CN113155583A - Calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2Is prepared by extracting - Google Patents
Calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2Is prepared by extracting Download PDFInfo
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- 239000010459 dolomite Substances 0.000 title claims abstract description 76
- 229910021532 Calcite Inorganic materials 0.000 title claims abstract description 70
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 68
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 60
- 239000011435 rock Substances 0.000 title claims abstract description 53
- 230000020477 pH reduction Effects 0.000 title claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 67
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000605 extraction Methods 0.000 claims abstract description 26
- 238000000746 purification Methods 0.000 claims abstract description 17
- 238000012360 testing method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
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- 238000005457 optimization Methods 0.000 abstract description 5
- 238000010998 test method Methods 0.000 abstract description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
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Abstract
The invention relates to the field of carbonate isotope test methods, in particular to calcite and dolomite CO in mixed carbonate rocks based on different acidification temperatures2The method for extracting the extract is high-efficiency. The method comprises the following steps: (1) setting the temperature of a phosphoric acid bath tub at 50 ℃, then putting the mixed carbonate rock sample into a constant-temperature phosphoric acid bath tub, setting the reaction time to be 10min, and adding CO generated after the reaction2Purified and collected as calcite reaction product; (2) when the reaction is finished for 10min, closing an inlet valve and an outlet valve in the constant-temperature phosphoric acid bath tub, and quickly adjusting the water bath temperature of the acid bath tub to 90 ℃; (3) purification of CO2A purification collection line; (4) dolomite CO in mixed carbonate rock2The extraction of (1). The invention is used for the CO of the traditional mixed carbonate sample2The optimization of the gas extraction method can greatly improve the gas separation efficiency and the test precision, andcomplete calcite and dolomite CO are established2Separating and extracting processes, and controlling the gas mixed dyeing proportion in a reasonable range.
Description
Technical Field
The invention relates to the field of carbonate isotope test methods, in particular to a method for testing calcite and CO in dolomite in mixed carbonate rock based on different acidification temperatures2The method for extracting the extract is high-efficiency.
Background
Carbonate rock is one of the important sedimentary rock types on the earth surface, and is different from clastic rock which is weathered, degraded and transported to be finally accumulated in a water body, and carbonate rock is directly precipitated out of the water body. Therefore, the carbonate rock itself records important physicochemical information of the water body in the deposition period, and the carbonate rock also becomes an important carrier for geologists to research the ancient environment and the ancient climate of the earth in the geological history period. Carbon and oxygen isotope analysis is a necessary method for developing the research, carbonate rock is dissolved by phosphoric acid, and generated CO is purified and collected2And putting the gas into a stable isotope mass spectrometer to obtain the carbon and oxygen isotope composition of the carbonate rock mineral.
The phosphoric acid method is a classical method for analyzing carbon and oxygen isotope composition of carbonate rock mineral, and the analysis process mainly comprises an off-line method (traditional manual sample injection) and an on-line method (automatic machine sample injection). Compared with the on-line method, the off-line method is widely used in various laboratories because of the advantages of the selection diversity of reaction conditions, the high air tightness of the reaction device and the low cost. The offline method was first initiated by american scientist mccaga in 1950, and the experiment followed substantially his steps in the next decades: (1) placing a carbonate sample and 100% phosphoric acid on two arms of a Y-shaped glass tube, combining the Y-shaped glass tube and a vacuum valve, and then accessing the Y-shaped glass tube to a vacuum system for vacuumizing; (2) after the vacuum degree is satisfied, transferring the reaction device from the vacuum system to a constant temperatureAfter the temperature is balanced in the warm water bath tub, obliquely placing a reaction device, and enabling the sample to be in contact reaction with phosphoric acid; (3) after the reaction is finished, the reaction device is connected with CO2Purification system for CO2Purifying and collecting; (4) collecting CO2And (5) sending the carbon isotope and the oxygen isotope into a mass spectrometer for carbon isotope and oxygen isotope determination.
However, the complex deposition environment and diagenesis often lead to the presence of multiple intergrown minerals, such as calcite and dolomite, in carbonate rock. At this time, if only CO of mixed minerals can be obtained using the conventional phosphoric acid method2The carbon and oxygen isotope composition of the gas also has no research value. Based on the difference in the reaction rates of calcite and dolomite with phosphoric acid, Epstein et al used the selective phosphoric acid process for the first time in 1964 to separate CO from calcite and dolomite in mixed carbonate samples2Gas and analyzed for the respective isotopic composition. After years of experiments by many scientists, the method is basically fixed as the following steps: (1) the mixed carbonate sample (calcite + dolomite) was reacted with phosphoric acid at 25 ℃ for at least 2h, the CO collected at this stage2The method is used for analyzing the composition of carbon and oxygen isotopes of calcite; (2) the mixed sample is then reacted with phosphoric acid<24h, CO formed in this stage2The gas is considered as the gas generated by the reaction of calcite and dolomite, and is discarded; (3) the reaction is continued at 25 ℃ or by heating the water bath apparatus to 50 ℃ and the CO collected in this stage2Used for analyzing the composition of carbon and oxygen isotopes of dolomite. It is to be noted that the reaction apparatus used in the phosphoric acid method is the same as that used in the conventional phosphoric acid method, but any 1 of the 3 steps of the phosphoric acid method is selected to be equivalent to performing the entire process in the conventional phosphoric acid method.
Liu et al optimized this method in 2018, reduced 3 steps of the traditional phosphoric acid method to 2 steps, and removed the step 2 of abandoning the mixed gas link in the original method. In order to give consideration to both reaction efficiency and reduction of mixed dyeing gas proportion, the particle size distribution of a sample is firstly fixed to be 75-80 microns; second, for calcite content>50%, 30-50% and<30 percent of three cases, the step 1 of the traditional phosphoric acid selection method is respectively adjusted to react for 10 to 15 minutes at 50 ℃ and react at 50 DEG CThe reaction was carried out for 6 minutes at 25 ℃ for 45 minutes. The experimental result shows that the CO of the calcite can be extracted from the mixed sample2Gas, calcite CO extracted in most cases at the same time2The carbon and oxygen isotope values are basically consistent with the true values, and the success of the optimization method is shown.
The above method has some drawbacks. Aiming at the traditional phosphoric acid selecting method, in order to reduce the occurrence of gas mixed dyeing as much as possible, after the reaction temperature and the reaction time are limited, the carbonate sample calcite and dolomite CO are mixed for 1 time2The gas extraction process becomes very cumbersome and inefficient. In addition to the extensive manual operations, it takes more than 24 hours to perform each gas separation extraction of 1 mixed sample, greatly increasing the time cost of stable isotope analysis and research. The optimization method established in 2018 by Liu et al, although greatly improves calcite CO in mixed carbonate samples2The problem of high-efficiency extraction of gas; he believes that the dolomite CO in the mixed sample was present2Is greatly influenced by factors such as gas mixed dyeing, isotope fractionation effect and the like, so that dolomite CO in a mixed sample is not established2The optimized extraction method of (1). In addition, the method of Liu et al adopts different optimization strategies for different proportions of calcite in the mixed carbonate sample, which requires that before the carbon and oxygen isotope experiments are performed, mineral X-ray diffraction whole rock analysis (abbreviated as XRD) is performed on the sample to determine the respective contents of calcite and dolomite, which substantially increases the experiment cost and the experiment period and requires more sample amount to support different experiments.
Therefore, in practical application, a more effective and complete gas extraction method is urgently expected to be provided, and calcite and dolomite CO of the mixed carbonate sample can be efficiently extracted without depending on complicated reaction instrument and equipment2Gas and the gas mixed dyeing proportion can be controlled within an acceptable range.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the mixed carbonate rock with different acidification temperatures based on calcite and CO in dolomite2Is high efficiencyAn extraction method.
The technical scheme of the invention is as follows:
calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2The high-efficiency extraction method comprises the following steps:
(1) sample and phosphoric acid solution preparation
The mixed carbonate samples were milled to a particle size range of 75-80 μm using an agate mortar and different pore size sieves and the prepared samples were placed in a high temperature vacuum oven to remove moisture content. Meanwhile, the phosphoric acid solution with the mass concentration of 100-104% is prepared.
(2) CO in calcite in mixed carbonate rock2Is extracted
Placing the prepared sample into an automatic sample feeder or a Y-shaped tube, connecting the sample and a phosphoric acid bathtub into a purification-gas collection pipeline, vacuumizing the purification-gas collection pipeline, setting the temperature of the phosphoric acid bathtub at 48.5-51.5 ℃, putting the mixed carbonate rock sample into a constant-temperature phosphoric acid bathtub, setting the reaction time at 10min, and adding CO generated after the reaction2And collecting the calcite product as the calcite product in the mixed sample after purification by a purification-gas line.
(3) Phosphoric acid bath warming
When the reaction is finished for 10min, the inlet valve and the outlet valve in the constant temperature phosphoric acid bath tub are closed, and the temperature of the water bath in the constant temperature phosphoric acid bath tub is quickly adjusted to 88.5-91.5 ℃.
(4) Purification of CO2Purification collection pipeline
To be subjected to step (2) CO2After collection, the purification-gas line is evacuated and baked to remove residual CO from the line2And H2O。
(5) CO in dolomite in mixed carbonate rock2Is extracted
When residual CO in the pipeline2And H2After O is removed completely, an outlet valve in the constant temperature phosphoric acid bath is opened, and CO generated after the reaction is removed2And purifying and collecting the dolomite as a dolomite product in the mixed sample.
Preferably, the water bath temperature in step (2) is 50 ℃.
Preferably, the vacuumizing and baking time in the step (2) is 30-50 min.
Preferably, the temperature of the water bath in the step (3) is 90 ℃.
Preferably, the vacuum degree of the vacuum pumping in the step (4) is less than 100mtorr, and the baking temperature is 180-.
Preferably, calcite CO in mixed carbonate rock2And dolomite CO2The total reaction time is set to 80-100min during the extraction process.
Calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2The method can extract calcite and dolomite CO in the mixed carbonate rock samples with different components2The mutual gas pollution ratio is not more than 8%.
Preferably, the method is used for repeatedly testing for many times, and the error proportion of carbon isotope values of calcite and dolomite CO2 in the extracted mixed carbonate rock sample with different component proportions is less than or equal to 5 percent, the error proportion of oxygen isotope values is less than or equal to 8 percent, and the error proportion of cluster isotope values is less than or equal to 4 percent.
The invention achieves the following beneficial effects:
the invention relates to calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2Compared with the traditional selective phosphoric acid method, the efficient extraction method has the advantages that the single-time complete mixed carbonate rock sample contains calcite and dolomite CO2The gas extraction period is shortened from more than 24 hours to 90min, and the time cost of stable isotope analysis in the mixed carbonate rock is greatly reduced.
Compared with the method established in 2018 by Liu et al, the method supplements dolomite CO in the mixed sample2Partial extraction processes can adopt a set of experimental processes (the method of Liu et al adopts three experimental processes according to different proportions) according to various mixing proportions, and the whole rock X-ray diffraction analysis is not required before the experiment, so that the preliminary requirements of the experiment are simplified.
Under the conditions of different mixing ratios of the mixed carbonate rock sample, the precision of the method for obtaining the carbon isotopes of the calcite and the dolomite is equal to that of Liu et al in 2018, but the efficiency is greatly improved. The error in obtaining the dolomite oxygen isotope is obviously smaller than that of the experimental method of Liu et al in 2018.
Drawings
FIG. 1 is a schematic view of the structure of a reaction apparatus in the present invention.
Fig. 2 is a graph showing the results of the carbon isotope test.
Fig. 3 is a graph showing the results of the oxygen isotope test.
Fig. 4 is a graph of cluster isotope test results.
Fig. 5 is a graph comparing the accuracy of the present invention with that of the prior art.
In the figure, 1, a sample reaction system; 11. an inlet valve; 12. a sample machine is fed; 13. a constant temperature phosphoric acid bath tub; 14. an outlet valve; 2. CO22A purification system; 21. a first dewar tank; 22. a second dewar tank; 23. PoraPak; 24. a third dewar tank; 25. a fourth dewar tank; 3. CO22A gas collection system; 31. an outlet valve; 32. and (5) sealing the tube.
Detailed Description
To facilitate an understanding of the present invention by those skilled in the art, specific embodiments thereof are described below with reference to the accompanying drawings.
Examples
The invention provides a method for preparing CO in calcite and dolomite in mixed carbonate rock based on different acidification temperatures2The efficient extraction method (2) is an extraction method using the apparatus shown in FIG. 1. The whole extraction device comprises a sample reaction system 1 and CO2Purification System 2 and CO2A gas collection system 3. The sample reaction system 1 comprises a constant temperature acid bath basin, a sample feeder 12 connected with the constant temperature acid bath basin, and an outlet pipeline, wherein an outlet valve 14 is arranged on the outlet pipeline. The upper end of the sample feeder 12 is connected with a vacuum system, and an inlet valve 11 is arranged on a pipeline of the vacuum system. CO22The purification system 2 comprises CO connected in sequence2Purification line of said CO2Purification pipeline is used for CO in sequence2Purified first Dewar flask 21 (filled with alcohol/dry ice mixture at temperature of ≥ 80 deg.C), second Dewar flask 22 (filled with liquid nitrogen at temperature of-170 deg.C), Porapak23 (polymer porous micro-nano-scaleBalls for adsorbing organic matter possibly mixed in the gas), a third dewar 24 (containing an alcohol/dry ice mixture at a temperature of ≥ 80 ℃) and a fourth dewar 25 (containing liquid nitrogen at a temperature of-170 ℃). The CO is2The gas collection system 3 comprises a gas outlet valve 31 and a sealing tube 32, said sealing tube 32 being for CO2And collecting and storing the gas.
In particular to calcite and CO in dolomite in mixed carbonate rock based on different acidification temperatures2The high-efficiency extraction method comprises the following steps:
(1) sample and phosphoric acid solution preparation
The mixed carbonate samples were milled to a particle size range of 75-80 μm using an agate mortar and different pore size sieves and the prepared samples were placed in a high temperature vacuum oven to remove moisture content. Meanwhile, the phosphoric acid solution with the mass concentration of 100-104% is prepared, and the step is a basic operation method in a chemical experiment and is not described in more detail here.
(2) CO in calcite in mixed carbonate rock2Is extracted
Placing the prepared sample into an automatic sample feeder 12 or a Y-shaped tube, connecting the prepared sample into a purification-gas collecting pipeline together with a phosphoric acid bathtub, vacuumizing the purification-gas collecting pipeline, setting the temperature of the phosphoric acid bathtub to be 48.5-51.5 ℃, setting the temperature of the water bath selected in the embodiment to be 50 ℃, reacting for 10min, and reacting to generate CO2By CO2Purification System 2 and CO2And a gas collection system 3 for collecting purified gas. Since the specific purification and collection process is a conventional operation in the prior art, it is not described herein again.
(3) Phosphoric acid bath warming
When the reaction is completed for 10min, the inlet valve 11 and the outlet valve 14 of the constant temperature phosphoric acid bath 13 are closed, and the temperature of the water bath of the constant temperature phosphoric acid bath 13 is rapidly adjusted to 88.5-91.5 ℃. In this example, the temperature of the water bath was rapidly adjusted to 90 ℃.
(4) Purification of CO2Purification collection pipeline
To be subjected to step (2) CO2After collection, the lines are evacuated and baked to remove residual CO from the purge-gas collection lines2And H2And O. Vacuumizing and baking for 30-50 min.
(5) CO in dolomite in mixed carbonate rock2Is extracted
When residual CO in the pipeline2And H2After the O is removed, an outlet valve 14 in a constant temperature phosphoric acid bath 13 is opened, and CO generated after the reaction is removed2And purifying and collecting the dolomite as a dolomite product in the mixed sample.
On the basis of the prior art, the method improves the prior reaction steps and conditions, improves the gas separation efficiency, and establishes complete calcite and dolomite CO2Separating and extracting processes, and controlling the gas mixed dyeing proportion in a reasonable range.
Test examples
To verify the effectiveness of the process of the invention, a sample powder was prepared using laboratory pure calcite and dolomite standard samples, with reference to the size recommended by Liu et al in 2018 (75-80 μm), and the ratio of calcite: the test was carried out by preparing mixed samples of dolomite in different proportions (0: 10, 3: 7, 7: 3, 10: 0).
(1)CO2Blend ratio test
In order to test the calcite and dolomite CO obtained by this method2And (3) carrying out mixed dyeing in gas according to the proportion by respectively using pure calcite and dolomite samples according to the experimental process, and respectively recording the numerical values of the gas pressure sensors in the step (2) and the step (5) (table 1).
TABLE 1 reaction information recording sheet for pure calcite and dolomite samples
As shown in Table 1, although optimization of the reaction is possible in terms of both the improvement of the reaction efficiency and the reduction of the mixing ratio, the presence of calcite and dolomite CO is unavoidable2And (4) gas mixed dyeing. Records show that the proportion of gas mixed dyeing is about 7-8%, and is in a reasonable range.
(2) Carbon isotope test results
In order to test whether the carbon isotopes obtained by the method can react with real values, pure calcite and pure dolomite samples are used for respectively obtaining respective carbon isotope compositions (calcite delta) according to reaction processes13CVPDB(%) -2.13 ± 0.05; dolomite delta13CVPDB(%) -1.27 ± 0.02) as reference standard. Multiple replicates were then run using mixed samples (3: 7 and 7: 3) at different ratios to observe the deviation of the carbon isotope values from the true values.
The experimental results show (figure 2) that under the conditions of different mixing ratios, calcite and dolomite CO in the mixed carbonate sample obtained by the method2The carbon isotope value in (1) fluctuates within a small range from the true value to the true value. The carbon isotope value of the dolomite carbon is positively deviated to a certain degree under the condition of lower content (30 percent content), and the maximum deviation degree is less than 5 percent.
(3) Oxygen isotope test results
According to the standard experimental process, the oxygen isotope composition (calcite delta) of pure calcite and dolomite samples is also obtained18OVPDB(%) -14.63 ± 0.05; dolomite delta18OVPDB(%) -7.64 ± 0.21) as reference standard.
The random error of the experimental result shows (fig. 3), under the condition of repeated experiments, the standard deviation of the oxygen isotopes of different components of dolomite is small (not more than +/-0.1 and 1 delta), which indicates that the random error of the method to the oxygen isotopes of the dolomite is small. For experimental results, the oxygen isotope value is gradually positively biased along with the reduction of the calcite content, and when the calcite content is 30%, the positive bias amplitude is about 8%; in comparison, the dolomite oxygen isotope value is relatively stable, and no deviation is seen.
(4) Cluster isotope test results
The cluster isotope is an effective method for quantitatively analyzing the diagenesis temperature and the diagenesis mechanism of carbonate rock minerals which is internationally rising in recent years. Cluster isotopes are generally denoted CO2Medium and light isotopes (12C、16O) is heavily isotopic (13C、18O) case of binary substitution: (18O-13C-16O); by modifying a traditional isotope mass spectrometer, the signals of the cluster isotopes can be received.
Since the cluster isotope becomes an important stable isotope analysis tool after carbon and oxygen isotopes in recent years, the effect of the improved test method on the acquisition of the cluster isotope is also tested.
The experimental result shows (figure 4), under the condition of repeated experiments, the method can accurately extract the calcite and dolomite cluster isotope values in the mixed samples with different proportions, and the error proportion is not more than 4%. The isotope values of the calcite clusters in the samples with different mixing ratios have small negative deviations, and relatively, the isotope values of the dolomite clusters fluctuate above and below the true values, so that no obvious deviation rule is found.
Conclusion
The method aims at the improvement of the traditional selective phosphoric acid method and the method of Liu et al in 2018, and equipment required by the reaction is consistent with the traditional phosphoric acid method. The method does not need to carry out the preliminary full-rock X-ray diffraction quantitative analysis on the sample, adopts the same set of analysis process aiming at the samples with various mixing ratios, and reduces the experimental requirements. In addition, the reaction condition of rapidly heating to 90 ℃ is adopted for the dolomite in the mixed sample, compared with the previous experimental method, the experimental efficiency is greatly improved, and the experimental time is shortened. Through testing of pure calcite and dolomite samples and samples with different mixing ratios, the method improves the reaction efficiency and simultaneously reduces the reaction error as much as possible, so that the obtained carbon, oxygen and cluster isotope values are as close to the true values as possible. Wherein, under the condition of different mixing proportions, the obtained isotope values of calcite (carbon and cluster) and dolomite (carbon, oxygen and cluster) deviate from the true values by less than 5 percent. In addition, random error analysis of the experimental results shows that the standard deviation of the test results is small under repeated experiments, and the stability and repeatability of the experiments are shown. In conclusion, the method can effectively separate the calcite and the dolomite CO in the mixed carbonate rock2The reaction efficiency is improved to a greater extent, andand reaction error is controlled to a small range.
Precision comparative example
In order to compare the experimental accuracy of the method with that of the existing test method, the measured values of carbon and oxygen isotopes in calcite and dolomite obtained under the conditions of different mixing ratios are subtracted from the true values, wherein delta13C＝δ13CTrue value-δ13CMeasured value，Δ18O＝δ18OTrue value-δ18OMeasured valueAnd compared with the previous study analysis (fig. 5). As shown in fig. 5, under the conditions of different mixing ratios, the accuracy of the method for obtaining the carbon isotopes of calcite and dolomite is equal to that of the experimental method of 2018 of Liu et al, and the error of the method for obtaining the oxygen isotopes of dolomite is significantly smaller than that of the experimental method of 2018 of Liu et al. In addition, as can be seen from fig. 4, the method has a very good effect on extracting calcite and dolomite cluster isotopes in the mixed carbonate rock.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. Calcite in mixed carbonate rock and CO in dolomite based on different acidification temperatures2The efficient extraction method is characterized by comprising the following steps:
(1) sample and phosphoric acid solution preparation
Grinding the mixed carbonate sample to a particle size range of 75-80 μm, placing the prepared sample in an oven to remove water content, and preparing 100-104% phosphoric acid solution by mass concentration;
(2) calcite CO in mixed carbonate rock2Is extracted
Placing the prepared sample into an automatic sample feeder or a Y-shaped tube, connecting the sample and a phosphoric acid bath into a purification-gas collection pipeline, vacuumizing the purification-gas collection pipeline, setting the temperature of the phosphoric acid bath at 48.5-51.5 ℃, and putting the mixed carbonate rock sample into a constant temperature furnaceWarm phosphoric acid bathtub, setting reaction time to 10min, and reacting to generate CO2Purifying by a purification-gas collection pipeline and collecting to obtain a calcite product in the mixed sample;
(3) phosphoric acid bath warming
When the reaction is finished for 10min, closing an inlet valve and an outlet valve in the constant-temperature phosphoric acid bath tub, and quickly adjusting the water bath temperature of the constant-temperature phosphoric acid bath tub to 88.5-91.5 ℃;
(4) purification of CO2Purification collection pipeline
To be subjected to step (2) CO2After collection, the purification-gas collection line is evacuated and baked to remove residual CO from the purification-gas collection line2And H2O；
(5) Dolomite CO in mixed carbonate rock2Is extracted
When CO remaining in the purification-gas collecting line2And H2After O is removed completely, an outlet valve in the constant temperature phosphoric acid bath is opened, and CO generated after the reaction is removed2And purifying and collecting the dolomite as a dolomite product in the mixed sample.
2. The different acidizing temperature based mixed carbonate rock of claim 1 wherein the temperature is selected from the group consisting of calcite and CO of dolomite2The high-efficiency extraction method is characterized in that: in the step (2), the temperature of the phosphoric acid bath is set to be 50 ℃.
3. The different acidizing temperature based mixed carbonate rock of claim 1 wherein the temperature is selected from the group consisting of calcite and CO of dolomite2The high-efficiency extraction method is characterized in that: and (3) rapidly raising the temperature of the water bath to 90 ℃ by a temperature adjusting knob.
4. The different acidizing temperature based mixed carbonate rock of claim 1 wherein the temperature is selected from the group consisting of calcite and CO of dolomite2The high-efficiency extraction method is characterized in that: and (4) vacuumizing and baking for 30-50 min.
5. According to claim 1 or4 the mixed carbonate rock based on different acidification temperatures contains calcite and CO in dolomite2The high-efficiency extraction method is characterized in that: degree of vacuum of evacuation in step (4)<100mtorr, baking temperature 180-.
6. The different acidizing temperature based mixed carbonate rock of claim 1 wherein the temperature is selected from the group consisting of calcite and CO of dolomite2The high-efficiency extraction method is characterized in that: calcite CO in para-mixed carbonate rock2And dolomite CO2The total reaction time is set to 80-100min during the extraction process.
7. The different acidizing temperature based mixed carbonate rock of claim 1 wherein the temperature is selected from the group consisting of calcite and CO of dolomite2The high-efficiency extraction method is characterized in that: the method can extract calcite and dolomite CO in the mixed carbonate rock samples with different components2The mutual gas pollution ratio is lower than 8%.
8. The different acidizing temperature based mixed carbonate rock of claim 7 wherein the CO is in calcite and dolomite2The high-efficiency extraction method is characterized in that: repeatedly testing for many times, and extracting calcite and dolomite CO in the carbonate rock sample with different components2The error ratio of carbon isotope value is less than or equal to 5 percent, the error ratio of oxygen isotope value is less than or equal to 8 percent, and the error ratio of cluster isotope value is less than or equal to 4 percent.
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