CN104502440A - Method for online testing carbon and oxygen isotopes of calcite and dolomite in mixed sample - Google Patents
Method for online testing carbon and oxygen isotopes of calcite and dolomite in mixed sample Download PDFInfo
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- CN104502440A CN104502440A CN201410835794.3A CN201410835794A CN104502440A CN 104502440 A CN104502440 A CN 104502440A CN 201410835794 A CN201410835794 A CN 201410835794A CN 104502440 A CN104502440 A CN 104502440A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000012360 testing method Methods 0.000 title claims abstract description 37
- 239000010459 dolomite Substances 0.000 title claims abstract description 29
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 29
- 229910021532 Calcite Inorganic materials 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000001301 oxygen Substances 0.000 title abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 31
- 238000004458 analytical method Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000011435 rock Substances 0.000 claims abstract description 19
- 238000012937 correction Methods 0.000 claims abstract description 4
- 239000001307 helium Substances 0.000 claims description 25
- 229910052734 helium Inorganic materials 0.000 claims description 25
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 238000002307 isotope ratio mass spectrometry Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000010998 test method Methods 0.000 abstract description 4
- 201000004569 Blindness Diseases 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 5
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 230000005445 isotope effect Effects 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000010430 carbonatite Substances 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 210000004884 grey matter Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Abstract
The invention provides an online test method for carbon and oxygen isotopes of calcite and dolomite in a mixed sample. The method comprises the following steps: adopting a carbonate sample with the particle size range of r being more than or equal to 76 mu m and less than or equal to 154 mu m to be analyzed and used; reacting phosphoric acid with the sample powder at a constant temperature of 25 ℃; staged extraction of CO produced by the reaction2Carrying out carbon and oxygen isotope analysis on the gas to obtain carbon and oxygen isotope values of calcite and dolomite in the mixed sample; and correcting the carbon and oxygen isotope values of the calcite obtained by measurement through a correction formula. By utilizing the method for testing the carbon and oxygen isotopes of the calcite and the dolomite in the mixed sample on line, the determination of the carbon and oxygen isotopes of the calcite and the dolomite in the constant sample and the trace sample can be realized, a single-phase diagenesis group can be used as an experimental analysis unit, the blindness of the traditional whole rock analysis is avoided, and the method has the characteristics of high precision, quick test, accurate result and the like.
Description
Technical field
The invention relates to carbonate C-O isotopes method of testing field, specifically about kalzit in biased sample and rauhkalk C-O isotopes on-line testing method.
Background technology
Since McCrea nineteen fifty proposes carbonate and phosphatase reaction measures carbonatite C-O isotopes method, carbonate C-O isotopes is developed greatly in fields such as geoscience, thalassography, hydrology, paleoclimatology, environmental science, archaeology, each area research achievement emerges in an endless stream, and C-O isotopes Research Significance is self-evident.Carbonate C-O isotopes is applied more and more extensive in STUDY OF CARBONATE ROCK RESERVOIR, from the differentiation of sedimentary environment to geology thermometric etc., in reservoir Forming and evolution process, plays unique effect in research.These achievements obtain too busy to get away suitable sample, as pure kalzit, pure rauhkalk etc.But pure kalzit and rauhkalk sample are often difficult to obtain, particularly for geological sample in reality sampling; Geological sample is due to the complicacy in deposition, diagenetic process, and sample is usually impure, and great majority are grey matter cloud rock or cloud matter limestone, not only contains kalzit but also account for absolute great majority containing rauhkalk in sample.Conventional whole-rock sample C-O isotopes measures and obtains the mixing mean value that result is wherein kalzit and rauhkalk C-O isotopes, and market demand effect is poor, pure carbonate samples choose the application that a difficult problem affects carbonate C-O isotopes always.In biased sample, the C-O isotopes method of testing of kalzit and rauhkalk is just equivalent to extract pure kalzit in biased sample and rauhkalk carries out C-O isotopes test, thus can solve carbonate samples sampling problem very well.
Forefathers did some researchs in this respect, mainly contained two classes: one, Chemical Decomposition method: the pure minerals mainly isolating rauhkalk with chemical reagent, then measured its C-O isotopes value; Two, off-line process measures (Wu Jingshu etc. " in METHOD FOR CONTINUOUS DETERMINATION kalzit and rauhkalk the method for C-O isotopes ratio and meaning thereof " the petromineralogy magazine of kalzit and rauhkalk C-O isotopes value in carbonate respectively, phase nineteen ninety the 5th): utilize kalzit and rauhkalk two kinds of mineral different activities, different from the time in phosphatase reaction, control time and temperature, the CO of kalzit and rauhkalk reaction is collected in distribution
2gas, then measures its C-O isotopes value; Owing to extracting CO
2gas methods is that the sample size of needs is large, and analyze time and effort consuming, workload is very large with off-line purifies and separates device.From effect, these two kinds of methods are not very desirable, for the first Chemical Decomposition method, isolate pure kalzit and rauhkalk is very difficult, and are almost impossible concerning the carbonatite of some particulate, thus limit the application of the method; For the second off-line extracting method, due to CO
2gas is temperature variation and vibration impact in generation and purge process, and can produce the kinetic isotope effect of oxygen isotope, data precision is not high, and the sample size simultaneously needed is large, limits its application.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide kalzit and rauhkalk C-O isotopes on-line testing method in a kind of biased sample, it has the features such as precision is high, test is quick, result is accurate.
For achieving the above object, the invention provides kalzit and rauhkalk C-O isotopes on-line testing method in a kind of biased sample, it comprises the following steps:
(1) process of sample:
Impurity, organic removal are carried out to carbonate samples, then grinds, filter out the sample powder of particle size range 76 μm≤r≤154 μm, use to be analyzed;
Filter out the sample powder of particle size range in r≤76 μm simultaneously, the mineralogical analysis of X diffraction total rock is carried out to it, obtains the relative content of kalzit and rauhkalk in sample;
According to the relative content of kalzit in the sample that the mineralogical analysis of X diffraction total rock obtains and rauhkalk, take particle size range containing the pure kalzit of 250 μ g or the 250 μ g pure Dolomite sample powder 76 μm≤r≤154 μm, be placed in constant temperature at 25 DEG C (making the temperature constant of sample powder at 25 DEG C);
Phosphoric acid constant temperature at 25 DEG C is placed;
(2) mensuration of C-O isotopes:
Under 25 DEG C of constant temperature, continuing to blow helium to blow away the air in container to being equipped with particle size range in the container of the sample powder of 76 μm≤r≤154 μm, making to be full of helium in container;
Then add phosphoric acid in this embodiment, react with sample powder;
React after 2 hours, the CO that abstraction reaction produces
2gas carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of kalzit in biased sample;
Continue reaction after 6 hours, continue to blow helium to blow away the CO in container in container
2gas, makes again to be full of helium in container;
Continue reaction more than 80 hours, the CO that abstraction reaction produces
2gas carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of rauhkalk in biased sample;
(3) error analysis and correction:
The C-O isotopes value by following updating formula step (2) being measured to the kalzit obtained is corrected,
Updating formula is: δ
calcite=[δ
calcite+dolomite-δ
dolomite× d/ (c+d)]/[c/ (c+d)],
In formula, δ
calcitethe isotope value of the kalzit after representative corrects,
δ
dolomiterepresent the isotope value that step (2) measures the rauhkalk obtained,
δ
calcite+dolomiterepresent the isotope value of blending ingredients, the CO that namely in step (2), reaction produces for 2 hours
2gas isotope measured value (namely step (2) measures the isotope value of the kalzit obtained),
C/c+d represents the reaction ratio (repeatedly testing according to the weight content of kalzit in the sample that the mineralogical analysis of X diffraction total rock obtains and pure kalzit the 2 hours kalzits obtained reacted the data of 80wt% and calculated) of kalzit,
D/c+d represents the reaction ratio (repeatedly testing according to the weight content of rauhkalk in the sample that the mineralogical analysis of X diffraction total rock obtains and pure Dolomite the 2 hours rauhkalks obtained reacted the data of 2wt% and calculated) of rauhkalk.
In the methods described above, preferably, the carbonate samples adopted is the description according to aspects such as rock type, sedimentary structure, diagenetic phenomenon and reservoir characteristics, in conjunction with geologic background, and the representative carbonate samples picked out.That is, the carbonate samples adopted can for having the sample of geological Significance, by this area routine techniques means, those skilled in the art can learn which kind of carbonate samples is have geological Significance.
In the methods described above, preferably, microscope is utilized to carry out, to reject the impurity in sample to the place to go that sample carries out impurity in step (1).
In the methods described above, preferably, in step (1) to sample carry out organic place to go be sample is placed in not higher than the high-temperature vacuum baking oven of 400 DEG C to remove organic matter.
In the methods described above, preferably, in step (1), by after sample grind into powder, sample powder is dried 2-4 hour at 105 DEG C.
In the methods described above, the mineralogical analysis of X diffraction total rock is carried out to the sample powder of particle size range in r≤76 μm, obtains the relative content of kalzit and rauhkalk in sample.
In the methods described above, preferably, taking particle size range containing the pure kalzit of 250 μ g or 250 μ g pure Dolomite in the sample powder of 76 μm≤r≤154 μm is employing 1,000,000/electronic balance.
In the methods described above, preferably, described phosphoric acid is phosphoric acid solution or the phosphoric acid of mass concentration 90%-100%.The phosphoric acid concentration adopted at least will more than 90%, otherwise the moisture in phosphoric acid can exchange with oxygen isotope in kalzit and rauhkalk, affects the accuracy of oxygen isotope test; Phosphoric acid concentration then can solidify more than 100% under 25 DEG C of conditions in thin stainless steel pipeline, and acid is dripped not out, and test can not be carried out.More preferably, described phosphoric acid is the phosphoric acid solution of mass concentration 96%, and as Merk (Merck & Co., Inc., the lower same) phosphoric acid of mass concentration 96%, its impurity content is few, effective.
In the methods described above, preferably, be more than 12h by the phosphoric acid time that constant temperature is placed at 25 DEG C, make the temperature constant of phosphoric acid at 25 DEG C.
In the methods described above, phosphoric acid and sample are all constant in 25 DEG C.Temperature constant can improve the precision of experimental analysis, temperature variation can cause the change of kalzit or rauhkalk C-O isotopes fractionation factor, thus the result accuracy of impact experiment, traditional offline mode carries out kalzit and the analysis of rauhkalk C-O isotopes in sample, due at CO
2gas produces and accomplishes that temperature is consistent with being difficult in purge process, and data error is comparatively large, and therefore in experimentation, control temperature is very important at 25 DEG C, and the temperature regulating device error of Gasbench is at ± 0.1 DEG C, and precision is very high.
In the methods described above, preferably, the consumption of described phosphoric acid is the phosphoric acid solution every milligram carbonate samples powder of 0.5-1mL mass concentration 96%.
In the methods described above, preferably, the flow continuing to blow helium is 100-150mL/min (being more preferably 150mL/min), and the time is 5-6min.
In the methods described above, preferably, whether being full of helium in container is by detecting peak intensity (employing conventional instrument), working as N
2o peak intensity≤60mv, CO
2during gas first highest peak intensity≤40mv, then prove to be full of helium in container, at this moment think that air is all drained only in container, CO in air
2gas can not have interference to sample test, otherwise prolongation blows the helium time until reach These parameters.
In the methods described above, the mensuration of C-O isotopes adopts GasBench-IRMS coupling equipment (i.e. GasBench coupling isotope-ratio mass spectrometer).
Method of the present invention adopts GasBench-IRMS coupling equipment, under 25 DEG C of constant temperature, utilizes phosphoric acid different from the reactivity of kalzit and rauhkalk, the CO that stage extraction kalzit and rauhkalk and phosphatase reaction produce
2the gas also online isotope-ratio mass spectrometer that imports measures.Utilize kalzit and rauhkalk C-O isotopes on-line testing method in biased sample provided by the invention, the mensuration of kalzit and rauhkalk C-O isotopes value in constant and micro-example can be realized, because sample size can be low to moderate 500 μ g, can with single diagenetic fabric for experimental analysis unit, avoid the blindness that traditional total rock is analyzed, there is the features such as precision is high, test is quick, result is accurate simultaneously.
Accompanying drawing explanation
Fig. 1 is kalzit and rauhkalk C-O isotopes method of testing process flow diagram in the biased sample of embodiment 1;
Fig. 2 A is the productive rate-time chart of kalzit powder at 25 DEG C of the different-grain diameter scope of embodiment 1;
Fig. 2 B is the productive rate-time chart of rauhkalk powder at 25 DEG C of the different-grain diameter scope of embodiment 1;
Fig. 2 C is different-grain diameter kalzit oxygen isotope and productive rate graph of a relation at 25 DEG C of embodiment 1;
Fig. 2 D is the kalzit of particle diameter 76 μm≤r≤154 μm and rauhkalk productive rate-time chart at 25 DEG C of embodiment 1;
Fig. 2 E is different-grain diameter rauhkalk oxygen isotope and productive rate graph of a relation at 25 DEG C of embodiment 1.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide kalzit and rauhkalk C-O isotopes on-line testing method in a kind of biased sample, as shown in the flow process of Fig. 1, it comprises the following steps:
(1) process of sample:
According to the description of the aspects such as rock type, sedimentary structure, diagenetic phenomenon and reservoir characteristic, in conjunction with geologic background, pick out representative carbonate samples, utilize the impurity in microscope rejecting sample, be placed in not higher than the high-temperature vacuum baking oven of 400 DEG C to remove organic matter, then grind, filter out the sample powder of particle size range 76 μm≤r≤154 μm, 2-4 hour is dried, use to be analyzed at 105 DEG C;
Filter out the sample powder of particle size range in r≤76 μm, the mineralogical analysis of X diffraction total rock is carried out to it, obtains the relative content of kalzit and rauhkalk in sample;
According to the relative content of kalzit in the sample that the mineralogical analysis of X diffraction total rock obtains and rauhkalk, adopt 1,000,000/electronic balance to take particle size range containing the pure kalzit of 250 μ g or the 250 μ g pure Dolomite sample powder 76 μm≤r≤154 μm, be placed in constant temperature at 25 DEG C (making the temperature constant of sample powder at 25 DEG C);
The Merk phosphoric acid of mass concentration 96% constant temperature at 25 DEG C is placed more than 12h;
(2) mensuration of C-O isotopes:
Adopt GasBench-IRMS coupling equipment, under 25 DEG C of constant temperature, perform Flush to blow, continue to blow helium to blow away the air in container in the container of the sample powder of 76 μm≤r≤154 μm to being equipped with particle size range, the flow blowing helium is 100-150mL/min, and the time is 5-6min, makes to be full of helium in container, whether being full of helium in container is by detecting peak intensity, works as N
2o peak intensity≤60mv, CO
2during gas first highest peak intensity≤40mv, then prove to be full of helium in container, otherwise prolongation blows the helium time until reach These parameters;
Then add the Merk phosphoric acid of the mass concentration 96% of 0.5mL every milligram carbonate samples powder in this embodiment, react with sample powder;
React after 2 hours, the CO that abstraction reaction produces
2gas imports isotope-ratio mass spectrometer and carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of kalzit in biased sample;
Continue reaction after 6 hours, perform Flush and blow, continue to blow helium to blow away the CO in container in container
2gas, makes again to be full of helium in container;
Continue reaction after 80 hours, the CO that abstraction reaction produces
2gas carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of rauhkalk in biased sample;
(3) error analysis and correction:
The C-O isotopes value by following updating formula step (2) being measured to the kalzit obtained is corrected,
Updating formula is: δ
calcite=[δ
calcite+dolomite-δ
dolomite× d/ (c+d)]/[c/ (c+d)],
In formula, δ
calcitethe isotope value of the kalzit after representative corrects,
δ
dolomiterepresent the isotope value that step (2) measures the rauhkalk obtained,
δ
calcite+dolomiterepresent the isotope value of blending ingredients, the CO that namely in step (2), reaction produces for 2 hours
2gas isotope measured value (namely step (2) measures the isotope value of the kalzit obtained),
C/c+d represents the reaction ratio (repeatedly testing according to the weight content of kalzit in the sample that the mineralogical analysis of X diffraction total rock obtains and pure kalzit the 2 hours kalzits obtained reacted the data of 80wt% and calculated) of kalzit,
D/c+d represents the reaction ratio (repeatedly testing according to the weight content of rauhkalk in the sample that the mineralogical analysis of X diffraction total rock obtains and pure Dolomite the 2 hours rauhkalks obtained reacted the data of 2wt% and calculated) of rauhkalk.
The method of the present embodiment is adopted to analyze the pure kalzit sample powder of different-grain diameter scope or pure Dolomite sample powder, reaction 2 hours in step (2), continue 6 hours, continue to carry out carbon respectively after 80 hours, oxygen isotope analysis, the kalzit powder of the different-grain diameter scope the obtained productive rate-time chart at 25 DEG C as shown in Figure 2 A, the rauhkalk powder of the different-grain diameter scope productive rate-time chart at 25 DEG C as shown in Figure 2 B, at 25 DEG C, different-grain diameter kalzit oxygen isotope and productive rate graph of a relation are as shown in Figure 2 C, at 25 DEG C, the kalzit of particle diameter 76 μm≤r≤154 μm and rauhkalk productive rate-time chart are as shown in Figure 2 D, at 25 DEG C, different-grain diameter rauhkalk oxygen isotope and productive rate graph of a relation are as shown in Figure 2 E.As can be seen from Fig. 2 A, at 25 DEG C, particle diameter has reacted more than 95% at the kalzit of 2 μm≤r≤5 μm at 2 hours, and particle diameter has reacted more than 90% at the kalzit of 10 μm≤r≤38.5 μm at 2 hours, and particle diameter has reacted more than 80% at the kalzit of 76 μm≤r≤154 μm at 2 hours.As can be seen from Fig. 2 B, at 25 DEG C, particle diameter has reacted 10-15% at the rauhkalk of 10 μm≤r≤38.5 μm at 2 hours, and particle diameter has reacted 1-3% at the rauhkalk of 76 μm≤r≤154 μm at 2 hours.Visible, react 2 hours, more than 90% has been reacted at the kalzit of 10 μm≤r≤38.5 μm at 2 hours at particle diameter, the extent of reaction is very high, but particle diameter has also reacted 10-15% at the rauhkalk of 10 μm≤r≤38.5 μm, reaction ratio is also very high, rauhkalk is to kalzit carbon, the interference that oxygen isotope produces is very large, even if by calculating the error concealment that this part rauhkalk is produced, error is also very large, exceed the requirement of industry standard error, therefore particle diameter 10 μm≤r≤38.5 μm are for kalzit and rauhkalk carbon in mensuration biased sample, oxygen isotope is inappropriate.And the kalzit of particle diameter 76 μm≤r≤154 μm and rauhkalk and phosphatase reaction speed difference are apart from large, kalzit reaction more than 80%, rauhkalk only reacts 1-3%, and rauhkalk is less on the impact of kalzit C-O isotopes.As can be seen from Fig. 2 C, reach more than 80% in kalzit reaction, kalzit C-O isotopes kinetic isotope effect error is very little, does not need to correct, at the CO that reaction gathers for 2 hours
2gas, the C-O isotopes value of kalzit in its isotope value representative sample.In continuation reaction after 6 hours, as can be seen from Fig. 2 A, now kalzit complete reaction, rauhkalk reaction about 5%.In continuation reaction after 80 hours, as can be seen from Fig. 2 D, now kalzit is at earlier stage complete reaction and the CO produced
2gas full scale clearance, the CO of rauhkalk
2productive rate reaches about 95%.Have Fig. 2 E to find out, when rauhkalk 95% participates in reaction, the impact of its oxygen isotope kinetic isotope effect is very little, and the error of generation, within industry critical field, therefore extracts the CO of this stage generation
2the C-O isotopes value of rauhkalk in the C-O isotopes value representative sample that gas test obtains.
Embodiment 2
Choose the pure pierite of dam, Peng Lai, Tarim Basin section stromatolite, the pure limestone in the bight ditch section Strike-slip faulted of Tarim Basin; Below with these two pieces of samples be example describe in detail technical scheme of the present invention and as checking.
Step 1: first select pure kalzit and rauhkalk sample by naked eyes and microscopic examination, the purity of kalzit and rauhkalk is checked with X diffractometer, the pure kalzit chosen and pure Dolomite sample are placed in microscope removing impurities, then be placed in and do not remove organic higher than the high-temperature vacuum baking oven of 400 DEG C, grind and filter out the part of particle diameter 76 μm≤r≤154 μm.
Step 2: the sample handled well is put in baking oven and dries 2-4 hour at 105 DEG C, wherein moisture oven dry.
Step 3: take 3 parts, about 200 μ g kalzit sample with 1,000,000/electronic balance, 200 1 part, μ g rauhkalk samples, 400 1 part, μ g rauhkalk samples, 600 1 part, μ g rauhkalk samples; According to kalzit: rauhkalk weight ratio 1:1,1:2,1:3 mix, three kinds of ratio blending ingredients respectively prepare portion.
Step 4: ready sample is put in the tray of Gasbench, 25 DEG C of constant temperature more than 12 hours, makes sample constant in 25 DEG C.
Step 5: perform Flush blowing operation, utilize the helium flow of 100-150ml/min to continue to blow 5-6min, drive the air of bottle away, allows in bottle and is full of He gas.
Step 6: start to instill 96%Merk (Merck) phosphoric acid in bottle, the amount of phosphoric acid wants sufficient, guarantee reacts completely, and general 0.5mL phosphoric acid amount can meet the amount of 1mg carbonate samples, instills appropriate phosphoric acid according to this ratio in conjunction with the sample size of real reaction.
Step 7: treat sample and phosphatase reaction 2 hours, start to extract the CO produced in sample
2gas also imports isotope-ratio mass spectrometer and measures its C-O isotopes value, and this test value can represent the C-O isotopes value of kalzit in biased sample, and the C-O isotopes value of this kalzit need correct.
Step 8: continue reaction 6 hours, performs Flush blowing operation again, blows away the CO that bottle is produced by kalzit and few part rauhkalk before this
2gas, allows bottle be full of He gas.
Step 9: continue reaction more than 80 hours, treat the rauhkalk complete reaction in bottle, extracts the CO produced
2gas also imports isotope-ratio mass spectrometer and measures its C-O isotopes value, i.e. the C-O isotopes value of rauhkalk.
Step 10: corrected by the C-O isotopes value of following updating formula to the kalzit that step 7 draws,
Updating formula is: δ
calcite=[δ
calcite+dolomite-δ
dolomite× d/ (c+d)]/[c/ (c+d)],
In formula, δ
calcitethe isotope value of the kalzit after representative corrects,
δ
dolomiterepresent the isotope value of the rauhkalk that step 9 draws,
δ
calcite+dolomiterepresent the isotope value of blending ingredients, namely in step 7, react the CO produced for 2 hours
2gas isotope measured value (i.e. step 7 draw the isotope value of kalzit),
C/c+d represents the reaction ratio (per sample the weight content of kalzit and pure kalzit repeatedly test the 2 hours kalzits obtained reacted the data of 80wt% and calculated) of kalzit,
D/c+d represents the reaction ratio (per sample the weight content of rauhkalk and pure Dolomite repeatedly test the 2 hours rauhkalks obtained reacted the data of 2wt% and calculated) of rauhkalk.
Step 11: the testing procedure through above completes the test of a sample, is all completed remaining sample according to this program, obtains result as shown in table 1.
Table 1
Note: w
calcite (dolomite): the weight representing kalzit and rauhkalk, cal: represent kalzit, dol: represent rauhkalk.
Error analysis is carried out to the kalzit C-O isotopes value that step 7 draws, acquired results is as shown in table 2, kalzit carbon isotope true value is-2.459, oxygen isotope true value is-10.40, rauhkalk carbon isotope true value is-1.012, oxygen isotope true value is-6.88, kalzit and rauhkalk C-O isotopes true value adopt pure kalzit and pure Dolomite particle diameter at the sample of 76 μm≤r≤154 μm, and at 25 DEG C, experiment obtains repeatedly.
Table 2
Note: w
calcite/ w
dolomite: the weight ratio representing kalzit and rauhkalk, △
13c (
18o): represent the C-O isotopes test value of kalzit and the error of true value.
As can be seen from the error analysis of table 2, at 25 DEG C, the kalzit of particle diameter 76 μm≤r≤154 μm and rauhkalk compound sample are at W
calcite/ W
doloomiteunder the condition of>=1:3, the error of kalzit C-O isotopes test value is very little, meets industry standard carbonate C-O isotopes permissible error (industry standard carbonate C-O isotopes permissible error: δ
13c: ± 0.2 ‰, δ
18o: ± 0.3 ‰).As can be seen here, in biased sample of the present invention, high, the result of the degree of accuracy of kalzit and rauhkalk C-O isotopes on-line testing method is accurately and reliably.
Claims (10)
1. kalzit and a rauhkalk C-O isotopes on-line testing method in biased sample, it comprises the following steps:
(1) process of sample:
Impurity, organic removal are carried out to carbonate samples, then grinds, filter out the sample powder of particle size range 76 μm≤r≤154 μm, use to be analyzed;
Filter out the sample powder of particle size range in r≤76 μm, the mineralogical analysis of X diffraction total rock is carried out to it, obtains the relative content of kalzit and rauhkalk in sample;
According to the relative content of kalzit in the sample that the mineralogical analysis of X diffraction total rock obtains and rauhkalk, take particle size range containing the pure kalzit of 250 μ g or the 250 μ g pure Dolomite sample powder 76 μm≤r≤154 μm, constant temperature at being placed in 25 DEG C;
Phosphoric acid constant temperature at 25 DEG C is placed;
(2) mensuration of C-O isotopes:
Under 25 DEG C of constant temperature, continuing to blow helium to blow away the air in container to being equipped with particle size range in the container of the sample powder of 76 μm≤r≤154 μm, making to be full of helium in container;
Then add phosphoric acid in this embodiment, react with sample powder;
React after 2 hours, the CO that abstraction reaction produces
2gas carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of kalzit in biased sample;
Continue reaction after 6 hours, continue to blow helium to blow away the CO in container in container
2gas, makes again to be full of helium in container;
Continue reaction more than 80 hours, the CO that abstraction reaction produces
2gas carries out C-O isotopes analysis, and the C-O isotopes value obtained represents the C-O isotopes value of rauhkalk in biased sample;
(3) error analysis and correction:
The C-O isotopes value by following updating formula step (2) being measured to the kalzit obtained is corrected,
Updating formula is: δ
calcite=[δ
calcite+dolomite-δ
dolomite× d/ (c+d)]/[c/ (c+d)],
In formula, δ
calcitethe isotope value of the kalzit after representative corrects,
δ
dolomiterepresent the isotope value that step (2) measures the rauhkalk obtained,
δ
calcite+dolomiterepresent the isotope value of blending ingredients, the CO that namely in step (2), reaction produces for 2 hours
2gas isotope measured value,
C/c+d represents the reaction ratio of kalzit,
D/c+d represents the reaction ratio of rauhkalk.
2. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, the carbonate samples adopted is the description according to rock type, sedimentary structure, diagenetic phenomenon and reservoir characteristic aspect, in conjunction with geologic background, the representative carbonate samples picked out.
3. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, utilizes naked eyes and microscope to carry out, to reject the impurity in sample to the place to go that sample carries out impurity in step (1); To sample carry out organic place to go be sample is placed in not higher than the high-temperature vacuum baking oven of 400 DEG C to remove organic matter.
4. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, in step (1), dry 2-4 hour by sample powder by after sample grind into powder at 105 DEG C.
5. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, described phosphoric acid is phosphoric acid solution or the phosphoric acid of mass concentration 90%-100%; Preferably, described phosphoric acid is the phosphoric acid solution of mass concentration 96%.
6. the phosphoric acid time that constant temperature is placed at 25 DEG C wherein, is more than 12h by kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1.
7. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1 or 5, wherein, the consumption of described phosphoric acid is the phosphoric acid solution every milligram carbonate samples powder of 0.5-1mL mass concentration 96%.
8. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, the flow continuing to blow helium is 100-150mL/min, and the time is 5-6min.
9. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, whether being full of helium in container is by detecting peak intensity, works as N
2o peak intensity≤60mv, CO
2during gas first highest peak intensity≤40mv, then prove to be full of helium in container, otherwise prolongation blows the helium time until reach These parameters.
10. kalzit and rauhkalk C-O isotopes on-line testing method in biased sample according to claim 1, wherein, the mensuration of C-O isotopes adopts GasBench-IRMS coupling equipment.
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