CN113087007A - Device for extracting protogenic carbonate crystal lattice sulfate in carbonate rock - Google Patents
Device for extracting protogenic carbonate crystal lattice sulfate in carbonate rock Download PDFInfo
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- CN113087007A CN113087007A CN202110212067.1A CN202110212067A CN113087007A CN 113087007 A CN113087007 A CN 113087007A CN 202110212067 A CN202110212067 A CN 202110212067A CN 113087007 A CN113087007 A CN 113087007A
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Abstract
The invention provides a device for extracting native carbonate crystal lattice sulfate from carbonate rock. The device includes: the device comprises a carbonate rock-acetic acid reaction unit, an acetic acid feeding unit, a sulfate radical-barium salt reaction unit and a barium salt feeding unit; the discharge port of the acetic acid feeding unit is communicated with the feed port of the carbonate rock-acetic acid reaction unit, and the discharge port of the carbonate rock-acetic acid reaction unit and the discharge port of the barium salt feeding unit are both communicated with the feed port of the sulfate radical-barium salt reaction unit. The device is simple in connection among all units, good in sealing performance, capable of effectively isolating air, preventing sulfur isotopes from generating sulfur in the operation process, preventing sulfur isotopes in other minerals from influencing sulfur isotopes in the CAS, and accordingly extracting the primary CAS with high purity.
Description
Technical Field
The invention relates to the technical field of petroleum and natural gas geochemistry, in particular to a device for extracting native carbonate lattice sulfate from carbonate rock.
Background
Carbonate rock refers to rock with a carbonate mineral content of more than 50%. The carbonate rock can be used as a reservoir stratum or a hydrocarbon source rock stratum of petroleum and natural gas, the oil-gas resource reserve of the carbonate rock accounts for about 50% of the total reserve of the world, and the oil-gas yield of the carbonate rock accounts for more than 60% of the total oil-gas yield of the world. The carbonate rock oil gas is also very important in China, and except for traditional carbonate rock oil gas reservoirs of Reqiu Yuan ancient times, Chuanxi North Viridam-pilaster times and Zhanhua sinking ancient times, the newly discovered peak yield equivalent of the Ordovician ultra-deep carbonate rock oil gas reservoir in the Talima basin exceeds 3.7 multiplied by 106t, becoming an important field of oil and gas resource exploration in China.
Carbonate-associated sulfate (CAS) is formed by the substitution of sulfate from seawater into carbonate crystal lattice during carbonate deposition. Because the sulfate is hardly fractionated when entering the carbonate rock crystal lattice, and the sulfur isotope is hardly influenced by the change of temperature and pressure conditions, the sulfur isotope of the CAS can reflect the composition of the sulfate sulfur isotope of the original ancient seawater when the carbonate rock is deposited, is an important index for reconstructing the ancient marine environment and sulfate concentration, is a main basis for restoring the ancient marine environment in the depositing period of the petroleum and natural gas hydrocarbon source rock, can judge the formation period by the CAS sulfur isotope of the natural gas hydrate authigenic carbonate mineral, is an important basis for carrying out oil-gas-source comparison, and has important significance for the exploration of petroleum, natural gas and natural gas hydrate.
But the content of the primary CAS in the sedimentary carbonate rock is extremely low (0-10)3ppm level) is highly susceptible to other minerals in the sample during extraction. For example, carbonate samples often contain siderite (FeCO)3) The chemical property of the method is unstable, the method is easy to react with weak acid, the molecular weight, the molar weight of hydrogen ions consumed by the reaction with acetic acid and products of the method are similar to those of calcite minerals in carbonate minerals, and the calculation of the content of the calcite after dissolution is interfered, so that relatively accurate primary CAS content data cannot be obtained; as another example, carbonate samples typically contain small amounts of pyrite (10)5～106ppm level), the pyrite can generate oxidation reaction to generate sulfate radical under the air and acid condition, and the process is as follows:
FeS2+3.5O2+H2O→Fe2++2SO4 2-+2H+
Fe2++H++0.25O2→Fe3++0.5H2O
FeS2+14Fe3++8H2O→15Fe2++2SO4 2-+16H+
in the experimental process, sulfate radicals generated after pyrite oxidation can be mixed into the solution containing the primary CAS to cause pollution, and because the content of pyrite is far higher than that of the primary CAS, the distribution range of the common sulfur isotope composition (minus 20-minus 10 per thousand) is also greatly different from that of the primary CAS sulfur isotope (10-24 per thousand). Therefore, oxidation of a very small amount of pyrite has a great influence on the extraction purity of the primary CAS, thereby seriously affecting the primary CAS content and the test results of sulfur isotopes.
With the deep research of our country on the emerging energy fields of deep-ultra deep carbonate oil and gas reservoirs, natural gas hydrate deposits and the like, the precision required by exploration is higher and higher, and the purity requirement of the required primary CAS is also stricter, but the prior art has no instrument and equipment conditions which can meet the high-precision extraction of the primary CAS of the carbonate rock sample.
Disclosure of Invention
The invention provides a device for extracting native carbonate lattice sulfate from carbonate rock, which can not only effectively extract native CAS in a carbonate rock sample, but also eliminate the influence of sulfur elements in other minerals in the extraction process, and cannot cause sulfur isotope fractionation.
The invention provides a method for extracting native carbonate lattice sulfate from carbonate rock, which is convenient to operate and low in cost.
The invention provides a device for extracting native carbonate crystal lattice sulfate from carbonate rock, which comprises: the device comprises a carbonate rock-acetic acid reaction unit, an acetic acid feeding unit, a sulfate radical-barium salt reaction unit and a barium salt feeding unit;
the discharge port of the acetic acid feeding unit is communicated with the feed port of the carbonate rock-acetic acid reaction unit, and the discharge port of the carbonate rock-acetic acid reaction unit and the discharge port of the barium salt feeding unit are both communicated with the feed port of the sulfate radical-barium salt reaction unit.
The device as described above, further comprising a shielding gas unit, wherein the shielding gas unit is respectively communicated with the shielding gas inlet of the carbonate rock-acetic acid reaction unit and the shielding gas inlet of the sulfate-barium salt reaction unit.
The device as described above, wherein a control unit is provided between the shielding gas unit and the carbonate rock-acetic acid reaction unit.
The device as described above, further comprising an air tightness detection unit, wherein the air tightness detection unit is communicated with the air tightness detection port of the sulfate-barium salt reaction unit.
The device as described above, wherein, further comprising a suck-back prevention unit, the air tightness detection port of the sulfate-barium salt reaction unit is communicated with the inlet of the air tightness detection unit through the suck-back prevention unit.
The device as described above, further comprising a condensing unit, wherein an inlet of the suck-back prevention unit is communicated with an air tightness detection port of the sulfate-barium salt reaction unit through the condensing unit.
The device as described above, further comprising a cooling liquid circulation unit, wherein a cooling liquid outlet of the cooling liquid circulation unit is communicated with a cooling liquid inlet of the condensation unit, and a cooling liquid inlet of the cooling liquid circulation unit is communicated with a cooling liquid outlet of the condensation unit.
The apparatus as described above, further comprising a stirring unit for stirring the reactants in the sulfate-barium salt reaction unit.
The device as described above, wherein, still include the filter unit, the discharge gate of carbonate rock-acetic acid reaction unit passes through filter unit and the pan feeding mouth of sulfate-barium salt reaction unit communicates.
The invention also provides an extraction method of the native carbonate crystal lattice sulfate in the carbonate rock, which is used for extracting the native carbonate crystal lattice sulfate in the carbonate rock.
The invention relates to a device for extracting protogenic carbonate crystal lattice sulfate in carbonate rock, which comprises: the device comprises a carbonate rock-acetic acid reaction unit, an acetic acid feeding unit, a sulfate radical-barium salt reaction unit and a barium salt feeding unit; the discharge port of the acetic acid feeding unit is communicated with the feed port of the carbonate rock-acetic acid reaction unit, and the discharge port of the carbonate rock-acetic acid reaction unit and the discharge port of the barium salt feeding unit are both communicated with the feed port of the sulfate radical-barium salt reaction unit. The device is simple in connection among all units, good in sealing performance, capable of effectively isolating air, preventing sulfur isotopes from generating sulfur in the operation process, preventing sulfur isotopes in other minerals from influencing sulfur isotopes in the CAS, and accordingly extracting the primary CAS with high purity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a first embodiment of the present invention;
FIG. 2 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a second embodiment of the present invention;
FIG. 3 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a third embodiment of the present invention;
FIG. 4 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a fourth embodiment of the present invention;
FIG. 5 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a fifth embodiment of the present invention;
FIG. 6 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a sixth embodiment of the present invention;
FIG. 7 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to a seventh embodiment of the present invention;
FIG. 8 is a schematic view of an apparatus for extracting native carbonate lattice sulfates from carbonate rock according to an eighth embodiment of the present invention;
fig. 9 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a ninth embodiment of the present invention.
Description of reference numerals:
1: a carbonate rock-acetic acid reaction unit;
2: an acetic acid feeding unit;
3: a sulfate-barium salt reaction unit;
4: a barium salt feeding unit;
5: a shielding gas unit;
6: a control unit;
7: an air-tightness detection unit;
8: an anti-suck-back unit;
9: a condensing unit;
10: a coolant circulation unit;
11: a filtration unit;
12: a stirring unit;
13: a cold circulation liquid outlet;
14: a cold circulation fluid inlet;
15: qualitative filter paper;
16: a carbonate rock sample;
17: and a rotor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first aspect of the invention provides an apparatus for extracting native carbonate lattice sulphate from carbonate rock. Fig. 1 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a first embodiment of the present invention. As shown in fig. 1, the apparatus includes: the device comprises a carbonate rock-acetic acid reaction unit 1, an acetic acid feeding unit 2, a sulfate radical-barium salt reaction unit 3 and a barium salt feeding unit 4;
the discharge port of the acetic acid feeding unit 2 is communicated with the feed port of the carbonate rock-acetic acid reaction unit 1, and the discharge port of the carbonate rock-acetic acid reaction unit 1 and the discharge port of the barium salt feeding unit 4 are both communicated with the feed port of the sulfate radical-barium salt reaction unit 3.
Specifically, the discharge port of the acetic acid feeding unit 2 is communicated with the feed port of the carbonate rock-acetic acid reaction unit 1, and is used for feeding the acetic acid stored in the acetic acid feeding unit 2 into the carbonate rock-acetic acid reaction unit 1, an acetic acid solution flows out from the discharge port of the acetic acid feeding unit 2 and enters the carbonate rock-acetic acid reaction unit 1 through the feed port of the carbonate rock-acetic acid reaction unit 1, and the acetic acid solution dissolves the native CAS in the carbonate rock sample placed in the carbonate rock-acetic acid reaction unit 1 to obtain a native CAS acidolysis solution; the primary CAS acidolysis solution flows out from a discharge port of the carbonate rock-acetic acid reaction unit 1 and enters the sulfate radical-barium salt reaction unit 3 through a feed port of the sulfate radical-barium salt reaction unit 3.
The discharge port of the barium salt feeding unit 4 is communicated with the feed port of the sulfate radical-barium salt reaction unit 3, and is used for feeding the barium salt stored in the barium salt feeding unit 4 into the sulfate radical-barium salt reaction unit 3, and the barium salt solution flows out of the discharge port of the barium salt feeding unit 4 and enters the sulfate radical-barium salt reaction unit 3 through the feed port of the sulfate radical-barium salt reaction unit 3; in the sulfate-barium salt reaction unit 3, barium ions in the barium salt are combined with sulfate radicals in the primary CAS acidolysis solution to form barium sulfate precipitate, and the obtained barium sulfate is the primary CAS in the carbonate rock.
The invention is not limited to a specific type of barium salt, and any barium salt that can convert sulfate to a precipitate is within the scope of the invention. In a specific embodiment, the barium salt is selected from barium chloride.
It should be noted that, in the invention, the number of the feeding ports of the sulfate-barium salt reaction unit 3 can be one or more, and when the number of the feeding ports of the sulfate-barium salt reaction unit 3 is one, the discharge port of the barium salt feeding unit 4 and the discharge port of the carbonate rock-acetic acid reaction unit 1 are simultaneously communicated with the feeding ports; when two feeding ports of the sulfate-barium salt reaction unit 4 are provided, the discharge port of the barium salt feeding unit 4 and the discharge port of the carbonate-acetic acid reaction unit 1 can be simultaneously communicated with any one feeding port, the other feeding port is sealed, and the discharge port of the barium salt feeding unit 4 and the discharge port of the carbonate-acetic acid reaction unit 1 can be respectively communicated with one feeding port; when the number of the discharge ports of the sulfate-barium salt reaction unit 3 is larger than two, the discharge port of the barium salt feeding unit 4 and the discharge port of the carbonate rock-acetic acid reaction unit 1 can be simultaneously communicated with any one of the feed ports, other feed ports are sealed, the discharge port of the barium salt feeding unit 4 and the discharge port of the carbonate rock-acetic acid reaction unit 1 can be respectively communicated with one feed port, and other feed ports are sealed.
The invention does not limit the specific structure of the acetic acid feeding unit 2, and all structures which can be used for feeding acetic acid into the carbonate rock-acetic acid reaction unit 1 belong to the protection scope of the invention. In some embodiments, the acetic acid addition unit 2 may be selected from a constant pressure dropping funnel.
The invention does not limit the concrete structure of the barium salt feeding unit 4, and all structures which can be used for adding barium salt into the sulfate radical-barium salt reaction unit 3 belong to the protection scope of the invention. In some embodiments, the barium salt addition unit 4 may be selected from a constant pressure dropping funnel.
The invention does not limit the concrete structure of the carbonate rock-acetic acid reaction unit 1, and all structures capable of carrying out the reaction of the acetic acid solution and the barium salt belong to the protection scope of the invention. In some embodiments, the structure of the carbonate-acetic acid reaction unit 1 may be selected from a rotary receiver or a reaction vessel.
The invention does not limit the concrete structure of the sulfate radical-barium salt reaction unit 3, and all structures which can combine sulfate radical and barium salt belong to the protection scope of the invention. In some embodiments, the structure of the sulfate-barium salt reaction unit 3 may be selected from a round bottom flask, a three-neck flask, or a reaction kettle.
The device of the invention has the advantages of simple connection among the units and good sealing performance, can effectively isolate air, prevent sulfur isotopes from generating sulfur separation in the operation process, prevent sulfur elements in other minerals from influencing the sulfur isotopes in the primary CAS, and can extract the high-purity primary CAS.
Fig. 2 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a second embodiment of the present invention. As shown in fig. 2, in some embodiments of the present invention, the apparatus further comprises a shielding gas unit 5, and the shielding gas unit 5 is respectively communicated with the shielding gas inlet of the carbonate-acetic acid reaction unit 1 and the shielding gas inlet of the sulfate-barium salt reaction unit 3.
The outlet of the protective gas unit 5 is respectively communicated with the protective gas inlet of the carbonate rock-acetic acid reaction unit 1 and the protective gas inlet of the sulfate-barium salt reaction unit 3, and is used for introducing protective gas into the carbonate rock-acetic acid reaction unit 1 and the sulfate-barium salt reaction unit 3, discharging air in the carbonate rock-acetic acid reaction unit 1 and the sulfate-barium salt reaction unit 3, enabling the carbonate rock and acetic acid to react in an environment completely isolated from air, and enabling the sulfate radical and barium salt to react in an environment completely isolated from air. The sulfur isotope can be more effectively prevented from being separated from sulfur, and sulfur elements in other minerals can be prevented from influencing the sulfur isotope in the primary CAS, so that the primary CAS with higher purity can be extracted.
The invention does not limit the concrete structure of the protective gas unit 5, and all structures which can introduce protective gas into the carbonate rock-acetic acid reaction unit 1 and the sulfate radical-barium salt reaction unit 3 belong to the protection scope of the invention; the invention also does not limit the specific type of the protective gas, and all gases which are not easy to react with the carbonate rock belong to the protection scope of the invention. In a particular embodiment, the shielding gas unit 5 is selected from high pressure nitrogen gas cylinders.
Fig. 3 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a third embodiment of the present invention. As shown in fig. 3, in some embodiments of the present invention, a control unit 6 is disposed between the shielding gas unit 5 and the carbonate-acetic acid reaction unit 1. The control unit 6 can flexibly control whether the protective gas in the protective gas unit 5 is input into the carbonate rock-acetic acid reaction unit 1 or not, so that the protective gas input into the carbonate rock-acetic acid reaction unit 1 and the protective gas input into the sulfate radical-barium salt reaction unit 3 are mutually independent, and the operation convenience of the device is improved.
The invention is not limited to the specific structure of the control unit 6, and any structure which can control whether the protective gas in the protective gas unit enters the carbonate rock-acetic acid reaction unit or not belongs to the protection scope of the invention. In one embodiment, the control unit 6 may be a switch.
Fig. 4 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a fourth embodiment of the present invention. As shown in fig. 4, in some embodiments of the present invention, the apparatus further comprises an air-tightness detecting unit 7, and the air-tightness detecting unit 7 is communicated with the air-tightness detecting port of the sulfate-barium salt reaction unit 3.
The air tightness detection unit 7 is filled with liquid, and a pipeline for communicating the air tightness detection unit 7 with the sulfate radical-barium salt reaction unit 3 extends below the liquid level of the liquid. The airtightness in the carbonate rock-acetic acid reaction unit 1 and the sulfate-barium salt reaction unit 3 is detected by observing whether the liquid in the airtightness detection unit 7 has bubbles. The reaction of the carbonate rock and the acetic acid and the reaction of the sulfate radical and the barium salt can be ensured to be carried out in an environment completely isolated from air by detecting the air tightness in the carbonate rock-acetic acid reaction unit 1 and the sulfate radical-barium salt reaction unit 3. The sulfur isotope can be more effectively prevented from being separated from sulfur, and sulfur elements in other minerals can be prevented from influencing the sulfur isotope in the primary CAS, so that the primary CAS with higher purity can be extracted.
Specifically, the switch of the shielding gas unit 5 is turned on, the flow rate of the shielding gas in the shielding gas unit 5 is adjusted, and when bubbles exist in the liquid of the air tightness detection unit 7, the air tightness of the sulfate-barium salt reaction unit 3 is good; subsequently, the opening and closing of the vent port of the acetic acid feeding unit 2 and the control unit 6 are sequentially opened, the vent port of the acetic acid feeding unit 2 is closed when there is no bubble in the liquid of the airtightness detecting unit 7, and the airtightness of the carbonate-acetic acid reaction unit 1 is good when there is a bubble in the liquid of the airtightness detecting unit 7.
The invention is not limited to the specific structure of the air tightness detecting unit 7, and any container capable of containing liquid is within the protection scope of the invention. In some embodiments, the air-tightness detecting unit 7 may be selected from a conical flask, a beaker, or a jar.
Fig. 5 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a fifth embodiment of the present invention. As shown in fig. 5, in some embodiments of the present invention, the apparatus further comprises a suck-back prevention unit 8, and the air tightness detection port of the sulfate-barium salt reaction unit 3 is communicated with the inlets of the air tightness detection unit 7 through the suck-back prevention unit 8.
In the invention, the suck-back prevention unit 8 is used for preventing liquid or water vapor in the air tightness detection unit 7 from being sucked back into the sulfate radical-barium salt reaction unit 3 in the operation process of the device, so that the purity of the finally obtained primary CAS is influenced.
Specifically, the air tightness detection port of the sulfate-barium salt reaction unit 3 is communicated with the inlet of the suck-back prevention unit 8, and the outlet of the suck-back prevention unit 8 is communicated with the inlet of the air tightness detection unit 7.
Fig. 6 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a sixth embodiment of the present invention. As shown in fig. 6, in some embodiments of the present invention, the apparatus further includes a condensing unit 9, and the inlets of the suck-back prevention unit 8 are communicated with the airtightness detection port of the sulfate-barium salt reaction unit 3 through the condensing unit 9.
In the invention, because the reaction generated in the sulfate-barium salt reaction unit 3 is an exothermic reaction, and the condensation unit 9 is arranged, the phenomenon of temperature rise in the sulfate-barium salt reaction unit 3 caused by the exothermic reaction can be relieved, and the safety performance of the device is improved.
Specifically, one end of the condensing unit 9 is communicated with an inlet of the suck-back prevention unit 8, and the other end of the condensing unit 9 is communicated with an air tightness detection port of the sulfate-barium salt reaction unit 3. In a specific condensation process, the cooling liquid enters the condensation unit 9 through the cooling liquid inlet of the condensation unit 9 and flows out through the cooling liquid outlet of the condensation unit 9, and as known to those skilled in the art, the position of the cooling liquid inlet is lower than that of the cooling liquid outlet.
The invention does not limit the concrete structure of the condensation unit 9, and all structures which can condense the sulfate radical-barium salt reaction unit 3 belong to the protection scope of the invention. In some embodiments, the condensing unit 3 may be a condensing tube.
Fig. 7 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a seventh embodiment of the present invention. As shown in fig. 7, in some embodiments of the present invention, the apparatus further includes a cooling liquid circulation unit 10, a cooling liquid outlet of the cooling liquid circulation unit 10 is communicated with a cooling liquid inlet of the condensation unit 9, and a cooling liquid inlet of the cooling liquid circulation unit 10 is communicated with a cooling liquid outlet of the condensation unit 9.
The present invention uses the cooling liquid circulating unit 10 to supply the cooling liquid to the condensing unit 9. The present invention is not limited to the specific structure of the cooling liquid circulation unit 10, and any structure capable of inputting the cooling liquid to the condensation unit 9 falls within the protection scope of the present invention. In some embodiments, the coolant circulation unit 10 may be a coolant circulation pump.
In some embodiments of the present invention, the apparatus further comprises a stirring unit for stirring the reactants in the sulfate-barium salt reaction unit. The stirring unit is used for stirring the reactants in the sulfate-barium salt reaction unit to promote the full reaction of sulfate and barium salt to generate the primary CAS.
The invention does not limit the concrete structure of the sulfate radical-barium salt reaction unit, and all structures capable of stirring the sulfate radical-barium salt reaction unit belong to the protection scope of the invention. In some embodiments, the stirring unit may be selected from a magnetic stirrer, a stirring paddle, or a thermostated magnetic water bath.
Fig. 8 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to an eighth embodiment of the present invention. In some embodiments of the present invention, as shown in fig. 8, the above apparatus further comprises a filtering unit 11, and the discharge port of the carbonate-acetic acid reaction unit 1 is communicated with the feed port of the sulfate-barium salt reaction unit 3 through the filtering unit 11.
The filtering unit 11 of the invention is used for filtering impurities in the carbonate rock-acetic acid reaction unit 1, and can improve the purity of the primary CAS acidolysis solution entering the sulfate-barium salt reaction unit 3, thereby extracting high-purity CAS.
Specifically, the primary CAS acidolysis solution in the carbonate-acetic acid reaction unit 1 is output from the discharge port of the carbonate-acetic acid reaction unit 1, enters the filter unit 11 through the feed port of the filter unit 11, is filtered by the filter unit 11, is output from the discharge port of the filter unit 11, enters the sulfate-barium salt reaction unit 3 through the feed port of the sulfate-barium salt reaction unit 3, and is combined with barium salt to finally obtain the primary CAS.
The invention is not limited to the specific structure of the filtering unit, and any structure capable of filtering the primary CAS acidolysis solution obtained from the carbonate rock-acetic acid reaction unit 1 falls within the protection scope of the invention. In some embodiments, the filtration unit 11 may be selected from a filter screen or a vacuum filtration device.
The second aspect of the invention also provides a method for extracting the native carbonate crystal lattice sulfate from the carbonate rock, which uses the device to extract the native carbonate crystal lattice sulfate from the carbonate rock.
The extraction method is simple to operate, and the primary CAS in the carbonate rock sample can be extracted at low cost.
The device of the invention will be further described below with reference to specific embodiments, which are exemplified by a laboratory device.
Examples
Fig. 9 is a schematic view of an apparatus for extracting native carbonate lattice sulfate from carbonate rock according to a ninth embodiment of the present invention. As shown in fig. 9, the apparatus of the present embodiment includes: the device comprises an air tightness detection unit 7, a protective gas unit 5, an anti-suck-back unit 8, a control unit 6, a sulfate-barium salt reaction unit 3, a stirring unit 12, a condensation unit 9, a barium salt feeding unit 4, a carbonate rock-acetic acid reaction unit 1, an acetic acid feeding unit 2 and a cooling liquid circulation unit 10;
wherein, the discharge port of the acetic acid feeding unit 2 is communicated with the feed port of the carbonate rock-acetic acid reaction unit 1, and the discharge port of the carbonate rock-acetic acid reaction unit 1 and the discharge port of the barium salt feeding unit 4 are both communicated with the feed port of the sulfate radical-barium salt reaction unit 3;
the protective gas unit 5 is respectively communicated with a protective gas inlet of the carbonate rock-acetic acid reaction unit 1 and a protective gas inlet of the sulfate radical-barium salt reaction unit 3; a control unit 6 is arranged between the protective gas unit 5 and the carbonate rock-acetic acid reaction unit 1;
an air tightness detection port of the sulfate-barium salt reaction unit 3 is communicated with an inlet of the condensation unit 9, an outlet of the condensation unit 9 is communicated with an inlet of the suck-back prevention unit 8, and an outlet of the suck-back prevention unit 8 is communicated with an inlet of the air tightness detection unit 7;
a cold circulation liquid outlet 13 of the cooling liquid circulation unit 10 is communicated with a cooling liquid inlet of the condensation unit 9, and a cold circulation liquid inlet 14 of the cooling liquid circulation unit 10 is communicated with a cooling liquid outlet of the condensation unit 9;
the sulfate-barium salt reaction unit 3 is disposed above the stirring unit 12.
In this embodiment, the above device is used to extract the primary CAS from the carbonate sample, and the specific steps include:
1) air tightness detection
Adding liquid into the air tightness detection unit 7, opening a switch of the cooling liquid circulation unit 10, setting the temperature of the cooling liquid to be 5 ℃, opening a switch of a nitrogen bottle (a protective gas unit 2) after the temperature of the cooling liquid is stable, and adjusting the nitrogen flow to stably generate 3-4 bubbles per second in the liquid of the air tightness detection unit 7, which indicates that the air tightness of the sulfate radical-barium salt reaction unit 3 is good;
then opening an exhaust port of the acetic acid feeding unit 2 and the control unit 6, closing the exhaust port of the acetic acid feeding unit 2 when the bubbles in the liquid of the air tightness detecting unit 7 obviously disappear, and indicating that the air tightness of the carbonate rock-acetic acid reaction unit 1 is good when 3-4 bubbles are stably generated every second after the liquid of the air tightness detecting unit 7 is recovered;
2) air in the emptying device
Opening an exhaust port of the acetic acid feeding unit 2 to a semi-open state, increasing the nitrogen flow to the liquid of the air tightness detection unit 7 to stably generate 3-4 bubbles per second, ventilating for 5min, and evacuating the air in the device;
3) acidolysis of carbonate rock samples
Folding two qualitative filter papers 15 into a funnel and placing the funnel in a carbonate rock-acetic acid reaction unit 1, placing a carbonate rock sample 16 in the carbonate rock-acetic acid reaction unit 1, opening a feeding port of an acetic acid feeding unit 2, adding an acetic acid solution with the concentration of 0.1mol/L into the carbonate rock-acetic acid reaction unit 1, closing the feeding port of the acetic acid feeding unit 2 when the liquid level of the acetic acid solution in the carbonate rock-acetic acid reaction unit 1 reaches half of the edge of the funnel folded by the qualitative filter paper 15, and reacting the acetic acid solution with the carbonate rock sample 16 to obtain a primary CAS acidolysis solution;
4) extraction of native CAS
Placing a polytetrafluoroethylene rotor 17 in a sulfate radical-barium salt reaction unit 3, opening a discharge port of the carbonate rock-acetic acid reaction unit 1 after acetic acid in the carbonate rock-acetic acid reaction unit 1 reacts with a carbonate rock sample 16 for 8min, allowing acidolysis solution to enter the sulfate radical-barium salt reaction unit 3, opening a discharge port of a barium salt feeding unit 4, adding 20mL of a barium chloride solution with the mass percentage of 10% into the sulfate radical-barium salt reaction unit 3, opening a magnetic stirrer (stirring unit 12), and allowing sulfate radicals in the acidolysis solution to react with barium chloride at 80 ℃;
repeating the steps, reacting for 30min after the primary CAS acidolysis solution is added into the sulfate-barium salt reaction unit 3 for the last time, stopping heating, and stopping stirring after the solution is cooled to obtain the primary CAS.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. An apparatus for extracting native carbonate lattice sulfate from carbonate rock, comprising: the device comprises a carbonate rock-acetic acid reaction unit, an acetic acid feeding unit, a sulfate radical-barium salt reaction unit and a barium salt feeding unit;
the discharge port of the acetic acid feeding unit is communicated with the feed port of the carbonate rock-acetic acid reaction unit, and the discharge port of the carbonate rock-acetic acid reaction unit and the discharge port of the barium salt feeding unit are both communicated with the feed port of the sulfate radical-barium salt reaction unit.
2. The apparatus of claim 1, further comprising a shielding gas unit in communication with a shielding gas inlet of the carbonate-acetic acid reaction unit and a shielding gas inlet of the sulfate-barium salt reaction unit, respectively.
3. The apparatus of claim 2, wherein a control unit is disposed between the shielding gas unit and the carbonate-acetic acid reaction unit.
4. The apparatus of claim 3, further comprising an air tightness detection unit, wherein the air tightness detection unit is communicated with the air tightness detection port of the sulfate-barium salt reaction unit.
5. The device of claim 4, further comprising a suck-back prevention unit, wherein the air tightness detection port of the sulfate-barium salt reaction unit is communicated with the inlet of the air tightness detection unit through the suck-back prevention unit.
6. The device of claim 5, further comprising a condensing unit, wherein the inlet of the suck-back prevention unit is communicated with the air tightness detection port of the sulfate-barium salt reaction unit through the condensing unit.
7. The apparatus of claim 6, further comprising a cooling fluid circulation unit, wherein a cooling fluid outlet of the cooling fluid circulation unit is communicated with a cooling fluid inlet of the condensation unit, and a cooling fluid inlet of the cooling fluid circulation unit is communicated with a cooling fluid outlet of the condensation unit.
8. The apparatus of any one of claims 1-7, further comprising a stirring unit for stirring the reactants in the sulfate-barium salt reaction unit.
9. The device of claim 1, further comprising a filtering unit, wherein a discharge port of the carbonate rock-acetic acid reaction unit is communicated with a feed port of the sulfate-barium salt reaction unit through the filtering unit.
10. A method for extracting native carbonate lattice sulphate from carbonate rock, characterised in that the device of any one of claims 1-9 is used to extract native carbonate lattice sulphate from carbonate rock.
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