CN108956251A - Preparation method of carbonate phase of carbonate rock in old stratum - Google Patents

Preparation method of carbonate phase of carbonate rock in old stratum Download PDF

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CN108956251A
CN108956251A CN201810863791.9A CN201810863791A CN108956251A CN 108956251 A CN108956251 A CN 108956251A CN 201810863791 A CN201810863791 A CN 201810863791A CN 108956251 A CN108956251 A CN 108956251A
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赵悦
胡斌
高建飞
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Institute of Mineral Resources of Chinese Academy of Geological Sciences
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    • G01N1/00—Sampling; Preparing specimens for investigation
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    • G01—MEASURING; TESTING
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    • 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
    • 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
    • G01N27/626—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 using heat to ionise a gas

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Abstract

The invention provides a preparation method of a carbonate phase of carbonate rock in an old stratum, belonging to the field of mineral treatment. The invention provides a preparation method of an old stratum carbonate phase based on split-phase dissolution, which realizes the separation of the carbonate phase by removing surface adsorption of the old stratum carbonate, avoids the influence of impurities such as clay in the old stratum carbonate on a detection result, and has reference and guidance significance for the application of a carbonate mineral selective extraction technology in geology.

Description

A kind of preparation method of old stratum carbonate rock carbonate facics
Technical field
The present invention relates to mineral processing technique field more particularly to a kind of preparation sides of old stratum carbonate rock carbonate facics Method.
Background technique
Forefathers' researchs for carrying out substep Leaching Experiments in the research of Carbonate geochemistry, display spirit of vinegar can be with more Dissolve most of carbonate and minimal amount of noncarbonate phase.These mostly researchs are to dissolve for carbonate to Sr isotope It influences.The selective dissolution method of existing carbonate mineral boron istope analysis includes that spirit of vinegar, dust technology and dilute hydrochloric acid are molten Solution has been applied to general geological sample.But many carbonate samples existing in the prior art are compared with the research sample of forefathers Product are more complicated, and carbonate rock type mainly has micrite, oolitic limestone, calcarenite, molar limestone, argillaceous dolomite, powder Fine grain dolomite, calcite dolomite etc., the age is older, is not uniform carbonate, it is likely that by deposition later period recrystallization Influence.1N NH is thought in the prior art4The processing step of Ac be it is essential, clay mineral adsorption can be removed The influence of phase and ion-exchange sites.Since the measuring accuracy of strontium isotope is not achieved in existing boron, lithium isotope analysis test, and It is much lower to be directed to the marine carbonates contents such as content (< 1ppm) the relatively modern Quaternary Period of old stratum carbonate samples boron, lithium, Because of the processing without taking into account capable substep leaching.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation methods of old stratum carbonate rock carbonate facics.This The method that the preparation method that invention provides is dissolved based on split-phase, old stratum carbonate rock are adsorbed through removing surface layer, realize carbonic acid The separation of salt phase avoids influence of the impurity such as clay to testing result in old stratum carbonate rock.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of old stratum carbonate rock carbonate facics, comprising the following steps:
(1) by old stratum carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product；
(2) solid product that the step (1) obtains is mixed with nitric acid and metathesis reaction occurs, obtain carbonate facics.
Preferably, the partial size of old stratum carbonate rock is greater than 200 mesh in the step (1).
Preferably, in the step (1) old stratum carbonate rock quality and NH4The volume ratio of Ac solution be 2g:40~ 50mL, the NH4The concentration of Ac solution is 1mol/L.
Preferably, the supernatant obtained after the absorption of surface layer is removed in the step (1) and solid product is obtained through washing Product liquid constitute absorption phase.
Preferably, in the step (2) after metathesis reaction further include: by the product of the metathesis reaction successively pass through from The heart, solid phase washing and filtering, obtain carbonate facics.
Preferably, the filtering uses 0.45 μm of nylon leaching film.
Preferably, nitric acid substep is added in the step (2).
The present invention provides a kind of preparation methods of old stratum carbonate rock carbonate facics, comprising the following steps: will always Layer carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product；By the solid product and nitric acid Metathesis reaction occurs for mixing, obtains carbonate facics.The present invention provides a kind of old stratum carbonate rocks based on split-phase dissolution The preparation method of carbonate facics, old stratum carbonate rock are adsorbed through removing surface layer, realize the separation of carbonate facics, are avoided old Influence of the impurity such as clay to testing result in the carbonate rock of stratum.
Also, present invention uses the spirit of vinegar (10%v/v, 1mol/L and 0.5mol/L) for not having to concentration, 2%HNO3 Or 0.5mol/L HCl has at normal temperature carried out point the Ji County such as limestone, stromatolite, laminated limestone typical carbonate rock sample Phased soln, researches show that the Ji County 200mg carbonate samples to use 2 times 5mL1N NH4Ac, 5 drop H2O2Treated, and absorption is compared Boron, lithium content after 10mL MQ water process is higher, and carbonate facics boron, lithium content are low, it is seen that NH4The effect of Ac processing absorption phase It is more significant.Comparison uses NH4Ac treated absorption mutually and carbonate facics: absorption phase Rb/Sr, Sr/Ca high, Mg/Ca, Fe/Ca, Mn/Ca, Mn/Sr are low；After carbonate dissolution, lead to the reduction of Rb/Sr, Sr/Ca ratio, Mg/Ca, Fe/Ca, Mn/Ca, Mn/Sr ratio Value increases.Treated, and carbonate facics can more reflect primary deposit information.Various concentration and the acid dissolution carbonate of type difference Not less, finally consider from effect, stability, convenience etc., it is believed that it is best that 2% nitric acid dissolves carbonate facics.The present invention There is reference and directive significance in geologic application for the selective extraction technology of carbonate mineral.
Detailed description of the invention
Fig. 1 is the constituent content comparison diagram under the conditions of different elution.
Specific embodiment
The present invention provides a kind of preparation methods of old stratum carbonate rock carbonate facics, comprising the following steps:
(1) by old stratum carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product；
(2) solid product that the step (1) obtains is mixed with nitric acid and metathesis reaction occurs, obtain carbonate facics.
The present invention is by old stratum carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product. In the present invention, the old stratum carbonate rock is preferably the Precambrian period, more preferably the Ordovician period, the devonian period or the Carboniferous Period The old stratum carbonate rock of layer.In the present invention, the carbonate rock includes limestone, dolomite, dolomitic limestone, shale white clouds Rock, all kinds of rocks based on calcite, dolomite.
In the present invention, the partial size of the old stratum carbonate rock is preferably greater than 200 mesh.
In the present invention, the old stratum carbonate rock is preferably successively selected and surface cleaning processing by hand specimen.This The hand specimen is selected in invention and the concrete mode of surface cleaning processing does not have special restriction, using those skilled in the art Well known mode.
In the present invention, the quality and NH of the old stratum carbonate rock4The volume ratio of Ac solution be preferably 2g:40~ 50mL, the NH4The concentration of Ac solution is preferably 1mol/L.In the present invention, the NH4Ac solution can remove old formation carbon The influence of the surface layer absorption and clay mineral ion-exchange sites of Carbonate Rocks.
In the present invention, the quality and H of the old stratum carbonate rock2O2Volume ratio be preferably 2g:4~10mL, depending on having Depending on machine matter content is how many, bubble is no longer generated with reaction system and judges organic matter fully reacting.In the present invention, described H2O2Organic matter can be removed.
In the present invention, the H2O2Mass concentration be preferably 30%.
In the present invention, the old stratum carbonate rock, NH4Ac solution and H2O2Mixing preferably carries out under ultrasound, described The time of ultrasound is preferably 40min.
After the completion of ultrasound, ultrasonic product is preferably centrifuged by the present invention, obtains solid product.In the present invention, the centrifugation Revolving speed be preferably 2000~4000rpm, more preferably 3000rpm, the time of the centrifugation is preferably 15~25min, more excellent It is selected as 20min.In the present invention, the number of the centrifugation is preferably 4~5 times.
In the present invention, the product liquid structure that the supernatant obtained after the absorption of surface layer and solid product are washed is removed At absorption phase.In the present invention, solid product is obtained preferably through washing and separation of solid and liquid after the completion of the ultrasound.The present invention There is no special restriction to the dosage of the water, using dosage well known to those skilled in the art, specifically, as 2g always 10mL water is added in layer carbonate rock.In the present invention, the separation of solid and liquid is preferably centrifuged, parameter of the present invention to the centrifugation There is no special restriction, using consistent with above-mentioned parameter, details are not described herein.
After obtaining solid product, the present invention, which mixes the solid product with nitric acid, occurs metathesis reaction, obtains carbonic acid Salt phase.In the present invention, the nitric acid is preferably added step by step.In the present invention, carbonate and nitric acid in the solid product are sent out Raw metathesis reaction can discharge CO2If too many nitric acid is once added, it is violent for reacting excessively sometimes, will cause liquid ejection, damage Sample is lost, substep, which is added, also can be such that nitric acid sufficiently reacts with solid product.The present invention is to total dosage of the nitric acid and every time The dosage of nitric acid does not have special restriction, can guarantee that the carbonate in solid product reacts completely and not will cause sample loss , specifically, as the solid product that the old stratum carbonate rock of 2g obtains is first and 10mL 2%HNO3, after water bath sonicator 40min Add 10mL 2%HNO3Water bath sonicator 40min.In the present invention, bubble is no longer generated with reaction system judge that double decomposition is anti- It should terminate.
It in the present invention, further preferably include by metathesis product after the completion of the metathesis reaction successively through centrifugation, solid phase Washing and filtering, obtain carbonate facics.The present invention does not have special restriction to the concrete operations of the centrifugation and solid phase washing, adopts With mode of operation well known to those skilled in the art.In the present invention, the supernatant that the centrifugation and solid phase are washed Collectively form the carbonate facics.
In the present invention, it is preferable to use 0.45 μm of nylon leaching films for the filtering.
After obtaining carbonate facics, obtained carbonate facics is preferably carried out isotope detection by the present invention.
Old stratum carbonate rock carbonate facics provided by the invention is described in detail below with reference to embodiment, but cannot They are interpreted as limiting the scope of the present invention.
Instrument
Lithium isotope forms test analysis and receives the Neptune type of Isotope Geology key lab of Ministry of Land and Resources more It is completed on plasma mass spectrograph (MC-ICP-MS).9 Faraday cups of the instrument configuration and 5 ion counters.8 farads The configuration carries out accurate position adjusting in centerpiece two sides, with motor driving；One electron multiplier is housed after centerpiece, 4 ion counters are housed on the outside of minimum quality number glass.MC-ICP-MS is double focusing (Voice segment and quality focus) type mass spectrum Mass dispersion can be extended to 17% using dynamic zoom (ZOOM) patented technology by instrument.Enter the said firm after sample atomization to produce Stabilization sampling system (stable introduction system, SIS), this stable sampling system is cyclone and Si Kete The combination of atomizer can provide more stable signal and shorten scavenging period.
Labware and main agents
The pre-treatment work of sample is completed in the Superclean Lab of isotope key lab of Ministry of Land and Resources, indoor clean Cleanliness is thousand grades, is hundred grades in superclean bench.
Vessel used are polypropylene or polytetrafluoroethylene material in experiment flow, using stringent cleaning process, with drop The background of low vessel: first washing-excellent pure grade HNO3(7mol/L) immersion-ultrapure water cleaning, immersion-excellent pure grade HCl (6mol/L) immersion-ultrapure water cleaning is impregnated-is dried for standby.
It tests ultrapure water used to be made by Millipure purifying, resistivity is 18.2M Ω cm.Main chemical reagent There is HNO3、NH4Ac and H2O2, wherein HNO3It is steamed by MOS grades of pure acid by Savillex DST-1000 sub-boiling distillation secondary system Evaporate gained；NH4Ac is guaranteed reagent, content >=99.0%, H2O2For guaranteed reagent, concentration 30%.
Laboratory sample
Select Ji County exemplary carbonate rock samples such as limestone, stromatolite, laminated limestone, argillaceous dolomite, dolomitic limestone Product after screening by hand specimen, are ground into 200 mesh powder.
Embodiment 1
2g sample is weighed, the NH of 10mL, 1mol/L is added4Ac, 20 drop H2O2, shake up abundant reaction, water bath sonicator 40min, 3000rpm is centrifuged 20min, collects supernatant, obtains solid product, repeat the step 3 time, it is clear to be eventually adding 10mL ultrapure water It washes, 3000rpm is centrifuged 20min, and the supernatant 50mL collected in total is to adsorb phase.
10mL 2%HNO is added in solid product3, 10mL2%HNO is added after water bath sonicator 40min3Water bath sonicator 40min adds 20mL 2%HNO3It stands overnight for 24 hours, reacts incomplete sample and still need to that 2%HNO is added3The reaction was continued, directly To solid product, there is no bubbles to emerge, and 3000rpm is centrifuged 20min, collects supernatant, is eventually adding 10mL ultrapure water 3000rpm is centrifuged 10min, and the 50mL supernatant collected in total is carbonate facics.By 0.45 μm of nylon leaching film of supernatant Filtering and heating evaporation is spare, is evaporated to 3mL or so and saline crystallization does not occur.
Since old stratum carbonate rock lithium content is too low, sample size can only be increased, but excessive sample size causes main amount member It is plain excessive.Ion exchange column usesThe PFA ion exchange resin column that company provides, internal diameter 6.4mm, column length 250mm loads AG50W-X12 (100~200 mesh) cation exchange resin of 8mL.It is firstly added 4mL2%HNO3Leacheate 3 Secondary, total 12mL balances pillar, then takes 1mL carbonate facics sample loading.Select 2%HNO3For leacheate, with dissolution carbonate Medium it is identical, do not have to still further conversion medium.Collect the leacheate in the section 19~49mL, and the leaching to 2mL before and after the section Wash pools are monitored, and carry out two for the leacheate in the macroscopic section 9~49mL of sample collection sticky, viscosity is big It is secondary to cross column, obtain eluent.
The 30mL eluent of collection is evaporated, 2mL 2%HNO is added3, it is ready for mass spectrometric measurement.Use Neptune type MC-ICP-MS is tested, and sample introduction concentration is 100 μ g/L.Sample introduces Ar ion plasma by atomizer,7The signal of Li is 5V。7Li and6Li uses Faraday cup H4 and L4 respectively while measuring.Instrument working parameter: RF power 1200W, cooling air 15L/ Min assists gas 0.6L/min, carrier gas 1.15L/min, and atomizer type is Menhard atomizer (50 μ L/min), and analyzer is true Sky 4 × 10-9~8 × 10-9Pa.Accurately to test, it is substantially stabilized that instrument needs 1~2h can be only achieved.In entire test process In, instrument operating condition and sample signal are all more stable.In the analysis process, using standard-sample cross method (Standard-Sample-Bracketing, SSB) come the mass fractionation that rectifies an instrument, standard sample and sample feeding solution Concentration relative deviation controls within 10%.
Measure sample before, instrument is adjusted under optimum Working, first measurement experiment room standard solution CAGS-Li or The boron isotopic abundance ratio for the standard solution that international lithium standard substance IRMM-016 is prepared, to7Li/6Li ratio is stablized, laboratory Standard specimen determination data stablize within the scope of long term monitoring or the isotopic ratio of IRMM-016 in error range with true value one It causes, sample test can be carried out.
Sample measurement uses automatic sampling, and the background measurement for carrying out 20s is needed before every group of data acquisition.Test result indicates Are as follows: δ7LiL-SVEC=[(RSP/RST)-1]×1000‰+δ7LiIRMM-016–L-SVEC, wherein RSPFor sample7Li/6The measurement of Li ratio Value, RSTFor the twice standard specimen adjacent with sample7Li/6Li ratio measurement value is averaged.20 data of every group of collection when test sample, altogether 2~4 groups of data are acquired,7Li/6Li measurement accuracy≤± 0.2 ‰ (2SD).System is cleaned with 2% nitric acid between sample and standard sample Unite 2min, and signal is washed till within the scope of background.Test result is shown in Table 1.
The test result of the old stratum carbonate rock lithium isotope analysis method of 1 embodiment 1 of table
Embodiment 2
2g sample is weighed, the NH of 10mL, 1mol/L is added4Ac, 20 drop (1mL) H2O2, shake up abundant reaction, water bath sonicator 40min, 3000rpm are centrifuged 20min, collect supernatant, obtain solid product, repeat the step 3 time, and it is super to be eventually adding 10mL Pure water cleaning, 3000rpm are centrifuged 20min, and the supernatant 50mL collected in total is to adsorb phase.
10mL2%HNO is added in solid product3, 10mL 2%HNO is added after water bath sonicator 40min3Water bath sonicator 40min is eventually adding 20mL 2%HNO3It stands overnight for 24 hours, reacts incomplete sample and still need to that 2%HNO is added3The reaction was continued, Up to solid product, there is no bubbles to emerge, and 3000rpm is centrifuged 20min, collects supernatant, is eventually adding 10mL ultrapure water 3000rpm is centrifuged 10min, and the 50mL supernatant collected in total is carbonate facics.By 0.45 μm of nylon leaching film of supernatant Filtering and heating evaporation is spare.
Ion exchange resin column uses the U.S.The PFA ion exchange resin column of company, diameter 3.2mm are high For 3.5cm.It takes B total amount to be greater than the sample of 500ng, uses NH3·H2The pH value that O adjusts sample is 6.0, then leads to sample solution Crossing effects of boron resin Amberlite IRA 743 (being crushed to 60~80 mesh) separation and concentration, (effects of boron resin prepares: 2mLH2O, 2mL2%HNO3, 3mL sodium acetate-hac buffer, 1mLH2O, detection pH value are 5.0~6.0), resin is drenched through 2mL high purity water Elution cation, finally uses 6mL 2%HNO3Adsorbed boron is eluted, eluent is collected.
The test analysis of B isotope is completed on Thermo Neptune type MC-ICP-MS, and sample introduction concentration is about 100 μ g/ L.Using NIST SRM951 as standard substance in test process.11B and10B uses H3 and L3 Faraday cup to receive respectively.Instrument Device running parameter: RF power 1280W, cooling air 16L/min assist gas 0.8L/min, carrier gas 1.0L/min.Running parameter is because of instrument Device state does a little adjustment sometimes, but general variation is little.Accurately to test, it is sufficiently steady that instrument needs 1~2h can be only achieved It is fixed.In entire test process, instrument operating condition and sample signal are all more stable.In experiment, using 100 μ g/L NIST 951 adjusting instrument parameters, to obtain optimum sensitivity,11The signal of B is 1.5V or so.In the analysis process, using standard-sample Product interior extrapolation method (Standard-Sample-Bracketing, SSB) come the mass fractionation that rectifies an instrument, standard sample and sample into The concentration relative deviation of sample solution controls within 10%.
δ11B (‰)=[(RSP/RST) -1] × 1000, wherein RSP is sample11B/10The measured value of B ratio, RSTFor with sample The standard specimen twice of condition neighbour11B/10B ratio measurement value is averaged.20 data of every group of collection when test sample acquire 2~4 groups of numbers altogether According to.For boron in MC-ICP-MC sampling system, memory effect is very strong, and effective and efficient cleaning process is the key that test.For Memory effect is reduced, uses 2%HNO between adjacent test twice3, Milli-Q H2O and 1%HNO3Intersect cleaning, signal is washed till Within the scope of background.Test result is shown in Table 2.
The test result of the carbonate rock boron istope analysis method of 2 embodiment 2 of table
Comparative example
It is identical as embodiment 1,2, difference be only that used without concentration spirit of vinegar (10%v/v, 1mol/L and 0.5mol/L), 2%HNO3Or Ji County typical carbonate rock sample such as 0.5mol/L HCl dissolution limestone, stromatolite, to determine most Excellent split-phase extraction conditions.The absorption of acquisition is mutually and carbonate facics has only carried out the analysis of constituent content, does not carry out isotope Test, thus sample size and corresponding reagent dosage are lower.
Select limestone (JEY-1), stromatolite (TL-3), laminated limestone (JX-14-51), argillo arenaceous dolomite (JX-14- 67) after 4 kinds of Ji County typical carbonate rock samples are screened by hand specimen, 200 mesh powder are ground into.Limestone international standards (IAEA- B7) this comparative experiments that variety classes acid has only been carried out as uniform pure carbonate samples.
By two 8 equal parts of sample of JEY-1 and TL-3, every part weighs 200mg；Two samples 10 of JX-14-51 and JX-14-67 Equal part, every part weighs 200mg.Rinsing step I is carried out first: compared NH4Ac, a few drop H2O2It is mutually imitated with the extraction absorption of no boron water The experiment of fruit, remaining carbonate facics and IAEA-B7 carry out rinsing step II:10%HAc, 1mol/L HAc, 0.5mol/L HAc, 2%HNO3Or the comparative experiments of 0.5mol/L HCl (8 aliquot samples do not carry out the conditions correlation) dissolution conditions, it is specific to test Condition list is as shown in table 3.
Researches show that the Ji County 200mg carbonate samples to use 2 times 5mL 1N NH4Ac, 5 drop H2O2Absorption phase that treated Higher compared with boron, the lithium content after 10mL MQ water process, carbonate facics boron, lithium content are low, it is seen that NH4The effect of Ac processing absorption phase Fruit is more significant.Comparison uses NH4Ac treated absorption mutually and carbonate facics: absorption phase Rb/Sr, Sr/Ca high, Mg/Ca, Fe/ Ca, Mn/Ca, Mn/Sr are low；After carbonate dissolution, lead to the reduction of Rb/Sr, Sr/Ca ratio, Mg/Ca, Fe/Ca, Mn/Ca, Mn/Sr Ratio increases (see Fig. 1), and Fig. 1 is the constituent content comparison diagram under the conditions of different elution.Treated, and carbonate facics can more reflect Primary deposit information.The acid dissolution carbonate facics difference of various concentration and type is little, finally from effect, stability, convenience Etc. consider, it is believed that 2% nitric acid dissolve carbonate facics it is best.
3 carbonate split-phase dissolution experiment condition list of table
The present invention provides a kind of preparation methods of old stratum carbonate rock carbonate facics, comprising the following steps: will always Layer carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product；Solid product is mixed with nitric acid Metathesis reaction occurs, obtains carbonate facics.The present invention provides a kind of old stratum carbonate rock carbonic acid based on split-phase dissolution The preparation method of salt phase, old stratum carbonate rock adsorb through removing surface layer, realize the separation of carbonate facics, avoid always The influence of the impurity to testing result such as clay in layer carbonate rock, for carbonate mineral selective extraction technology in geology Application have use for reference and directive significance.
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 (7)

1. a kind of preparation method of old stratum carbonate rock carbonate facics, comprising the following steps:
(1) by old stratum carbonate rock and NH4Ac solution and H2O2Mixing removes surface layer absorption, obtains solid product；
(2) solid product that the step (1) obtains is mixed with nitric acid and metathesis reaction occurs, obtain carbonate facics.
2. preparation method according to claim 1, which is characterized in that the grain of old stratum carbonate rock in the step (1) Diameter is greater than 200 mesh.
3. preparation method according to claim 1 or 2, which is characterized in that old stratum carbonate rock in the step (1) Quality and NH4The volume ratio of Ac solution is 2g:40~50mL, the NH4The concentration of Ac solution is 1mol/L.
4. preparation method according to claim 1, which is characterized in that obtained after removing surface layer absorption in the step (1) Supernatant and solid product washed obtained product liquid and constitute absorption phase.
5. preparation method according to claim 1, which is characterized in that in the step (2) after metathesis reaction further include: The product of the metathesis reaction is successively washed and filtered through centrifugation, solid phase, carbonate facics is obtained.
6. preparation method according to claim 5, which is characterized in that the filtering uses 0.45 μm of nylon leaching film.
7. preparation method according to claim 1, which is characterized in that nitric acid substep is added in the step (2).
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T.R. BAILEY ET AL.: "Dissolution methods for strontium isotope stratigraphy: whole rock analysis", 《CHEMICAL GEOLOGY》 *
苟龙飞 等: "高效分离Li及其同位素的MC-ICP-MS精确测定", 《地球化学》 *

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