CN108398481A - A kind of method of inclusion gas phase constituent in analysis metal sulfide - Google Patents

Abstract

The invention discloses a method for analyzing gas phase components of inclusions in metal sulfides, the method comprising: using a vacuum grinding device for extracting fluid inclusion gas to grind a sample (4) to extract the sample (4) The fluid inclusion gas in the sample (4) includes metal sulfide; and the extracted fluid inclusion gas is analyzed by a quadrupole mass spectrometer to analyze the inclusion gas phase composition in the metal sulfide .

Description

A method for analyzing gas phase components of inclusions in metal sulfides

technical field

The invention relates to the field of geological sample analysis, in particular to a method for analyzing gas phase components of inclusions in metal sulfides.

Background technique

The fluid trapped during the growth of minerals (which can be called fluid inclusions) preserves various geological and geochemical information (such as temperature, pressure, system composition, pH value, etc.) of the geological environment at that time. The material composition in fluid inclusions is the code of related geological processes. Therefore, systematic research on fluid inclusions can obtain information such as temperature and pressure conditions during diagenesis and mineralization, the chemical composition of fluids, and the source of fluids, so as to find out the behavior and role of geological fluids in the process of diagenesis and mineralization, and explain The processes and conditions of diagenesis and mineralization.

Fluid inclusion analysis has been widely used in many research fields such as geology and mineral resources, oil and gas, building materials, and gemstones. In theory, all minerals contain inclusions, but the ones used for research are mainly minerals that are commonly found and abundant in rocks and ores, such as quartz, fluorite, calcite, halite, apatite, barite, Cassiterite, sphalerite, etc.

As shown in Fig. 1, at present, an ordinary quadrupole mass spectrometer is generally used to realize mass spectrometric analysis of fluid inclusions (for example, gaseous components in fluid inclusions, which may be called fluid inclusion gases). In the field of geological analysis, the quadrupole mass spectrometer is an important instrument for analyzing the composition of fluid inclusions. Its main components are four straight poles as mass analyzers. These four straight poles are parallel to the axis and equidistant from the axis. Suspension; and the same magnitude of direct current and radio frequency voltage are applied to the four straight rods. At this time, particles with different charge-to-mass ratios can move in the alternating electric field generated by these four parallel poles, and realize mass separation according to their motion trajectories, and then after being detected by the detector, the sample molecules (or atoms) mass spectrum. Since the mass spectrum of the sample contains the qualitative and quantitative information of the sample, the mass spectrum analysis result of the sample can be obtained through data processing.

Specifically, the common quadrupole mass spectrometer shown in Figure 1 includes the following structures: SV1, SV2, SV3, SV4, ISV are gas control valves; DG is a membrane pressure gauge; VLV is a needle valve; IG is a vacuum ionization gauge ; QMS is a quadrupole mass spectrometer; TMP is a molecular valve; TV1, TV2, FV are electromagnetic valves; RP1, RP2 are mechanical pumps. The connections between these components are shown in Figure 1.

When using the quadrupole mass spectrometer shown in Figure 1, the pretreated sample can be placed in the quartz glass tube 500, heated by the heating furnace 600 to make the sample in the quartz glass tube 500 reach 100 ° C, and then open SV2, Use RP2 for initial vacuuming. Then, close SV2, open SV1, use RP1 to further evacuate, and when the vacuum in the analysis system reaches 5x10 ^-6 Pa, open SV3 to remove the sample adsorbed gas. Then, turn off SV1, raise the temperature of the heating furnace to the set temperature at a rate of 1°C/5s, then turn on VLV, use QMS to detect the gas phase components in different temperature ranges, and finally go through corresponding data processing (such as processing software) to Calculate the mole percent of different gas components.

Since the current quadrupole mass spectrometry technology is obtained by obtaining (associated) transparent gangue minerals (such as quartz, fluorite, apatite, garnet, barite, etc. in space), among them, quartz is the best choice. ) to indirectly reflect the properties of ore-forming fluids, so it is inferred from the spatial co-occurrence (associated) that ore minerals (mostly opaque metal sulfide minerals) and gangue minerals (mostly transparent minerals) from Simultaneous precipitation in the same period of ore-forming fluids is not accurate. This is shown, for example, that the homogeneous temperature of fluid inclusions in minerals such as pyrite and cassiterite is 50-100°C higher than that of fluid inclusions in gangue minerals (quartz), and the salinity is 2-10wt% higher.

Therefore, the current quadrupole mass spectrometry technology can only obtain the gangue minerals (such as the above-mentioned quartz, fluorite, apatite, barite, calcite, etc. ) to indirectly reflect the properties of ore-forming fluids. However, it is not accurate to infer that the two were precipitated from the same period of ore-forming fluids only by the symbiosis (associated) relationship between ore minerals and gangue minerals in space. To address this issue, it is important to conduct tests directly on metal sulfide minerals to obtain direct evidence of the nature of the reactive fluids.

However, there are technical limitations in the direct analysis of metal sulfide minerals using existing quadrupole mass spectrometers. This is because the fluid inclusions in metal sulfide minerals cannot be extracted by vacuum thermal explosion, because these minerals will release a large amount of hydrogen sulfide (or other sulfur-containing gases) at a relatively high explosion temperature, and hydrogen sulfide is about 300 ° C The decomposition reaction will occur at a temperature above 100°C to generate hydrogen and solid sulfur (ie H ² S→H ² +S), so it is difficult to obtain the real gas composition and content in the fluid inclusions in the experiment. Moreover, since solid sulfur fine particles can easily block the gas pipelines and control valves of detection instruments (such as the existing quadrupole mass spectrometer) (such as the SV1~SV4 gas control valves, ISV gas control valves, and VLV needles in Fig. valves, etc.), so it is not feasible to extract metal sulfide minerals by vacuum thermal explosion method (as shown in Figure 1). In addition, a large amount of sulfur-containing gas generated during heating by the vacuum thermal explosion method is also corrosive to instruments (such as corresponding pipelines and mass spectrometers), thereby reducing the service life of the instruments.

Contents of the invention

The main purpose of the present invention is to provide a method for analyzing gas phase components of inclusions in metal sulfides, so as to solve the above problems and other potential problems in the prior art.

In order to achieve the above purpose, the present invention proposes a method for analyzing the gas phase components of inclusions in metal sulfides, the method comprising: using a vacuum grinding device for extracting fluid inclusion gas to grind the sample (4) to extract fluid inclusion gas in the sample (4), the sample (4) including metal sulfide; and analyzing the extracted fluid inclusion gas by using a quadrupole mass spectrometer to analyze the metal sulfide Inclusion gas phase composition; wherein, the vacuum grinding device for extracting fluid inclusion gas includes: a base (1) with a cavity (2) inside, and the cavity (2) is located on the base (1) There is an opening (11) on the top (10) of the top (11); the sample tank (3), which is set to be put into the cavity (2) through the opening (11), and is used to accommodate the sample (4) in the inside the sample tank (3); a motor (5), which is detachably installed on the top (10) of the base (1), and closes the opening (11) to seal the sample (4) in Inside the cavity (2); and the grinding hammer head (6), which is connected to the output shaft of the motor (5) via a coupling (7); wherein the side wall (12) of the base (1) ) is also provided with a side wall opening (13) communicating with the cavity (2), and a vacuum valve (8) is connected to the side wall opening (13), and the vacuum valve (8) is set In order to enable the cavity (2) to be evacuated; wherein the grinding hammer head (6) is set to be driven by the motor (5) and driven by the coupling (7), The sample (4) in the sample tank (3) is ground to extract fluid inclusion gas in the sample (4).

According to an embodiment of the present disclosure, the vacuum grinding device for extracting fluid inclusion gas further includes: a pressure adjustment knob (9), which has a first end (91) suitable for rotation and a second end for installing a spring (90). end (92), the spring (90) abuts against the bottom (30) of the sample tank (3), and the pressure adjustment knob (9) is set to adjust the spring (90) against the The supporting force of the bottom (30) of the sample tank (3) is described above.

According to an embodiment of the present disclosure, a bottom opening (15) is provided on the bottom (14) of the base (1), and the second end (92) passes through the bottom opening (15) and is connected to the Spring (90) is connected.

According to an embodiment of the present disclosure, a counterbore (31) is provided on the bottom (30) of the sample tank (3), one end of the spring (90) abuts into the counterbore (31), and the other end connected with the second end (92).

According to an embodiment of the present disclosure, the outer periphery of the spring (90) is also provided with a sealing bellows (93), and the pressure adjustment knob (9) is configured to adjust the pressure of the spring (90) on the sealing bellows. tube (93) in order to adjust the supporting force of the spring (90) against the bottom (30) of the sample tank (3).

According to an embodiment of the present disclosure, a heating plate (40) is further provided on the bottom (14) of the base (1), and the heating plate (40) is installed to the base (1) through a heat source fixing flange (50). ) on the bottom (14) of the heat source; the lower part of the heat source fixing flange (50) is also provided with hexagon socket screws, and the hexagon socket screws can fix the vacuum grinding device for extracting fluid inclusion gas to the test bench.

According to an embodiment of the present disclosure, a sealing magnetic fluid (60) for sealing the opening (11) is further provided between the motor (5) and the top (10) of the base (1); the The longitudinal section of the cavity (2) is T-shaped so that the base (1) has a step (16) on the inner wall, and the sample tank (3) is fixed on the step by the flange (32) at the top part (16); the motor includes a frequency-modulated stepping motor; the sample tank is made of high-gloss materials; the base (1) is made of high-strength stainless steel.

According to an embodiment of the present disclosure, the quadrupole mass spectrometer includes the following structures: gas control valve SV1, gas control valve SV2, gas control valve SV3, gas control valve SV4, gas control valve ISV, membrane pressure gauge DG, needle valve VLV , vacuum ionization gauge IG, quadrupole mass spectrometer QMS, molecular valve TMP, solenoid valve TV1, solenoid valve TV2, solenoid valve FV, mechanical pump RP1, and mechanical pump RP2; the vacuum valve (8) and the gas control valve SV3 connected to enable the chamber (2) to be evacuated by the quadrupole mass spectrometer.

According to an embodiment of the present disclosure, wherein the grinding of the sample (4) by using a vacuum grinding device for extracting fluid inclusion gas to extract the fluid inclusion gas in the sample (4) includes: After the sample (4) is put into the sample tank (3), assemble the vacuum grinding device for extracting fluid inclusion gas, and connect the vacuum valve (8) to the gas control valve SV3; open The vacuum valve (8) and the gas control valve SV3 use the mechanical pump RP1 and the mechanical pump RP2 to evacuate the vacuum grinding device, and close the vacuum valve after the vacuum degree reaches 5x10 ^-6 Pa (8) and the gas control valve SV3; and start the motor (5), set the initial grinding rate to 1r/min, and gradually increase the grinding rate after the grinding hammer (6) rotates, Then, when the sample (4) is ground to the desired particle size, the motor (5) is turned off to extract the fluid inclusion gas in the sample (4); Set different grinding rates.

According to an embodiment of the present disclosure, wherein the analysis of the extracted fluid inclusion gas by using a quadrupole mass spectrometer to analyze the gas phase composition of inclusions in the metal sulfide includes: opening the vacuum valve ( 8) and the gas control valve SV3 so that the extracted fluid inclusion gas enters the quadrupole mass spectrometer; and open the needle valve VLV so that the extracted fluid inclusion gas is The difference diffuses into the quadrupole mass spectrometer QMS, thereby using the quadrupole mass spectrometer QMS to detect the gas phase composition and mole percentage of inclusions in the metal sulfide.

Compared with the prior art, the present invention has the following advantages: the disclosed method for analyzing the gas phase components of inclusions in metal sulfides, since a vacuum grinding device for extracting fluid inclusion gas is used, the fluid inclusions can be (It can include metal sulfide) in all gas components (including gas phase components of inclusions in metal sulfide or noble gases) for testing, so the application range is wider. Moreover, due to the grinding method, the efficiency is higher and the speed is faster; and the particle size after grinding can be finer (for example, reaching about 150 mesh to 200 mesh), so 90% of the fluid inclusions can be opened, so that Reduce sample size. In addition, since manual operation can be replaced by automatic operation, the level of automation is increased and the efficiency is higher.

Description of drawings

In order to illustrate the technical solution of the present invention more clearly, the accompanying drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. Ordinary technicians can also obtain other drawings based on these drawings on the premise of not paying creative work.

Fig. 1 is a schematic structural diagram of an existing quadrupole mass spectrometer.

Fig. 2 is a schematic structural diagram of a vacuum grinding device for extracting fluid inclusion gas according to an embodiment of the present disclosure.

Fig. 3 is a schematic structural diagram of a vacuum grinding device for extracting fluid inclusion gas according to an embodiment of the present disclosure.

Fig. 4 is a schematic structural diagram of a vacuum grinding device for extracting fluid inclusion gas according to an embodiment of the present disclosure when it is used to analyze gas phase components of fluid inclusions in metal sulfide minerals.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on this The embodiments in the invention, and all other embodiments obtained by persons of ordinary skill in the art without creative effort, all belong to the scope of protection of the present invention.

The present disclosure provides a method for analyzing the gas phase composition of inclusions in metal sulfides to solve the above problems and other potential problems in the prior art (as shown in Figure 1), the method adopts a method for extracting fluid inclusion gas Vacuum grinding device to overcome the problems caused by the vacuum thermal burst method.

Specifically, in order to solve the technical problems existing in the existing quadrupole mass spectrometer in FIG. 1 , various embodiments of the present disclosure provide a method for analyzing gas phase components of inclusions in metal sulfides, the method comprising : using a vacuum grinding device for extracting fluid inclusion gas to grind sample 4 to extract the fluid inclusion gas in the sample 4, the sample 4 includes metal sulfide; and using a quadrupole mass spectrometer to extract The fluid inclusion gas is analyzed to analyze the inclusion gas phase composition in the metal sulfide.

Fig. 2 shows a schematic structural diagram of a vacuum grinding device for extracting fluid inclusion gas according to an embodiment of the present disclosure. FIG. 3 shows example dimensions (values are in millimeters, for example) of the vacuum grinding device of the present disclosure. The disclosed vacuum grinding device for extracting fluid inclusion gas includes a base 1 , a sample tank 3 , a motor 5 , and a grinding hammer 6 .

As shown in FIGS. 2-3 , the base 1 has a cavity 2 inside, and the cavity 2 has an opening 11 on the top 10 of the base 1 . The sample canister 3 is arranged to be put into the cavity 2 through the opening 11 and is used for accommodating the sample 4 in the sample canister 3 .

According to an embodiment of the present disclosure, the longitudinal section of the cavity 2 is T-shaped so that the base 1 has a step portion 16 on the inner wall, and the sample tank 3 is fixed on the step portion by a flange 32 at the top thereof. 16 on.

For example, the longitudinal section of the cavity 2 is T-shaped, for example, the section along the central axis of the base 1 is T-shaped (for example, the cavity 2 can be set as a cylinder with a larger diameter at the top and a cylinder with a smaller diameter at the bottom. shape). For example, through the mutual cooperation of the stepped portion 16 and the flange 32 of the present disclosure, the sample jar 3 can be conveniently put into the cavity 2 in the interior of the base 1 through the opening 11 . For example, the sample tank 3 can be made of high-quality materials to prevent gas adsorption.

According to an embodiment of the present disclosure, the motor 5 is detachably mounted on the top 10 of the base 1 and closes the opening 11 to seal the sample 4 in the cavity 2 .

For example, the motor 5 can be detachably installed on the top 10 of the base 1, and close the opening 11 to seal the sample 4 in the cavity 2, so that when the sample jar 3 is put into After being placed in the cavity 2 of the base 1, it is sealed in the cavity 2 of the base 1 to facilitate subsequent vacuuming and grinding of samples.

According to an embodiment of the present disclosure, a heating plate 40 is further provided on the bottom 14 of the base 1 , and the heating plate 40 is installed on the bottom 14 of the base 1 through a heat source fixing flange 50 .

For example, the heat source fixing flange is equipped with a heating plate, which can heat the sample in the sample tank 3. After heating, the gas in the cavity 2 is not easy to be adsorbed on the sample, and it is easy to be sucked away by the vacuum mechanical pump, so as to keep the gas in the cavity 2. high vacuum environment.

According to an embodiment of the present disclosure, the lower part of the heat source fixing flange 50 is further provided with an inner hexagonal screw, and the inner hexagonal screw can fix the vacuum grinding device for extracting fluid inclusion gas to an experimental bench.

For example, the heat source fixing flange 50 has an inner hexagonal screw at the lower part, which can fix the vacuum grinding device of the present disclosure on the test bench.

As shown in FIGS. 2-3 , according to an embodiment of the present disclosure, the grinding hammer head 6 is connected to the output shaft of the motor 5 via a coupling 7 . The side wall 12 of the base 1 is also provided with a side wall opening 13 communicating with the cavity 2, the side wall opening 13 is connected with a vacuum valve 8, and the vacuum valve 8 is set so that the The cavity 2 can be evacuated; wherein the grinding hammer head 6 is set to be driven by the motor 5 and driven by the coupling 7, to the sample in the sample tank 3 4 milling to extract fluid inclusion gases in said sample 4.

For example, the shaft coupling 7 is used to connect the output shaft of the motor 5 and the grinding hammer head 6, and its function is to keep the grinding hammer head 6 in a central rotation all the time without deflection. For example, the base 1 can be made of high-strength stainless steel, and a vacuum valve 8 can be connected to the side wall 12 of the base 1 .

According to an embodiment of the present disclosure, a sealing magnetic fluid 60 for sealing the opening 11 is also provided between the motor 5 and the top 10 of the base 1 (the sealing magnetic fluid 60 is not used in existing equipment does not exist, its sealing performance can reach 5x10 ^-12 Pa. The upper part of the sealing magnetic fluid 60 can also be provided with a corresponding sealing flange).

According to an embodiment of the present disclosure, the motor includes a frequency-tuned stepping motor; the vacuum valve 8 is connected to a vacuum pump (such as mechanical pumps RP1 and RP2 in a quadrupole mass spectrometer) so that the cavity 2 can be pumped by the vacuum pump Vacuumizing (for example, connected to the gas control valve SV3 in the quadrupole mass spectrometer, so that the cavity 2 can be evacuated by the mechanical pump in the quadrupole mass spectrometer); the sample tank is made of high-quality materials; The base 1 is made of high-strength stainless steel.

For example, the motor of the present disclosure is a frequency-modulated stepping motor, which adopts stepless speed change, and can rotate forward and reverse, and can adjust the speed in real time and the speed parameters can be displayed on the control panel in real time.

As shown in FIGS. 2-3 , the vacuum grinding device for extracting fluid inclusion gas of the present disclosure may further include: a pressure adjustment knob 9 having a first end 91 suitable for rotation and a second end for installing a spring 90 92 , the spring 90 abuts against the bottom 30 of the sample jar 3 , and the pressure adjustment knob 9 is configured to adjust the supporting force of the spring 90 abutting against the bottom 30 of the sample jar 3 .

For example, by rotating the first end 9 of the pressure adjustment knob 9 (threads are provided on it to facilitate turning, for example, with fingers), the spring 90 on the second end 92 can be adjusted to abut against the bottom 30 of the sample tank 3 Supporting force, so that different supporting forces (that is, upward force) can be used according to different samples, so as to adjust the grinding force between the sample jar and the grinding hammer, so as to meet the needs of different samples and set different grinding forces.

According to an embodiment of the present disclosure, the bottom 14 of the base 1 is provided with a bottom opening 15 , and the second end 92 passes through the bottom opening 15 and is connected with the spring 90 .

For example, the bottom 14 of the base 1 can be perforated so that a pressure adjustment knob can be attached. A spring 90 is placed above the pressure adjustment knob, and the upper part of the spring is pushed against the bottom of the sample jar.

According to an embodiment of the present disclosure, a counterbore 31 is provided on the bottom 30 of the sample tank 3 , one end of the spring 90 abuts into the counterbore 31 , and the other end is connected to the second end 92 .

For example, a counterbore 31 may be provided on the bottom 30 of the sample jar 3, so that one end of the spring 90 abuts into the counterbore 31, and the other end is connected with the second end 92, so that the upper part of the spring may Top the bottom of the sample jar.

According to an embodiment of the present disclosure, a sealing bellows 93 is provided on the periphery of the spring 90, and the pressure adjustment knob 9 is configured to adjust the stroke of the spring 90 in the sealing bellows 93 to adjust The spring 90 abuts against the supporting force of the bottom 30 of the sample jar 3 .

For example, the periphery of the spring can be wrapped with a sealing bellows 93, so that the pressure adjustment knob 9 can adjust the stroke of the spring in the sealing bellows 93 when rotating, so that when the stroke of the spring changes, its elastic force also changes accordingly. Therefore, the supporting force of the sample tank is changed, so as to meet the needs of different samples and set different grinding forces.

Based on the above introduction, for example, when the vacuum grinding device for extracting fluid inclusion gas of the present disclosure is working, a stepping motor can be used to drive the grinding hammer to rotate, and the coupling can ensure that the grinding hammer rotates centrally without deflection. The stepping motor can adjust the rotation rate in real time, from 1r/min to 100r/min continuously, so as to drive the grinding hammer to grind the sample.

At the same time, in the vacuum grinding device for extracting fluid inclusion gas in the present disclosure, there is also a pressure adjustment knob under the base, and the pressure adjustment knob is connected with the spring, and the spring is against the sample tank, so different samples can be used according to different samples. Upward force, so that the grinding force between the sample jar and the grinding hammer can be adjusted in real time.

After using the vacuum grinding device for extracting fluid inclusion gas of the present disclosure, for example, the sample can be ground within 0.5 hours at the slowest, and can be ground within 5 minutes at the fastest, thus saving time and cost. Moreover, since the particle size after grinding can be finer (for example, reaching about 150 mesh to 200 mesh), 90% of the fluid inclusions can be opened, which can reduce the sample amount. In addition, since manual operation can be replaced by automatic operation, the level of automation is increased and the efficiency is higher.

According to an embodiment of the present disclosure, after the sample is ground by using the vacuum grinding device for extracting fluid inclusion gas shown in FIGS. Analyze gas phase components of inclusions in the metal sulfides.

As an example, as shown in FIG. 4 , the quadrupole mass spectrometer used in the present disclosure includes the following structures: gas control valve SV1, gas control valve SV2, gas control valve SV3, gas control valve SV4, gas control valve ISV, membrane pressure Gauge DG, needle valve VLV, vacuum ionization gauge IG, quadrupole mass spectrometer QMS, molecular valve TMP, solenoid valve TV1, solenoid valve TV2, solenoid valve FV, mechanical pump RP1, and mechanical pump RP2; the extraction fluid inclusions in this disclosure The vacuum valve (8) in the gas vacuum grinding device is connected to the gas control valve SV3 in the quadrupole mass spectrometer so that the cavity (2) can be evacuated by the quadrupole mass spectrometer.

According to an embodiment of the present disclosure, the use of a vacuum grinding device for extracting fluid inclusion gas to grind the sample (4) to extract the fluid inclusion gas in the sample (4) includes: (4) After putting it into the sample tank (3), assemble the vacuum grinding device for extracting fluid inclusion gas, and connect the vacuum valve (8) to the gas control valve SV3; open the The vacuum valve (8) and the gas control ^valve SV3 use the mechanical pump RP1 and the mechanical pump RP2 to evacuate the vacuum grinding device, and close the vacuum valve (8 ) and the gas control valve SV3; and start the motor (5), set the initial grinding rate to 1r/min, gradually increase the grinding rate after the grinding hammer (6) rotates, and then wait for When the sample (4) is ground to the desired particle size, the motor (5) is turned off to extract the fluid inclusion gas in the sample (4); wherein, different settings are made depending on the sample (4) grinding rate.

As an example, when the vacuum grinding device for extracting fluid inclusion gas provided by the embodiments of the present disclosure is applied, the following steps can be used to operate:

1. Remove the stepper motor (with the structure of the sealed magnetic fluid 60 on it), and take out the sample tank.

2. Put the 5g sample into the sample tank and cover and fix the stepper motor (for example, tighten the screws).

3. Turn on the power, turn on the heating plate, set the temperature at 50°C, and keep the temperature constant for 10 minutes after reaching the set temperature. At this time, open the vacuum valve and use a vacuum mechanical pump (such as the vacuum mechanical pumps RP1 and RP2 in the quadrupole mass spectrometer) to evacuate. In this way, the gas adsorbed on the surface of the sample and the inner wall of the vacuum grinding device of the present disclosure can be eliminated, and the vacuum valve is closed after the vacuum degree in the vacuum grinding device of the present disclosure reaches 5x10 ^-6 Pa.

4. Start the stepper motor, set the initial speed to 1r/min, and after confirming the rotation of the grinding hammer head, gradually increase the speed. Different grinding rates can be set according to different samples. After grinding for a period of time, the sample is ground to the required particle size, the fluid inclusions in the sample are opened, and the gas is released.

5. Open the vacuum valve so that the gas slowly enters the external mass spectrometer (such as a quadrupole mass spectrometer) through the vacuum valve, so as to determine the components of different gases and the mole percentage of different gas components.

According to an embodiment of the present disclosure, the analysis of the extracted fluid inclusion gas by using a quadrupole mass spectrometer to analyze the inclusion gas phase composition in the metal sulfide includes: opening the vacuum valve (8) and the gas control valve SV3 so that the extracted fluid inclusion gas enters the quadrupole mass spectrometer; and open the needle valve VLV so that the extracted fluid inclusion gas Diffusion into the quadrupole mass spectrometer QMS, so as to use the quadrupole mass spectrometer QMS to detect the gas phase composition and mole percentage of the inclusions in the metal sulfide.

As an example, as shown in FIG. 4 , the vacuum grinding device for extracting gas from fluid inclusions of the present disclosure is particularly suitable for analyzing gas phase components of fluid inclusions in metal sulfide minerals, for example. This is because the existing quadrupole mass spectrometer generally adopts the vacuum thermal explosion method to extract the fluid inclusion gas, and as mentioned above, the metal sulfide minerals cannot be extracted by the vacuum thermal explosion method. Therefore, the vacuum grinding device of the present disclosure can avoid the defect of extracting fluid inclusion gas by the vacuum thermal burst method, so it is especially suitable for analyzing the gas phase composition of fluid inclusions in metal sulfide minerals, so as to overcome the technical defects of existing quadrupole mass spectrometers .

For example, in a high vacuum (for example, 10 ^-6 Pa) environment, using the vacuum grinding device for extracting gas from fluid inclusions of the present disclosure, fluid inclusions (such as fluid inclusions in metal sulfide minerals) can be opened in a grinding manner, thereby It can directly analyze the gas phase composition of fluid inclusions in opaque metal sulfide minerals. For specific operations, the following steps can be taken:

1. Weigh about 5g of sample, put it into the sample tank of the vacuum grinding device for extracting fluid inclusion gas in the embodiment of the present disclosure, assemble the vacuum grinding device of the present disclosure, and pass it through the vacuum valve and mass spectrometer (such as a quadrupole mass spectrometer) are connected to each other (as shown in Figure 4, the vacuum valve of the vacuum grinding device of the present disclosure can be connected to the SV3 of the quadrupole mass spectrometer);

2. Open SV2, use RP2 to initially vacuum; then close SV2, open SV1, use RP1 to further vacuum, open SV3 when the vacuum degree in the pipeline reaches 10 ^-5 Pa, in order to remove the gas adsorbed on the sample, and then close SV3 ;

3. Start the vacuum grinding device in the embodiment of the present disclosure. After a period of time, the sample is ground and broken, the inclusions are opened, and the internal gas is released;

4. At this time, open SV3 again, close SV1, and open VLV. The gas diffuses to the QMS due to the pressure difference, so that the QMS can be used to detect the gas composition. For example, the composition and mole percentage of different gas phases in the inclusion can be known (such as mole percentage) ;

Compared with the prior art, the embodiment shown in FIG. 4 that uses the vacuum grinding device in the embodiment of the present disclosure to analyze the gas phase composition of fluid inclusions in metal sulfide minerals has the following advantages:

1. The types of minerals suitable for quadrupole mass spectrometry analysis technology can be expanded from a single transparent mineral such as quartz and calcite to most metal sulfide minerals (such as pyrite, chalcopyrite, galena, etc.).

2. In the field of geological research, it can provide direct evidence of the nature and activity evolution of diagenetic ore-forming fluids (such as metal sulfide minerals as direct evidence of the characteristics of ore-forming fluids), thereby eliminating the inaccuracy caused by indirect evidence.

Through the description of the above embodiments, those skilled in the art can clearly understand that the present invention can also be implemented through other structures, and the features of the present invention are not limited to the above preferred embodiments. Any change or modification that can be easily conceived by any person familiar with the technology within the technical field of the present invention shall be covered by the patent protection scope of the present invention.

Claims (10)

1. a kind of method of the inclusion gas phase constituent in analysis metal sulfide, the method includes：

Using a kind of vacuum grinding device of extraction fluid inclusion gas to sample（4）It is ground to extract the sample （4）In fluid inclusion gas, the sample（4）It include metal sulfide；And

Quadrupole mass spectrometer is used to analyze to analyze in the metal sulfide fluid inclusion gas extracted Inclusion gas phase constituent；

Wherein, the vacuum grinding device of the extraction fluid inclusion gas includes：

Pedestal（1）, internal that there is cavity（2）, the cavity（2）In the pedestal（1）Top（10）It is upper that there is opening （11）；

Sample jar（3）, it is arranged to through the opening（11）It is put into the cavity（2）It is interior, and be used for sample（4）It is contained in The sample jar（3）It is interior；

Motor（5）, it is releasably attached to the pedestal（1）Top（10）On, and close the opening（11）With by institute State sample（4）It is enclosed in the cavity（2）It is interior；And

Grind tup（6）, via shaft coupling（7）With the motor（5）Output shaft be connected with each other；

The wherein described pedestal（1）Side wall（12）On be additionally provided with and the cavity（2）The side-wall hole of connection（13）, the side wall Trepanning（13）On be connected with vacuum valve（8）, the vacuum valve（8）It is provided so that the cavity（2）It can be taken out true It is empty；

The wherein described grinding tup（6）It is arranged in the motor（5）Driving under and in the shaft coupling（7）Drive Under, to the sample jar（3）The interior sample（4）It is ground to extract the sample（4）In fluid inclusion gas.

2. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 1, which is characterized in that institute State extraction fluid inclusion gas vacuum grinding device further include：

Pressure adjustment knob（9）, there is the first end suitable for rotation（91）With for installing spring（90）Second end（92）, The spring（90）Abut to the sample jar（3）Bottom（30）, the pressure adjustment knob（9）It is arranged to be used for adjusting The spring（90）Abut the sample jar（3）Bottom（30）Support force.

3. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 2, which is characterized in that institute State pedestal（1）Bottom（14）It is equipped with bottom opening（15）, the second end（92）Across the bottom opening（15）And with The spring（90）It is connected.

4. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 3, which is characterized in that institute State sample jar（3）Bottom（30）It is equipped with counterbore（31）, the spring（90）One end abut to the counterbore（31）In, separately One end and the second end（92）It is connected.

5. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 3, which is characterized in that institute State spring（90）Periphery be additionally provided with seal bellows（93）, the pressure adjustment knob（9）It is arranged to be used for adjusting institute State spring（90）In the seal bellows（93）In stroke, to adjust the spring（90）Abut the sample jar（3）'s Bottom（30）Support force.

6. special according to the method that claim 1-5 any one of them analyzes the inclusion gas phase constituent in metal sulfide Sign is, the pedestal（1）Bottom（14）On be additionally provided with heating plate（40）, the heating plate（40）Pass through heat source mounting flange （50）It is installed to the pedestal（1）Bottom（14）On；It is characterized in that, the heat source mounting flange（50）Lower part be additionally provided with Hexagon socket head cap screw, it is real that the hexagon socket head cap screw enables to the vacuum grinding device of the extraction fluid inclusion gas to be fixed to It tests on platform.

7. described according to the method that claim 1-5 any one of them analyzes the inclusion gas phase constituent in metal sulfide Motor（5）With the pedestal（1）Top（10）Between be additionally provided with for the opening（11）The sealing magnetic current being sealed Body（60）；The cavity（2）Longitudinal section it is T-shaped so that the pedestal（1）There is stage portion on inner wall（16）, the sample Product tank（3）Pass through the flange at the top of it（32）It is fixed on the stage portion（16）On；The motor includes frequency modulation stepper motor；Institute Sample jar is stated to be made by best bright finish material；The pedestal（1）It is made by high-strength stainless steel material.

8. special according to the method that claim 1-5 any one of them analyzes the inclusion gas phase constituent in metal sulfide Sign is that the quadrupole mass spectrometer includes with lower structure：Gas control valve SV1, gas control valve SV2, gas control valve SV3, Gas control valve SV4, gas control valve ISV, film pressure meter DG, needle-valve VLV, vacuum ionization ga(u)ge IG, four-electrode spectrum QMS, molecule Valve TMP, solenoid valve TV1, solenoid valve TV2, solenoid valve FV, mechanical pump RP1 and mechanical pump RP2；The vacuum valve（8）With The gas control valve SV3 connections are so that the cavity（2）It can be vacuumized by the quadrupole mass spectrometer.

9. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 8, which is characterized in that its In, it is described using it is a kind of extraction fluid inclusion gas vacuum grinding device to sample（4）It is ground to extract the sample Product（4）In fluid inclusion gas, including：

By the sample（4）It is put into the sample jar（3）In after, assemble it is described extraction fluid inclusion gas vacuum Grinding device, and by the vacuum valve（8）It is connect with the gas control valve SV3；

Open the vacuum valve（8）With the gas control valve SV3 to utilize the mechanical pump RP1 and mechanical pump RP2 The vacuum grinding device is vacuumized, waits for that vacuum degree reaches 5x10^-6The vacuum valve is closed after Pa（8）It is controlled with the gas Valve SV3；And

Start the motor（5）, initial grinding rate is set as 1r/min, waits for the grinding tup（6）After rotation again by Grinding rate is gradually increased, then waits for the sample（4）The motor is turned off when being ground to required granularity（5）To extract the sample （4）In fluid inclusion gas；Wherein, according to the sample（4）Difference set different grinding rates.

10. the method for the inclusion gas phase constituent in analysis metal sulfide according to claim 9, which is characterized in that Wherein, described to use quadrupole mass spectrometer to analyze the fluid inclusion gas extracted to analyze the metal vulcanization Inclusion gas phase constituent in object, including：

Open the vacuum valve（8）With the gas control valve SV3 so that the fluid inclusion gas extracted into Enter the quadrupole mass spectrometer；And

Open the needle-valve VLV so that the fluid inclusion gas extracted is diffused into described four due to pressure difference In the mass spectrum QMS of pole, to detect the inclusion gas phase constituent in the metal sulfide using the four-electrode spectrum QMS and rub That percentage composition.