passes through
Copper oxide furnace, being formed includes CO2And H2The mixed gas of O, the mixed gas carry out freezing collection in the first cold-trap；
(3) carrying out the first heating to the first cold-trap makes the CO in the mixed gas2It discharges and is collected into carbon dioxide receipts
In collector；
H in the mixed gas is made to the second heating of the first cold-trap progress2O is transferred in cold finger；
(4) carrying out heating to cold finger makes H2O, which enters, carries out reduction reaction in chromium powder furnace, by obtained Hydrogen collection in hydrogen
In collecting pipe；
(5) carbon dioxide being collected into and hydrogen are subjected to mass spectrum two-way off-line test.
Preferably, it is 100~110 DEG C that crushing, which takes the temperature of gas, in the step (2), pressure 20MPa；
The set temperature of the copper oxide furnace is 600~650 DEG C；
The temperature that the freezing is collected is -196 DEG C；The freezing is collected temperature and is reached by cooling first cold-trap of liquid nitrogen.
Preferably, the step (2) specifically: the 4th valve of control connect whole system with low vacuum extract system
Pumping low vacuum is carried out, when the first low vacuum table and the second low vacuum meter reading are less than 10Pa, then controls the 4th valve entire
Reaction system is connect with fine pumping system；When the first low vacuum table and the second low vacuum meter reading are 0Pa, and copper oxide
Furnace temperature reaches set temperature, when crushing device reaches crushing and takes the temperature of gas, controls the 8th valve, the 9th valve, the 11st
Valve, the 12nd valve and the 13rd valve are connected to crushing air-taking system, conversion with purification system, liquid nitrogen glass holder to first
On cold-trap, starts crushing and take gas and collect gas.
Preferably, the temperature of the first heating is -80 DEG C in the step (3)；The temperature of the first heating by using
Dry ice-crude alcohol mixture impregnates the first cold-trap and reaches；
CO is collected in the step (3)2Time be 5min；
The temperature of the second heating is room temperature in the step (3)；The temperature of second heating is cold by that will impregnate first
The dry ice of trap-crude alcohol mixture removal reaches；
The H2The transfer time of O is 5min.
Preferably, the temperature of reduction reaction is 830~860 DEG C in the step (4), time 6min；
The initial temperature of the cold finger is -196 DEG C；The initial temperature of the cold finger is reached by liquid nitrogen cooling；
The heating final temperature of the cold finger is 40~60 DEG C；The heating of the cold finger is reached by using hot-water soak cold finger.
Preferably, the step (4) specifically: the 5th valve of control, the 6th valve and the 7th valve, make cold finger only with chromium
Powder furnace is connected, and the liquid nitrogen for being used to cool down cold finger is removed, using hot-water soak cold finger, makes H2O enters chromium powder furnace in a gaseous form
Middle carry out reduction reaction.
Preferably, when mineral samplers be the mineral inclusion without transition-metal ions, and only to the hydrogen isotope in mineral into
When row test, the 11st valve and the 12nd valve are controlled, makes thermal explosion gas without copper dioxide furnace.
The present invention provides a kind of mineral fluid inclusions carbon-hydrogen isotopes analysis systems, including crush air-taking system, turn
Change and purification system, reduction hydrogen manufacturing and collection system and vacuum control and detection system.System provided by the invention is taken with crushing
Gas system is taken gas method to realize in mineral fluid inclusions ingredient and is come out with the form fractionation of gas by crush method, relative to heat
It is quick-fried to take gas method, save the time；Crushing air-taking system carry out crushing take gas can to avoid transition-metal ions at a high temperature of in thermal explosion method with
The reaction of water, for the mineral without valence variation element ion just without going through CuO furnace, another saves the time；The device is not only applicable in
In being not easily decomposed mineral, and the mineral easily thermally decomposed are also suitable, therefore are suitable for most of mineral samplers；Simultaneously originally
The chromium powder furnace for inventing the analysis system fixation provided replaces movable chromium powder reaction tube to keep hydrogen production reaction quick and complete；It will oxidation
Copper furnace is incorporated to system, can analyze the composition of hydrocarbon two kinds of isotopes simultaneously, while simplifying the test step being not required to through copper oxide furnace
Suddenly it (as only tested quartz specimen inclusion enclave water phase hydrogen isotope, can be controlled by valve after being directly entered the vapor of purifying
The chromium powder furnace in face)；It takes gas and chromium powder to restore hydrogen manufacturing crushing and is designed to relatively independent and connection two units, convenient for planning as a whole peace
Row's experiment, saves the time, so that the crushing of current sample is taken the reduction hydrogen manufacturing of gas and a upper sample while carrying out；And the present invention mentions
The system of confession only includes two cold-traps, and process is simple, easy to operate.
The present invention provides a kind of methods for carrying out the analysis of fluid inclusion carbon-hydrogen isotopes using above system.The present invention
It is collected after obtaining carbon dioxide and hydrogen using above system, then carries out mass spectrum two-way off-line test.Method provided by the invention
Step is simple, and analysis precision is high, reproducible.Embodiment the result shows that, using method of the invention to same quartz specimen into
Row test, test result is compared with thermal explosion method, test result difference≤3 ‰.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of mineral fluid inclusions carbon of the invention, hydrogen isotope analysis system；
In Fig. 1,2-1 crush device, the first cold-trap of 2-2,2-3 carbon dioxide collection pipe, 2-4 copper oxide furnace, 2-5 standard into
Sample device, 2-6 cold finger, 2-7 chromium powder furnace, the second cold-trap of 2-8,2-9 Hydrogen collection pipe, 2-10 low vacuum extract system, 2-11 Gao Zhen
Empty extract system, 2-12 the first low vacuum table, 2-13 the second low vacuum table；
The first valve of 1-, the second valve of 2-, 3- third valve, the 4th valve of 4-, the 5th valve of 5-, the 6th valve of 6-, 7-
7th valve, the 8th valve of 8-, the 9th valve of 9-, the tenth valve of 10-, the 11st valve of 11-, the 12nd valve of 12-, 13-
13 valves.
Specific embodiment
The present invention provides a kind of mineral fluid inclusions carbon, hydrogen isotope analysis system, and structure is as shown in Figure 1, Fig. 1
In, 2-1 be crushing device, 2-2 be the first cold-trap, 2-3 be carbon dioxide collection pipe, 2-4 be copper oxide furnace, 2-5 be standard into
Sample device, 2-6 are cold finger, and 2-7 is chromium powder furnace, and 2-8 is the second cold-trap, and 2-9 is Hydrogen collection pipe, and 2-10 is low vacuum pumping system
System, 2-11 are fine pumping system, and 2-12 the first low vacuum table, 2-13 is the second low vacuum table；
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.
Mineral fluid inclusions carbon provided by the invention, hydrogen isotope analysis system, including crushing air-taking system, conversion with
Purification system, reduction hydrogen manufacturing and collection system and vacuum control and detection system；
Crushing air-taking system, conversion and the purification system include the crushing device 2-1 being sequentially connected in series on pipeline, first
Cold-trap 2-2 and carbon dioxide collection pipe 2-3, is disposed with the 13rd valve between the crushing device 2-1 and the first cold-trap 2-2
The 12, the 12nd valve 12 of door and the 11st valve 11, it is also in parallel aerobic between the 12nd valve 12 and the 11st valve 11
Change copper furnace 2-4；The tenth valve 10 is provided between the first cold-trap 2-2 and carbon dioxide collection pipe 2-3；
The reduction hydrogen manufacturing and collection system include the cold finger 2-6 being sequentially connected in series on pipeline, chromium powder furnace 2-7, second cold
Trap 2-8 and Hydrogen collection pipe 2-9；The cold finger 2-6 is connected on pipeline by the 7th valve 7；The cold finger 2-6 and chromium powder 2-
The 6th valve 6 is provided between 7 furnaces；The 5th valve 5 is disposed among the second cold-trap 2-8 and Hydrogen collection pipe 2-9
With third valve 3；
The conversion is connected to purification system and reduction hydrogen manufacturing with collection system by the 9th valve 9, the setting of the 9th valve 9
Between carbon dioxide collection pipe 2-3 and cold finger 2-6；
The vacuum-control(led) system includes low vacuum extract system 2-10, fine pumping system 2-11, the first low vacuum
Table 2-12 and the second low vacuum table 2-13；The low vacuum extract system 2-10 and fine pumping system 2-11 passes through the 4th valve
Door 4 accesses pipeline；The first valve 1 is additionally provided between the fine pumping system 2-11 and the 4th valve 4；The low vacuum
The second valve 2 is provided between extract system 2-10 and the 4th valve 4；
4th valve 4 is connected to form main vacuum-pumping pipeline with the 13rd valve 13；
9th valve 9 is connected to main vacuum-pumping pipeline, and the 8th valve 8 is provided on connecting pipeline；Described first
Low vacuum table 2-13 is arranged between the 9th valve 9 and the 8th valve 8；
The second low vacuum table 2-14 is arranged between the 5th valve 5 and third valve 3, the 5th valve 5 and master
Vacuum-pumping pipeline connection；
First valve 1, the second valve 2, third valve 3, the 8th valve 8 and the tenth valve 10 are two two-way valves；
4th valve 4, the 11st valve 11 and the 12nd valve 12 are three two-way valves；5th valve 5, the 6th valve 6, the 7th valve
7, the 9th valve 9 and the 13rd valve 13 are three triple valves.
In the present invention, the material of the copper oxide furnace and chromium powder furnace is preferably quartz glass, the material of the crushing device
It is of fine quality to be selected as stainless steel.
In the present invention, the cylindrical body that is preferably shaped to for crushing device, the crushing device include crushing chamber.At this
In invention, the crushing chamber outer surface is covered with heating tape, by the temperature for obtaining crushing and taking gas for controlling the heating tape.At this
In invention, the inside of the crushing chamber is a rotary objective table, is loaded with the small column bucket that 12 internal diameters are 2cm, greatly
There is a handle that can rotate objective table outside cylindrical body crushing chamber, entire cylindrical body crushing chamber is fixed in a hydraulic system,
The system has the foot pedal being connected on ground to control hydraulic size, and mineral samplers (< 10g) are put into small column bucket, passes through hand
Handle controls the position of cask, controls hydraulic handle using foot pedal and rolls to the sample in specified small column, makes mineral
Inclusion enclave rupture, the ingredient in mineral inclusion is released in a gaseous form.
The present invention does not have particular/special requirement to the shape design of first cold-trap, using well known to those skilled in the art cold
Trap.
In the present invention, the copper oxide furnace preferably includes air inlet pipe and an air outlet pipe, and the air inlet pipe protrudes into copper oxide furnace
Bottom, escape pipe are located at copper oxide furnace roof portion, to ensure going on smoothly for reaction in furnace.In the present invention, the copper oxide furnace
Inside it is filled with copper oxide；The present invention does not have particular/special requirement to the specific loadings of the copper oxide, can be according to the use time of system
Several and mineral samplers amounts determine the loadings of copper oxide.When the only hydrogen isotope of test mineral package fluid, then lead to
Crossing the 11st valve of control and the 12nd valve makes to burst gas without copper dioxide furnace, to simplify testing procedure.
In the present invention, the carbon dioxide collection pipe is removable unloads down.The present invention does not have the carbon dioxide collection pipe
There is particular/special requirement, uses carbon dioxide collection pipe well known to those skilled in the art.
The present invention does not have particular/special requirement to the structure of the cold finger, uses cold finger well known to those skilled in the art；
The cold finger is connected on pipeline by the 7th valve；By the 7th valve may be implemented cold finger and pipeline be connected to or closing.
In the present invention, the structure of the chromium powder furnace is preferably consistent with copper oxide furnace, and details are not described herein；The chromium powder furnace
Inside it is filled with chromium powder；In an embodiment of the present invention, when chromium powder loadings are 120g, mineral sample 2000 of 2g can be tested
More than.In the present invention, it is provided with the 6th valve between the cold finger and chromium powder furnace, cold finger and chromium powder are realized by the 6th valve
Connection or closing between 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 use standard when preparing standard hydrogen with the hollow screw lid of rubber gasket
Sample injector injects standard water into system.
Reduction hydrogen manufacturing of the present invention and collection system include the second cold-trap after being connected on chromium powder furnace.In the present invention
In, the structure of second cold-trap is preferably consistent with the first cold-trap, and details are not described herein.
In the present invention, it is preferably filled with active carbon in the Hydrogen collection pipe, to realize the collection to hydrogen.In this hair
In bright, the 5th valve and third valve are disposed in second cold-trap and Hydrogen collection pipe；Wherein third valve is controllable
Hydrogen collecting pipe and pipeline be connected to or closing.
In the present invention, the reduction hydrogen manufacturing and the effect of collection system are collected and purification system to from thermal explosion
H2O is restored, and collects hydrogen.
In the present invention, the 9th valve is arranged between carbon dioxide collection pipe and cold finger, and the 9th valve can be controlled
Connection or closing between system processed.
In the present invention, the low extract system that vacuumizes is preferably low vacuum mechanical pump.
Vacuum-control(led) system of the present invention includes fine pumping system.In the present invention, the fine pumping
System preferably includes concatenated fore pump and high vacuum metal diffusion pump.
In the present invention, the low vacuum extract system and fine pumping system pass through the 4th valve access pipeline；Institute
It states and is additionally provided with the first valve between fine pumping system and the 4th valve, for controlling fine pumping system；It is described low
It is provided with the second valve between vacuum-pumping system and the 4th valve, for controlling low vacuum extract system.
In the present invention, the 9th valve is connected to main vacuum-pumping pipeline, and the 8th valve is provided on connecting pipeline；
The first low vacuum table is provided between 9th valve and the 8th valve；It is provided between 5th valve and third valve
Second low vacuum table.In the present invention, two low vacuum tables are used for the low vacuum state of detection system.
In the present invention, the vacuum-control(led) system becomes to react to provide vacuum condition and detect the physical chemistry in reaction
Change process.
In the present invention, first valve, the second valve, third valve, the 8th valve and the tenth valve are two two
Port valve；The 11st valve of 4th valve and the 12nd valve are preferably three two-way valves；5th valve, the 6th valve, the 7th valve
Door, the 9th valve and the 13rd valve are preferably three triple valves；The present invention by valve control crushing air-taking system, conversion with
The stream of connection and gas in system between purification system, reduction hydrogen manufacturing and collection system and vacuum control and detection system
Understanding and considerate condition.
In the present invention, in addition to copper oxide furnace and chromium powder furnace, the material of all valves and pipe-line system is preferably general
Logical glass.
Body of the present invention provide it is a kind of using system described in above scheme to mineral fluid inclusions carbon, hydrogen isotope into
The method of row analysis, comprising the following steps:
(1) vacuumize process is carried out to system；
(2) mineral samplers are packed into crushing device, then carry out crushing under vacuum conditions and take gas, the gas of generation passes through
Copper oxide furnace, being formed includes CO2And H2The mixed gas of O, the mixed gas carry out freezing collection in the first cold-trap；
(3) carrying out the first heating to the first cold-trap makes the CO in the mixed gas2It discharges and is collected into carbon dioxide receipts
In collector；
H in the mixed gas is made to the second heating of the first cold-trap progress2O is transferred in cold finger；
(4) carrying out heating to cold finger makes H2O, which enters, carries out reduction reaction in chromium powder furnace, by obtained Hydrogen collection in hydrogen
In collecting pipe；
(5) carbon dioxide being collected into and hydrogen are subjected to mass spectrum two-way off-line test.
The present invention carries out vacuumize process to system.In the present invention, the vacuumize process preferably includes successively to carry out
Pumping low vacuum and pumping high vacuum, specifically includes the following steps: control the 4th valve make whole system only with low vacuum be evacuated be
System connection carries out pumping low vacuum；During taking out low vacuum, the 5th valve and the 6th valve are controlled, opens chromium powder furnace, thus will
Miscellaneous gas is taken away in furnace；When the reading of the first low vacuum table and the second low vacuum table be 10Pa when, control the 4th valve make entirely be
System carries out pumping high vacuum with fine pumping system connectivity.The present invention is by taking out the miscellaneous gas in low vacuum removal system pipeline；It is logical
It crosses pumping high vacuum and provides good vacuum condition for reaction.
After the completion of vacuumize process, mineral samplers are packed into crushing device by the present invention, are then pressed under vacuum conditions
Broken to take gas, for the gas of generation by copper oxide furnace, being formed includes CO2And H2The mixed gas of O, the mixed gas are cold first
Freezing collection is carried out in trap.The present invention does not have special restriction to the source of the mineral, using known to those skilled in the art
, specifically, the mineral for being such as not easily decomposed mineral or easily thermally decomposing.
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 be dried is preferably
It is put into 105 DEG C of baking oven to toast 3~12 hours, for being easy to the mineral of the moisture absorption, such as halite, needs to toast 6~12 hours.
After carrying out vacuumize process to system, mineral samplers are packed into crushing device by the present invention, then under vacuum conditions
It carries out crushing and takes gas, for the crushing gas of generation by copper oxide furnace, being formed includes CO2And H2The mixed gas of O, the gaseous mixture
Body carries out freezing collection in the first 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 cooling first cold-trap of liquid nitrogen.
In the present invention, it is preferably 1~2 time that the crushing, which takes the number of gas,.
In the present invention, it includes CH in gas that the crushing, which takes,4With the gases such as CO, CO is reduced in aoxidizing logical furnace2And H2O,
Reaction equation is shown below:
CH4+ 4CuO=CO2+2H2O+4Cu；
CO+CuO=CO2+Cu。
In addition, for the mineral containing transition-metal ions, such as magnetic iron ore, garnet, Fe therein2+And/or Mn2+In height
Lower react with the water in inclusion enclave of temperature generates hydrogen, and hydrogen reacts in oxidation furnace and generates H2O, to prevent these hydrogen from escaping
It loses and causes isotope fractionation.Specific reaction equation are as follows:
H2+ CuO=H2O+Cu。
In a specific embodiment of the present invention, it is preferable to use liquid nitrogen glass holder lives the first cold-trap.At low temperature, H2O and CO2Quilt
Freezing is collected in the first cold-trap, and the gas not being frozen is preferably taken away by pumped vacuum systems, and impact analysis result is avoided.
In the present invention, it is preferred to specifically: the 4th valve of control makes whole system connect progress with low vacuum extract system
Low vacuum is taken out, when the first low vacuum table and the second low vacuum meter reading are less than 10Pa, then controls the 4th valve entire reaction
System is connect with fine pumping system；When the first low vacuum table and the second low vacuum meter reading are 0Pa, and copper oxide furnace temperature
Degree reaches set temperature, when crushing device reaches crushing and takes the temperature of gas, the 8th valve of control, the 9th valve, the 11st valve,
12nd valve and the 13rd valve are connected to crushing air-taking system, conversion with purification system, liquid nitrogen glass holder to the first cold-trap
On, start crushing and takes gas and collect gas.
After the completion of freezing is collected, the present invention, which carries out the first heating to the first cold-trap, makes the CO in mixed gas2It discharges and receives
Collect in carbon dioxide collection pipe.In the present invention, the temperature of the first heating is preferably -80 DEG C；The first heating
Temperature is preferably impregnated the first cold-trap by using dry ice-crude alcohol mixture and is reached；In a specific embodiment of the present invention, preferably will
The liquid nitrogen cup for entangling the first cold-trap replaces with dry ice-crude alcohol mixture cup.In the present invention, the dry ice-crude alcohol mixture
Temperature is preferably -80 DEG C, and the first cold-trap is gradually warmed up, CO2It is changed into gas to be released, and H2O then remains in the first cold-trap
In.The present invention makes the CO released by the tenth valve of control2It is collected into CO2In collecting pipe, CO is collected2Time be preferably
5min。
CO2After collection, the present invention makes the H in mixed gas to the second heating of the first cold-trap progress2O is transferred to cold finger
In.In the present invention, the temperature of second heating is preferably room temperature；The temperature of second heating, which preferably passes through, will impregnate the
The dry ice of one cold-trap-crude alcohol mixture removal reaches；In a specific embodiment of the present invention, dry ice-crude alcohol mixture cup is moved
It opens.In the present invention, the initial temperature of the cold finger is preferably -196 DEG C；The initial temperature of the cold finger preferably passes through liquid
Nitrogen cooling reaches, H2O is frozen in cold finger after releasing in the first cold-trap, to realize H2The transfer of O；The H2O
Transfer time be preferably 5min；H of the invention2O transfer time calculates since when removing dry ice-crude alcohol mixture cup.
The present invention, which carries out the first heating to the first cold-trap, makes the CO in thermal explosion gas2It discharges and is collected into carbon dioxide collection
Guan Zhong；H in thermal explosion gas is made to the second heating of the first cold-trap progress2O is transferred in cold finger.
In the present invention, it is preferred to specifically: after crushing takes gas, closing the 9th valve and the 11st valve makes gaseous mixture
Body is defined in the first cold-trap；The 8th valve and the 9th valve are opened, the gas not freezed by liquid nitrogen in the first cold-trap is taken out
It walks；The 9th valve is turned off, the liquid nitrogen cup outside the first cold-trap is changed into dry ice crude alcohol mixture cup, makes the CO in the first cold-trap2
It releases, and is collected into the CO below the tenth valve2In sample collection tube；Collect CO2After, then the 9th valve is opened, then
Once pump the gas not freezed；Controlling the 9th valve and the 7th valve is connected to the first cold-trap only with cold finger, and it is cold to remove first
Cold finger, is put on liquid nitrogen cup by the dry ice crude alcohol mixture cup outside trap, by the H in the first cold-trap2O is transferred in cold finger.
H2After O is shifted, the present invention, which carries out heating to cold finger, makes H2O, which enters, carries out reduction reaction in chromium powder furnace, will obtain
Hydrogen collection in Hydrogen collection pipe.In the present invention, the heating final temperature of the cold finger is preferably 40~60 DEG C, more preferably
50℃；The heating of the cold finger is reached by using hot-water soak cold finger, in a specific embodiment of the present invention, it is preferable to use temperature
Degree entangles cold finger for 40~60 DEG C of hot water cup.
After cold finger heating, H2O, which is released and enters, carries out reduction reaction in chromium powder furnace.In the present invention, described to go back
The temperature range of original reaction is 830~860 DEG C, and preferably 850 DEG C, the time is preferably 6min；In the present invention, the reduction reaction
Calculating when time certainly starts to warm up cold finger.In the present invention, the H2O is reduced to hydrogen in chromium powder furnace, specific to react
Formula is as follows:
2Cr+3H2O=Cr2O3+3H2↑。
The present invention, which carries out heating to cold finger, makes H2O, which enters, carries out reduction reaction in chromium powder furnace, by obtained Hydrogen collection in
In Hydrogen collection pipe.In the present invention, the reduction reaction is preferred specifically: the 5th valve of control, the 6th valve and the 7th valve
Door, makes cold finger only be connected with chromium powder furnace, the liquid nitrogen for being used to cool down cold finger is removed, using hot-water soak cold finger, make H2O is with gaseous state
Form, which enters, carries out reduction reaction in chromium powder furnace.
After the completion of reduction reaction, the Hydrogen collection that the present invention generates reaction preferably specifically includes in Hydrogen collection pipe
Following steps:
Upper liquid nitrogen cup is covered in the second cold-trap, the 5th valve of control is connected to the second low vacuum table and cuts off and fine pumping system
The connection of system；Then third valve is opened, in the Hydrogen collection pipe after Hydrogen collection to third valve.Hydrogen collection when collection
Liquid nitrogen cup on pipe sleeve, acquisition time are preferably 3 minutes.
After collection obtains carbon dioxide and hydrogen, the present invention by the carbon dioxide being collected into and hydrogen carry out mass spectrum two-way from
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 hydrogen isotope test result of the mineral samplers converts according to the test result of standard hydrogen
It arrives.Present invention preferably uses above systems to produce standard hydrogen, is then carried out using mass spectrum two-way off-line test to standard hydrogen
Test.
In the present invention, producing for the standard hydrogen preferably injects standard water in chromium powder furnace, collects reaction and obtains
Hydrogen, as standard hydrogen.In the present invention, the standard water is preferably national standard water, specific such as QYTB1 (seawater),
QYTB2 (Xi Zangshui) and laboratory standard Beijing tap water QYTB.
In the present invention, the producing for standard hydrogen preferably includes following steps:
(a) vacuumize process is carried out to system；
(b) standard water injected system is entered standard water in chromium powder furnace with gaseous state and is restored by standard sample injector
Reaction；
(c) after the completion of reduction reaction, by the standard Hydrogen collection of generation in Hydrogen collection pipe.
In the present invention, the mode of the vacuumize process of the step (a) is preferably consistent with above scheme, no longer superfluous herein
It states；
In the present invention, the reduction reaction temperature in the step (b) is preferably consistent with above scheme with the time, herein not
It repeats again；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 chromium powder furnace reaches reduction reaction temperature (such as 850 DEG C), controlling the 5th valve is isolated chromium powder furnace with other with the 6th valve, and
It is connected to standard sample injector；Then standard syringe is used, 2 μ L of standard water is taken, injects reduction reaction system, standard water is in heating tape
Or in the case where external heat source, enter Cr powder furnace in a gaseous form, redox reaction occurs.
In the present invention, the mode that hydrogen is collected in the step (c) is preferably consistent with above scheme, no longer superfluous herein
It states.
In the present invention, the mineral samplers inclusion enclave carbon isotope test result is according to standard carbon dioxide test result
Conversion obtains, and 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.
In the present invention, when only testing the hydrogen isotope in the mineral without transition-metal ions, control the 11st
Valve and the 12nd valve, make thermal explosion gas around copper dioxide furnace, other steps and operations methods are consistent with above scheme.
Below with reference to embodiment to a kind of mineral fluid inclusions carbon provided by the invention, hydrogen isotope analysis system and side
Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Using system of the invention, to quartz in a magma hydrothermal Deposits ore, (granularity is 40-60 target minreal sample, is claimed
Good sample pours into the stainless steel small column bucket of carved with mark, is put into 105 DEG C of baking oven baking 3h) test comparison is carried out, often
Secondary test condition and operating method is consistent, test method the following steps are included:
(1) standard hydrogen and carbon dioxide are prepared
Preparation standard hydrogen
1) preparation.The prime mechanical pump and metal diffusion pump opened low vacuum mechanical pump, successively open high vacuum, and
Open the first valve and the second valve；Open CuO furnace, explosive spalling furnace and chromium powder furnace power supply；Controlling the 4th valve makes entirely instead
It answers device to be connected to low vacuum extract system after the second valve, and opens remaining valve of system；When low vacuum meter reading is less than
When 10Pa, then control the 4th valve be connected to the first valve after fine pumping system, and cut off simultaneously entire reaction unit with
The connection of low vacuum extract system.
2) hydrogen manufacturing is restored.When the first and second low vacuum meter readings are 0Pa, and chromium powder furnace is up to 850 DEG C, the 5th valve is controlled
Cr powder furnace is isolated with other in six valve of Men Yu, and is connected to standard sample injector；Then with special standard syringe, mark is taken
Quasi- 2 μ L of water injects reduction reaction system.Standard water enters Cr powder in the case where heating tape or external heat source in a gaseous form
Redox reaction occurs for furnace.Controlling the reaction time is 6 minutes.
3) hydrogen is collected.At the end of reduction reaction 6 minutes, upper liquid nitrogen cup is covered in the second cold-trap, the 5th valve of control connects
The connection of logical second low vacuum table and cutting and fine pumping system；The reading of vacuum meter is write down, third valve is then opened,
In the sample collection tube after Hydrogen collection to third valve.Sample collection tube is provided with active carbon, collection when collecting gas
Liquid nitrogen cup on pipe sleeve, acquisition time are 3 minutes.
Preparation standard carbon dioxide
Standard carbon dioxide gas is to be reacted to be made with anhydrous phosphoric acid by standard GB/T W04405 and GBW04406, then
Its result is measured using mass spectrum two-way off-line test.
(2) sample gas produces (including hydrogen and carbon dioxide)
1) preparation.Equipped with baked sample stainless steel cask by mark be put into crushing device objective table it is corresponding
Position on, in addition disposable copper gasket, in crushing chamber lid, and tighten sealing；Then the heating tape outside crushing chamber, control are opened
The temperature of system crushing chamber is 100-110 DEG C；The 4th entire reaction unit of valve is controlled again only to connect with low vacuum extract system, is beaten
All valves of remaining in reaction unit are opened, the low vacuum pumping of system is carried out；When left and right low vacuum meter reading is 10Pa, then
It controls the 4th valve and connects entire reaction unit and connect with fine pumping system and (while cutting off and the company of low vacuum extract system
It connects).
2) crushing takes gas.When the first and second low vacuum meter readings are 0Pa, and CuO furnace reaches 600 DEG C, control the 8th,
It is (i.e. low true first that the valve of nine, the 11st, the 12nd and the 13rd connect crushing air-taking system and conversion with purification system
Empty table, the first cold-trap, CuO furnace are connected to crushing air-taking system), and this two parts of connection are isolated with other parts；Again
On liquid nitrogen glass holder to the first cold-trap；Then the rotating handle of objective table is rotated equipped with wanting the cask of crushing samples to be adjusted to liquid
The underface of pressure handle, the pressure for adjusting hydraulic press is 20MPa, and foot steps on control pedal and rolls sample in cask twice.
3) purification for gas and CO2Collection.At the end of crushing takes gas, closing the 9th valve and the 11st valve makes to crush out
And reacted with CuO generate gas be defined in the first cold-trap for being cased with liquid nitrogen cup；The liquid nitrogen cup for being cased with the first cold-trap
Liquid nitrogen is filled it up with, the 8th valve and the 9th valve is then opened, the gas not freezed by liquid nitrogen in the first cold-trap is taken away；It turns off
Liquid nitrogen cup outside first cold-trap is changed into dry ice crude alcohol mixture cup by the 9th valve, allows the CO of the first cold-trap2It releases, and
The CO being collected into below the tenth valve2In sample collection tube, CO is collected2Timing is 5 minutes；Collect CO2After, then open
Nine valves pump the gas not freezed again；The 9th valve and the 7th valve are controlled, is connected to the first cold-trap only with cold finger,
Remove the dry ice crude alcohol mixture cup outside the first cold-trap, cold finger is put on liquid nitrogen cup, in this way the H in the first cold-trap2O is transferred to
In cold finger, transfer time is 5 minutes.
4) hydrogen manufacturing is restored.At the end of previous step 5 minutes, the 5th valve of control, the 6th valve and the 7th valve make cold finger
Only it is connected to Cr powder furnace；Then remove the liquid nitrogen cup outside cold finger, change hot water cup (40~60 DEG C of hot water temperature), when record reacts
Between 6 minutes.
5) Hydrogen collection.It is consistent with the step of collecting standard hydrogen above.
The standard hydrogen come, sample hydrogen, backpack body CO are collected to above2And with phosphoric acid and national carbonatite standard
(GBW04405 and GBW04406) reacts standard CO obtained2, carry out mass spectrometric measurement.Test method is the two-way sample introduction used
Off-line test mode.The result of test is the isotopic ratio of sample or standard to reference gas, then according still further to following formula (1)
(2) value (value of opposite international standard) of mineral inclusion carbon-hydrogen isotopes is calculated separately out.
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.
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.
For the feasibility of inspection institute's inventive method, and gas method test analysis is taken to compare with thermal explosion, to a Quartz Vein Type
Five quartz specimens carry out the test analysis of two methods respectively in gold mine, the results are shown in Table 1.By 1 result of table, it will thus be seen that 1)
Same sample two methods test result difference≤3 ‰；2) crush method test result is always to be higher than same sample thermal explosion method test
As a result.This illustrate crushing take gas analysis method be it is stable, it is feasible.Crush method test result is always above same sample thermal explosion method
As a result the reason of, may is that the reason of kinetic fractionation increases under high temperature.
1 five quartz specimen crush method of table and thermal explosion method Measurement results
| Sample number | Sample type | Sample size/g | Test result/‰ | Using method |
| 15YE21 | Quartz | 2.5 | -84 | Thermal explosion method |
| 15YE21 | Quartz | 2.5 | -83 | Crush method |
| 15YE22 | Quartz | 2.5 | -81 | Thermal explosion method |
| 15YE22 | Quartz | 2.5 | -80 | Crush method |
| 15YE23 | Quartz | 2.5 | -87 | Thermal explosion method |
| 15YE23 | Quartz | 2.5 | -85 | Crush method |
| 15YE24 | Quartz | 2.5 | -92 | Thermal explosion method |
| 15YE24 | Quartz | 2.5 | -89 | Crush method |
| 15YE25 | Quartz | 2.5 | -91 | Thermal explosion method |
| 15YE25 | Quartz | 2.5 | -89 | Crush method |
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. a kind of mineral fluid inclusions carbon, hydrogen isotope analysis system, which is characterized in that including crushing air-taking system, conversion
With purification system, reduction hydrogen manufacturing and collection system and vacuum control and detection system；
Crushing air-taking system, conversion and the purification system include the crushing device being sequentially connected in series on pipeline, the first cold-trap and
Carbon dioxide collection pipe is disposed with the 13rd valve, the 12nd valve and between the crushing device and the first cold-trap
11 valves are also parallel with copper oxide furnace between the 12nd valve and the 11st valve；First cold-trap and titanium dioxide
The tenth valve is provided between carbon collecting pipe；
The reduction hydrogen manufacturing and collection system include that the cold finger being sequentially connected in series on pipeline, chromium powder furnace, the second cold-trap and hydrogen are received
Collector；The cold finger is connected on pipeline by the 7th valve；The 6th valve is provided between the cold finger and chromium powder furnace；It is described
The 5th valve and third valve are disposed among second cold-trap and Hydrogen collection pipe；
The conversion is connected to purification system and reduction hydrogen manufacturing with collection system by the 9th valve, and the 9th valve is arranged in dioxy
Change between carbon collecting pipe and cold finger；
The vacuum-control(led) system includes that low vacuum extract system, fine pumping system, the first low vacuum table and second are low true
Empty table；The low vacuum extract system and fine pumping system pass through the 4th valve access pipeline；The fine pumping system
The first valve is additionally provided between system and the 4th valve；The second valve is provided between the low vacuum extract system and the 4th valve
Door；
4th valve and the 13rd valve are connected to form main vacuum-pumping pipeline；
9th valve is connected to main vacuum-pumping pipeline, and the 8th valve is provided on connecting pipeline；First low vacuum
Table is arranged between the 9th valve and the 8th valve；
The second low vacuum table is arranged between the 5th valve and third valve, and the 5th valve and main vacuum-pumping pipeline connect
It is logical；
First valve, the second valve, third valve, the 8th valve and the tenth valve are two two-way valves；4th valve,
11 valves and the 12nd valve are three two-way valves；5th valve, the 6th valve, the 7th valve, the 9th valve and the 13rd
Valve is three triple valves.
2. system according to claim 1, which is characterized in that be additionally provided with standard sample injector on the 6th valve.
3. system according to claim 1, which is characterized in that the material of the copper oxide furnace and chromium powder furnace is quartzy glass
The material of glass, the crushing device is stainless steel.
4. a kind of divide mineral fluid inclusions carbon, hydrogen isotope using system described in 3 any one of claims 1 to 3
The method of analysis, comprising the following steps:
(1) vacuumize process is carried out to system；
(2) mineral samplers are packed into crushing device, then carry out crushing under vacuum conditions and take gas, the gas of generation passes through oxidation
Copper furnace, being formed includes CO2And H2The mixed gas of O, the mixed gas carry out freezing collection in the first cold-trap；
(3) carrying out the first heating to the first cold-trap makes the CO in the mixed gas2It discharges and is collected into carbon dioxide collection pipe
In；
H in the mixed gas is made to the second heating of the first cold-trap progress2O is transferred in cold finger；
(4) carrying out heating to cold finger makes H2O, which enters, carries out reduction reaction in chromium powder furnace, by obtained Hydrogen collection in Hydrogen collection
Guan Zhong；
(5) carbon dioxide being collected into and hydrogen are subjected to mass spectrum two-way off-line test.
5. according to the method described in claim 4, it is characterized in that, the step (2) in crushing take gas temperature be 100~
110 DEG C, pressure 20MPa；
The set temperature of the copper oxide furnace is 600~650 DEG C；
The temperature that the freezing is collected is -196 DEG C；The freezing is collected temperature and is reached by cooling first cold-trap of liquid nitrogen.
6. according to the method described in claim 5, it is characterized in that, the step (2) specifically: the 4th valve of control makes whole
A system connect with low vacuum extract system and carries out pumping low vacuum, when the first low vacuum table and the second low vacuum meter reading are less than
When 10Pa, then controls the 4th valve and entire reaction system is connect with fine pumping system；When the first low vacuum table and second
When low vacuum meter reading is 0Pa, and copper oxide furnace temperature reaches set temperature, when crushing device reaches crushing and takes the temperature of gas,
Control the 8th valve, the 9th valve, the 11st valve, the 12nd valve and the 13rd valve, make crush air-taking system, conversion with
Purification system is connected to, and on liquid nitrogen glass holder to the first cold-trap, is started crushing and is taken gas and collect gas.
7. according to the method described in claim 4, it is characterized in that, the temperature of the first heating is -80 DEG C in the step (3)；
The temperature of the first heating is impregnated the first cold-trap by using dry ice-crude alcohol mixture and is reached；
CO is collected in the step (3)2Time be 5min；
The temperature of the second heating is room temperature in the step (3)；The temperature of second heating will be by that will impregnate the first cold-trap
Dry ice-crude alcohol mixture removal reaches；
The H2The transfer time of O is 5min.
8. according to the method described in claim 4, it is characterized in that, in the step (4) reduction reaction temperature be 830~
860 DEG C, time 6min；
The initial temperature of the cold finger is -196 DEG C；The initial temperature of the cold finger is reached by liquid nitrogen cooling；
The heating final temperature of the cold finger is 40~60 DEG C；The heating of the cold finger is reached by using hot-water soak cold finger.
9. the method according to claim 4 or 8, which is characterized in that the step (4) specifically: the 5th valve of control, the
Six valves and the 7th valve, make cold finger only be connected with chromium powder furnace, and the liquid nitrogen for being used to cool down cold finger is removed, cold using hot-water soak
Refer to, makes H2O enters in a gaseous form carries out reduction reaction in chromium powder furnace.
10. according to the method described in claim 4, it is characterized in that, when mineral samplers are the mineral package without transition-metal ions
Body, and when only testing the hydrogen isotope in mineral, controls the 11st valve and the 12nd valve, make thermal explosion gas without
Copper dioxide furnace.
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| CN110031536A (en) * | 2019-04-30 | 2019-07-19 | 核工业北京地质研究院 | Oxygen isotope composition analysis extraction element and method in a kind of rock and mineral |
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