CN113720871B - Method for measuring isovolumetric line of salt water system - Google Patents
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention discloses a method for measuring an isovolumetric line of a saline system, which comprises the following steps: the quartz alpha-beta transformation temperature Ttr is obtained, and according to the relation Ptr (+ -5.6 MPa) =0.0008.Ttr 2 The + 2.8056.Ttr-1877.5 calculates Dan Ying-beta phase transition pressure Ptr corresponding to the Dan Ying-beta phase transition temperature Ttr; obtaining uniform temperature Th and freezing point temperature Tm of a salt water system, and calculating uniform pressure Ph of the salt water system; taking the Dan Ying-beta phase transition temperature Ttr and the uniform temperature Th of the brine system as the abscissa, taking the Dan Ying-beta phase transition pressure Ptr and the uniform pressure Ph of the brine system as the ordinate,fitting to obtain the product; wherein the Dan Ying-beta phase transition temperature Ttr is that quartz is 128cm ‑1 The characteristic peak of the Raman peak position reaches the temperature when the characteristic peak is stable; and the Dan Ying-beta phase transition temperature Ttr is measured by combining a hot liquid diamond pressure cavity with a laser Raman spectrometer. The method for measuring the isovolumetric line of the salt water system has high test precision and obviously improves the applicable temperature and pressure range.
Description
Technical Field
The invention relates to the field of high-temperature high-pressure fluid experiments, in particular to a method for measuring an isovolumetric line of a saline system.
Background
The isovolumetric line refers to the linear function relationship formed by pressure and temperature in a certain component fluid system when the system volume is kept unchanged, and is approximately a straight line on a P-T (pressure-temperature) state diagram of the system. Isovolumetric lines are one of the important contents of fluid pressure, volume, temperature and composition (PVTx) property studies, and have been widely used for calculation of fluid inclusion trapping pressure, and calibration of intra-hydrothermal diamond pressure cavity (HDAC) pressure. The hydrothermal diamond pressure cavity is high-temperature high-pressure equipment capable of in-situ observation under a microscope, the temperature and pressure conditions of the equipment can reach T <1200 ℃, and P <2.5Gpa, and the sample cavity has good sealing property and isovolumetric property, so the hydrothermal diamond pressure cavity is ideal equipment for researching the PVTx property of crustal fluid.
With NaCl-H 2 The brine system represented by O is the most widely distributed fluid system in geological environments and is also the most important fluid inclusion type captured by minerals, and its PVTx properties are commonly used to explain the cause of rock minerals. However, published references to NaCl-H 2 The temperature and pressure conditions suitable for the empirical and theoretical models of the isovolumetric line of O are still very limited, and the temperature and pressure range is limited to T<700℃，P<600Mpa. The main reason for this is the method used by the predecessor-the synthetic fluid inclusion method, which has many limitations. Specific: firstly, the high-temperature high-pressure equipment used in the method is a cold-sealed autoclave, and the temperature and pressure conditions which can be achieved by the equipment are usually T<900℃，P<300Mpa, and a sample thereof needs to be observed after quenching at high temperature, and quenching which cannot be observed in situ is one of important reasons for causing larger experimental errors; secondly, in the method, the influence of confining pressure on the uniform temperature cannot be considered when the uniform temperature of the artificially synthesized fluid inclusion is observed, so that a certain experimental error is caused, the method is complex in operation and high in consumable materials, and the time spent for synthesizing the fluid inclusion is different from a few days to a few months. Later, related researchers provided a method of using alpha-beta stoneThe method for determining the isovolumetric line of the fluid by the phase transition P-T track of quartz has the common defect of low measurement accuracy due to the experimental methods such as a thermal differential analysis method, a differential pressure analysis method, an interference color analysis method and a laser Raman spectrum analysis method which are used for determining the alpha-beta phase transition boundary line of quartz, although the experimental error is effectively reduced compared with the artificial synthetic fluid inclusion method. In recent years, quantitative study of quartz 464cm by combining a diamond pressure cavity with a micro-confocal Raman spectrometer has been proposed -1 The relation between the Raman peak frequency shift and the alpha-beta quartz phase transition temperature and pressure can improve the accuracy of measuring the alpha-beta phase transition boundary line of quartz, but the accuracy of measuring the isovolumetric line of a saline water system in a higher temperature and pressure range still needs to be further improved.
Disclosure of Invention
The invention aims to provide a method for measuring an isovolumetric line of a salt water system.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for measuring isovolumetric line of a saline system, which is characterized by comprising the following steps:
the quartz alpha-beta transformation temperature Ttr is obtained, and according to the relation Ptr (+ -5.6 MPa) =0.0008.Ttr 2 The + 2.8056.Ttr-1877.5 calculates Dan Ying-beta phase transition pressure Ptr corresponding to the Dan Ying-beta phase transition temperature Ttr;
obtaining uniform temperature Th and freezing point temperature Tm of a salt water system, and calculating uniform pressure Ph of the salt water system;
fitting by taking the Dan Ying-beta phase transition temperature Ttr and the uniform temperature Th of the salt water system as abscissa and the Dan Ying-beta phase transition pressure Ptr and the uniform pressure Ph of the salt water system as ordinate to obtain the water-based water separator;
wherein the Dan Ying-beta phase transition temperature Ttr is that quartz is 128cm -1 The characteristic peak of the Raman peak position reaches the temperature when the characteristic peak is stable; and the Dan Ying-beta phase transition temperature Ttr is measured by combining a hot liquid diamond pressure cavity with a laser Raman spectrometer.
Further, the method for obtaining the Dan Ying-beta phase transition temperature Ttr specifically comprises the following steps:
s1, placing deionized water and a quartz sample or a saline aqueous solution and a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
s2, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, heating, and recording the bubble disappearance temperature Th in the sample cavity 1 At the same time, the quartz sample is observed to be 128cm in the heating process -1 The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr when the characteristic peak is not shifted continuously in the direction of small wave number is recorded 1 ；
S3, suspending heating and slowly cooling, and recording the re-appearance bubble disappearance temperature Th when the re-appearance of the bubbles in the sample cavity is observed 2 The method comprises the steps of carrying out a first treatment on the surface of the At the same time, the quartz sample is observed to be 128cm in the heating process -1 The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr when the characteristic peak is not shifted continuously in the direction of small wave number is recorded 2 ；
S4, comparing the bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 And performing the following steps a and b;
a. at bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 The same or a difference of 2 ℃ or less, the temperature Ttr 2 Namely Dan Ying-beta phase transition temperature Ttr;
b. at bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 And if the difference is more than 2 ℃, repeating the steps S1-S4.
Further, the method for obtaining the uniform temperature Th of the brine system specifically comprises the following steps:
(1) Placing a sample of a salt water system into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
(2) Connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, heating, and recording the bubble disappearance temperature Th in the sample cavity 1 Then the temperature is reduced after the temperature rising is suspended, when the reappearance of the bubbles in the sample cavity is observed, the temperature rising is slowly performed again to record the reappearance of the bubblesTh 2 ；
(3) Comparing the bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 And performing the following steps a or b:
a. at bubble disappearance temperature Th 2 And bubble disappearance temperature Th 1 Equal or less than or equal to 2 ℃, the Th is considered 2 Is a uniform temperature Th;
b. when the bubble disappears at temperature Th 2 And bubble disappearance temperature Th 1 And (5) if the difference is more than 2 ℃, repeating the steps (1) - (3).
Further, the method for acquiring the freezing point temperature Tm of the brine system specifically comprises the following steps:
and placing a sample of the salt water system into a sample cavity of the hydrothermal diamond pressure cavity, sealing the sample cavity, placing the hydrothermal diamond pressure cavity into a cooling platform, reducing the temperature to be lower than-90 ℃, slowly heating, and recording the temperature as the freezing point temperature Tm of the salt water system by observing the melting temperature of the last ice crystal in the sample of the salt water system.
Further, the hydrothermal diamond press cavity is a Bassett hydrothermal diamond press cavity; the laser Raman is a microscopic confocal Raman spectrometer.
Further, the heating process in the step S2 or the step S3 specifically includes the following steps:
the temperature is increased at a rate of 20-30 ℃/min in a temperature range from room temperature to 300 ℃; a temperature range of 300-500 ℃ adopts a heating rate of 10-15 ℃/min; the temperature rising rate of 5-8 ℃/min is adopted above 500 ℃, and the temperature rising rate is 1-4 ℃/min when the alpha-beta phase transition point of quartz is heated.
The beneficial effects of the invention are as follows:
1) The method for measuring the isovolumetric line of the brine system is based on a high-pressure Raman technology, is easy to operate and has high test precision.
2) Compared with the prior art, the temperature and pressure range suitable for the method for measuring the isovolumetric line of the saline water system can be obviously improved, wherein the temperature can reach 860 ℃, the pressure can reach 1.2Gpa, and the blank of experimental data of fluid pvtx at high temperature and high pressure is made up.
3) The method for measuring the isovolumetric line of the brine system is suitable for measuring the isovolumetric line of other binary systems and multi-element brine systems.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a schematic structure of HDAC-VT used in example 1.
FIG. 2 is a schematic diagram showing the placement of the HDAC-VT used in the temperature ramp down stage in accordance with example 1.
FIG. 3 shows the acquired Raman spectra at different temperatures during the temperature increase process for example 1.
FIG. 4 shows a comparison of isovolumetric lines fitted using different methods for NaCl solutions of different salinity at different uniform temperatures in test example 2; wherein a shows a comparison graph of isovolumetric lines fitted with different methods for NaCl solutions with a salinity of 5wt% at different uniform temperatures; b shows a comparison plot of isovolumetric lines fitted with different methods for a 10wt% salinity NaCl solution at different uniform temperatures; c shows a comparison plot of isovolumetric lines fitted with different methods for NaCl solutions with a salinity of 15wt% at different uniform temperatures; d shows a comparison plot of isovolumetric lines fitted with different methods for NaCl solutions with salinity of 20wt% at different uniform temperatures.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a method for measuring an isovolumetric line of a saline system, which comprises the following steps:
the quartz alpha-beta transformation temperature Ttr is obtained, and according to the relation Ptr (+ -5.6 MPa) =0.0008.Ttr 2 Calculation of the quartz alpha with + 2.8056.Ttr-1877.5Dan Ying-beta phase transition pressure Ptr corresponding to the beta phase transition temperature Ttr;
obtaining uniform temperature Th and freezing point temperature Tm of a salt water system, and calculating uniform pressure Ph of the salt water system;
fitting by taking the Dan Ying-beta phase transition temperature Ttr and the uniform temperature Th of the salt water system as abscissa and the Dan Ying-beta phase transition pressure Ptr and the uniform pressure Ph of the salt water system as ordinate to obtain the water-based water separator;
wherein the Dan Ying-beta phase transition temperature Ttr is that quartz is 128cm -1 The characteristic peak of the Raman peak position reaches the temperature when the characteristic peak is stable; and the Dan Ying-beta phase transition temperature Ttr is measured by combining a hot liquid diamond pressure cavity with a laser Raman spectrometer. The Dan Ying-beta transformation temperature Ttr is that quartz is 128cm -1 The temperature at which the characteristic peak of the Raman peak position reaches a stable state means that the quartz is at 128cm -1 The raman peak position is no longer continuously shifted with the temperature and pressure.
The prior art discloses quantitative research of quartz 464cm by combining a diamond pressure cavity with a micro-confocal Raman spectrometer -1 The relation between the Raman peak frequency shift and the alpha-beta quartz phase transition temperature pressure can improve the accuracy of measuring the alpha-beta phase transition boundary line of quartz to a certain extent, but the invention discovers that when the variation of the external pressure and the variation of the temperature are the same, the quartz is 128cm -1 The frequency of the raman peak varies by about 464cm -1 The raman peak frequency is changed by 5 times or more, and therefore, the quartz is used at 128cm -1 The phase transition temperature is obtained according to the change relation of the Raman peak frequency shift along with the temperature, so that the accuracy of measuring the alpha-beta phase transition boundary line of quartz can be further improved, and the measuring accuracy of the isovolumetric line of a saline system is further improved.
According to a specific embodiment of the present invention, the relation Ptr (+ -5.6 MPa) =0.0008·ttr 2 The method for obtaining + 2.8056.Ttr-1877.5 specifically comprises the following steps:
the obtained Dan Ying-beta phase transition temperature Ttr and the corresponding Dan Ying-beta phase transition pressure Ptr;
determining Dan Ying-beta phase transition P-T relationship from said Dan Ying-beta phase transition temperature Ttr and corresponding said Dan Ying-beta phase transition pressure Ptr, expressed as follows:
Ptr(±5.6MPa)＝0.0008·Ttr 2 +2.8056·Ttr-1877.5；
wherein the Dan Ying-beta phase transition temperature Ttr is that quartz is 128cm -1 The characteristic peak of the Raman peak position reaches the stable temperature, ttr is more than or equal to 574 ℃ and less than or equal to 889 ℃, R 2 ＝0.9998。
Optionally, the hydrothermal diamond pressing cavity is a Bassett hydrothermal diamond pressing cavity; the laser Raman spectrometer is a microscopic confocal Raman spectrometer.
Optionally, the method for obtaining the Dan Ying- β phase transition temperature Ttr and the corresponding Dan Ying- β phase transition pressure Ptr includes the following step (1) or step (2):
step (1), when the Dan Ying-beta phase transition pressure Ptr is 0.1MPa,
placing a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, wherein the sample cavity is not sealed, then connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, starting heating, and observing that the quartz sample is 128cm in the heating process -1 The characteristic peak of the Raman peak position is shifted towards the direction of small wave number continuously, and the temperature when the characteristic peak is not changed is recorded as Dan Ying-beta phase transition temperature Ttr;
step (2), when Dan Ying-beta phase transition pressure Ptr is more than 0.1MPa,
s1, placing deionized water and a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
s2, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer; heating, and recording bubble disappearance temperature Th in the sample cavity 1 At the same time, the quartz sample is observed to be 128cm in the heating process -1 The characteristic peak of the Raman peak position is shifted continuously to the direction of small wave number, and the temperature Ttr when the characteristic peak is not changed is recorded 1 ；
S3, suspending heating and slowly cooling, and recording the re-appearance bubble disappearance temperature Th when the re-appearance of the bubbles in the sample cavity is observed 2 The method comprises the steps of carrying out a first treatment on the surface of the At the same time, the quartz sample is observed to be 128cm in the heating process -1 Special raman peak positionThe characteristic peak is shifted continuously in the direction of small wave number, and the temperature Ttr of the characteristic peak is recorded when the characteristic peak is not changed 2 ；
S4, comparing the bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 And performing the following steps a and b;
a. at bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 The same or a difference of 2 ℃ or less, the temperature Ttr 2 Namely Dan Ying-beta phase transition temperature Ttr; then obtaining corresponding Dan Ying-beta phase change pressure Ptr according to an IAPWS-95 pure water multiparameter state equation;
b. at bubble disappearance temperature Th 1 Bubble disappearance temperature Th 2 And if the difference is more than 2 ℃, repeating the steps S1-S4.
Optionally, the heating process of S2 of the step (1) or the step (2) or S3 of the step (2) specifically includes the following steps:
the temperature is increased at a rate of 20-30 ℃/min in a temperature range from room temperature to 300 ℃; a temperature range of 300-500 ℃ adopts a heating rate of 10-15 ℃/min; the temperature rising rate of 5-8 ℃/min is adopted above 500 ℃, and the temperature rising rate is 1-4 ℃/min when the alpha-beta phase transition point of quartz is heated.
Optionally, before the hydrothermal diamond plenum of the step (1) or the step (2) is connected to the laser raman spectrometer, the method further comprises performing linear calibration on the laser raman spectrometer.
According to an embodiment of the present invention, the Dan Ying- β phase transition temperature Ttr and the uniform temperature Th of the brine system may be obtained simultaneously, and only the aqueous salt solution is replaced with the sample of the brine system to be tested in step S2 of the method for obtaining the Dan Ying- β phase transition temperature Ttr.
According to an embodiment of the present invention, when determining Dan Ying- β transformation temperature Ttr, a training rhenium piece is further needed before the hydrothermal diamond plenum is connected to the laser raman spectrometer, and the training rhenium piece specifically includes the following steps:
heating, and recording bubble disappearance temperature Th in the sample cavity 1 Then the temperature is reduced after the temperature is stopped, and when the bubbles in the sample cavity are observed to be reextractedAt present, the re-occurrence of bubble disappearance temperature Th is recorded by slow temperature rise again 2 . In this way, the bubble is circulated until the bubble disappearance temperature Th is reached twice successively n And Th (Th) n+1 The rhenium plate training is completed if the same or a difference is less than 2 ℃. The training rhenium sheet can enable the metal rhenium sheet to reach a stable state so as to ensure isovolumetric performance of the sample cavity, and the rhenium sheet without high-temperature training can deform in the experimental process.
The hydrothermal diamond plenum and laser raman spectrometer used in the following examples of the present invention were Bassett hydrothermal diamond plenum (HDAC-VT) and HORIBA Jobin Yvon confocal LabRAM HR Evolution micro confocal raman spectrometer with three guide posts, respectively.
Example 1
Step one: preparation before sample loading
1) HDAC-VT line detection and leveling
The compression chamber used in the experiment was HDAC-VT (the structure diagram is shown in FIG. 1). The HDAC-VT sample cavity consists of an upper diamond anvil and a lower diamond anvil (the upper surface of the diamond anvil is cut into octagons, the opposite side length of the diamond anvil is about 1.0 mm) and a high-purity rhenium sheet (the thickness of the rhenium sheet is about 0.25mm, the peripheral diameter of the rhenium sheet is about 3mm, a hole with the diameter of about 0.5mm through laser breakdown is formed in the middle of the rhenium sheet), and the upper diamond anvil and the lower diamond anvil are respectively pressed on the upper surface and the lower surface of the rhenium sheet in an experiment to form a closed sample cavity with the diameter of about 0.5mm and the height of about 0.25mm, and light can pass through the diamond anvil with the help of a micro-optical observation platform so as to observe the change in the sample cavity in real time. Before the experiment starts, it is first checked whether the upper and lower diamond anvil surfaces are parallel, then the heating resistance wire of HDAC-VT and the exposed part of the thermocouple are visually observed for contact, and if there is a clear contact between them, they should be separated by a suitable tool to prevent short circuit. And then, a universal meter is used for respectively detecting whether the circuit of the heating resistance wire and the thermocouple is smooth, so that the phenomenon of circuit interruption is avoided. If the circuit is found to have interruption, the problem should be found out in time and repaired well.
2) HDAC-VT temperature calibration
a. At high temperature, experiments utilized high purity NaCl (800.75 ℃), naNO 3 The melting point of the (306.8 ℃) reagent was corrected for the measured temperature of HDAC-VT. And cleaning the unpolished rhenium sheet, selecting NaCl crystals with proper size and complete crystal forms, placing the NaCl crystals in the sample cavity, lightly closing the upper and lower diamond cavities, and ensuring that the diamond anvil surface and the rhenium sheet have no indentation, so that the pressure in the sample cavity is always standard atmospheric pressure. HDAC-VT was placed on a warming platform using a temperature controller Hydrothermal Diamond Anvil Cell Controller 1300. Heating at 30 ℃/min, continuously heating at 5 ℃/min when the temperature is raised to 750 ℃, heating at 1 ℃/min when the temperature reaches 790, and observing the crystal melting temperature when the temperature approaches the NaCl crystal melting point. By NaNO 3 The temperature calibration experiment operation is basically the same as the experiment, and only the crystal in the sample cavity is replaced by NaNO 3 And (5) a crystal.
b. Freezing point (-0.01 ℃) and NaCl-H of pure water system at low temperature 2 The initial melting temperature (-20.8 ℃) of NaCl of the O system is corrected for the measured temperature of HDAC-VT. The difference between the pressing cavity and the pressing cavity used in the heating platform is that the inner side of the used protective sleeve ring is wrapped with heat insulation paper, a square cavity is reserved in the middle of the sleeve ring, and the ceramic tube passes through the sleeve for displacement in the experimental process conveniently. The method comprises the following specific steps: cleaning and polishing the rhenium sheet, sealing a proper amount of ultrapure water (distilled water at 105 ℃) in a sample, and properly loosening a cavity pressing screw to enable a slightly larger bubble to appear in a sample cavity. The HDAC-VT is placed on a cooling platform (shown in figure 2), and the cooling platform mainly comprises a computer, a Nikon ECLIPSE LV POL microscope, an Omega TC-08 temperature measurement module, a precise manual platform and a liquid nitrogen freezing device. The liquid nitrogen refrigerating device is sequentially connected with a high-purity nitrogen bottle, a gas flowmeter, a liquid nitrogen tank and a tail gas guiding-out use antifreezing tank and a ceramic tube.
Before experimental test, HDAC-VT is placed under a microscope in a cooling platform, a K-type thermocouple used by the HDAC-VT is connected with an Omega TC-08 temperature measurement module, and a precise manual platform is adjusted to enable a ceramic tube to pass through a lantern ring and align with a sample cavity part pressed by diamond, wherein the ceramic tube is basically parallel to a microscope carrier. Before the experiment, the gas flowmeter is opened to introduce nitrogen, after the air in the refrigerating device is discharged, liquid nitrogen is poured into the refrigerating device, and the air in the pipe is prevented from being instantaneously frozen to block the air pipe. In the experimental process, firstly, the gas flow is increased by adjusting the gas flowmeter, the precise platform is adjusted to enable the ceramic pipe orifice to be close to the sample cavity, the temperature in the sample cavity is rapidly reduced to be in a supercooling state, and the precise platform is adjusted again to enable the measured temperature of the thermocouples connected up and down to be kept consistent (the temperature difference is not more than 0.5 ℃). When the temperature is reduced to-90 ℃, the gas flow is reduced, the temperature is increased, and meanwhile, the precise platform is regulated, so that the measured temperatures of the upper thermocouple and the lower thermocouple are always consistent. When the temperature rises to a higher temperature (generally about-20 ℃), the precise manual platform is regulated to gradually separate the porcelain tube from the sample cavity part, and the experimental method can keep the temperature change rate not to exceed 1 ℃/min. When the temperature rises to be close to the minus 1 ℃ of the observation point, the temperature is kept for a period of time, the temperature continues to rise slowly, and the melting temperature of the last ice crystal in the sample cavity is recorded. In the experimental process, the ceramic pipe orifice is not required to be opposite to the thermocouple in the pressing cavity, and when the temperature of the observation point is close to that of the ceramic pipe orifice, the air flow is not easy to be too large, otherwise, the experimental temperature is not accurately measured. The experimental result shows that the freezing point temperature of the ultrapure water is 0.1 ℃. The three-phase point temperature calibration of the NaCl solution and the freezing point calibration of the ultrapure water are basically the same as the above experiment, except that the pure water in the sample cavity is replaced by the NaCl solution with certain salinity. The experiment is carried out to prepare 5wt% NaCl solution, 1g of high-purity NaCl powder is weighed by a balance, all the NaCl powder is poured into a volumetric flask, 19ml of ultrapure water is measured by a burette, and the mixture is stirred uniformly. The experimental process can refer to the above-mentioned ultra-pure water freezing point calibration experimental process, when the darkness of supercooled water is observed to suddenly become bright, namely the three-phase point temperature of NaCl solution, the above-mentioned measured temperature is recorded, and the difference between the measured temperature and the theoretical temperature should be less than 0.5 ℃.
3) Preparing quartz sample and preparing sodium chloride solution
The invention adopts quartz in granite in the Sinkiang Alstoniebeing ore to make slices, double-sided polishing is carried out to 100 mu m, the quartz is unloaded from the glass slice, and the glue on the quartz is wiped clean by alcohol or acetone. A small sample was then taken on a quartz slide and cut to the desired size to be loaded into the HDAC-VT sample cavity. A 5% strength sodium chloride solution was prepared. Due to the evaporation effect, the concentration of the prepared sodium chloride can be remarkably increased after the sodium chloride is filled into the sample cavity, and the concentration of the sodium chloride solution prepared by experiments is not easy to exceed 20 weight percent.
4) Metal rhenium plate polishing and sample chamber cleaning
And polishing the two sides of the rhenium sheet until no scratch is shown, putting the rhenium sheet into an ultrasonic cleaner for cleaning, and wiping the surface of the cavity-pressing diamond anvil with alcohol to clean and dust-free.
Step two: sample cavity sealing and training rhenium sheet
The prepared 5wt% NaCl solution and quartz sample were placed in the HDAC-VT sample chamber and sealed. And adjusting the cavity pressing screw, observing that bubbles with a certain volume appear in the sample cavity, and screwing the screw until the annular belt on the rhenium sheet disappears. At the moment, a quartz sample, liquid water and a bubble exist in the sample cavity of the hydrothermal diamond pressure cavity, the temperature begins to rise, the volume of the bubble gradually reduces along with the gradual rise of the temperature, and when the bubble completely disappears (the gas phase completely unifies into the liquid phase), the uniform temperature Th is obtained 1 . Then slowly cooling until the bubbles reappear, then heating again and recording the bubble disappearance temperature as Th 2 Circularly heating for several times until the continuous two adjacent bubbles disappear to the temperature Th n And Th (Th) n+1 If the difference is equal to or less than 2 ℃, training of the rhenium sheet is completed, otherwise, if the difference is weak, the screw is required to be screwed or the sample is required to be reloaded when the gas leakage occurs.
Step three: determination of alpha-beta quartz phase transition temperature Ttr and uniform temperature Th of NaCl solution
And (5) performing linear calibration on the laser Raman spectrometer by using a low-pressure mercury lamp. And turning on a mercury lamp light source, operating in Labspec6 matched with a Raman instrument, firstly moving a grating to a position of 0nm, collecting a spectrum in an acquisition mode, and adjusting a parameter offset until the position of the collected spectrum peak is at the position of 0 nm. Thereafter the grating is moved to 546.07nm and the spectrum is acquired in acquisition mode, the parameter coefficient being adjusted until the acquired spectral peak is at 546.07 nm. YAG green laser with double frequency, excitation wavelength of 532nm, excitation light source and laser reaching sample surfaceThe power was about 100mW and 14mW, respectively; a1800 grooves/mm grating is selected, and the value of the confocal aperture is 100 mu m (the corresponding spectral resolution is +/-0.2 cm -1 ) And the focusing of the sample was accomplished by an olympuspplan 20x objective lens (numerical aperture of 0.35).
And (5) moving the hydrothermal diamond pressing cavity to the position below a laser micro-confocal Raman spectrometer for in-situ Raman peak acquisition. Raman spectrum acquisition uses a single window acquisition mode, at 320cm -1 The wavenumber is centered and the obtained Raman spectrum ranges from about 77cm -1 To 593cm -1 . And heating the sample, keeping the temperature for about 3-5 minutes after the temperature reaches a temperature value required by the experiment, and then collecting a Raman spectrum at the temperature. Taking an experiment (shown in FIG. 3) with the alpha-beta quartz phase transition temperature Ttr of 717 ℃ as an example, quartz Raman peaks are collected every 100 ℃ except room temperature, and the peak position deviation is smaller than 110cm at room temperature -1 When the temperature is increased by 10 ℃, a Raman peak is acquired, and when the peak position deviation is smaller than 100cm -1 At 1 deg.C, a Raman peak is acquired until the peak is no longer shifted, and the temperature Ttr at which the characteristic peak is no longer changed is recorded 1 . The temperature interval can also be adjusted appropriately according to the shift of the actual peak so as to determine the phase transition temperature point more quickly. A temperature rising rate of 20 ℃/min is adopted in a temperature range from room temperature to 300 ℃; a temperature range of 300-500 ℃ adopts a heating rate of 10 ℃/min; the temperature rising rate of 5 ℃/min is adopted above 500 ℃, and the temperature rising rate is reduced to 1 ℃/min when the alpha-beta phase transition point of quartz is heated. The cumulative time of 30 seconds (single point acquisition time) is used when the temperature is less than 700 ℃, and the cumulative time of 60 seconds is used when the temperature is greater than 700 ℃, and the cycle is twice.
In addition, the bubble disappearing temperature Th in the sample cavity needs to be recorded in the heating process 1 To be Ttr 1 After the determination, the temperature is reduced to 500 ℃ at 5 ℃/min, the temperature is reduced to bubble occurrence at 20 ℃/min, and the bubble disappearance temperature Th is recorded by slowly rising the temperature again 2 While recording the quartz at 128cm -1 Temperature Ttr at which the characteristic peak of raman peak position no longer changes 2 . Th at this time 2 Should be matched with Th 1 Equal or less than 2 ℃, th is considered to be 2 Ttr is a system uniform temperature Th 2 Is alpha-beta quartz phase transition temperature Ttr. Otherwise, the rhenium plate needs to be retrained and the third step is repeated.
Step four: determination of the freezing point Tm of NaCl solution
And after the collection of Raman is completed, placing the pressure cavity on a cooling platform. The experimental process can refer to the NaCl initial dissolution temperature calibration process and the inclusion freezing point measurement method. Firstly, cooling to supercooling (-90 ℃), slowly heating to observe a three-phase point (-20.8 ℃) of a system so as to test the temperature measurement accuracy of a refrigerating system; if the difference between the three-phase observed value and the true value is less than 0.5 ℃, continuing to heat up and observing the temperature of the last ice crystal in the system, and recording the temperature as the solution freezing point temperature Tm.
Step five: fitting of single isovolumetric lines
The salt water system salinity (in wt%) is calculated from the NaCl solution freezing point temperature Tm as shown in formula a according to the salinity calculation model proposed by Bodnar (1993),
NaCl wt％＝1.78×Tm-0.0442×Tm 2 +0.000 557×Tm 3 a formula (a);
using computing software hokieflincs_h 2 O-NACL (on-line version doi: 10.1016/j.cageo.2012.01.022) calculates from the uniform temperature Th and salinity of the salt water system to obtain a uniform pressure (Ph);
according to the relationship Ptr (+ -5.6 MPa) =0.0008·ttr 2 + 2.8056.Ttr-1877.5, the Dan Ying-. Beta.phase transition pressure Ptr is calculated from the Dan Ying-. Beta.phase transition temperature Ttr;
finally, fitting is carried out according to the obtained data points (Th, ph) and (Ttr, ptr) to obtain the isovolumetric line of the salinity. The specific calculation results are shown in Table 1.
As can be seen from FIG. 3, the quartz is 128cm -1 The frequency of the raman peak varies by about 464cm -1 The raman peak frequency is changed by 5 times or more, and therefore, the quartz is used at 128cm -1 The phase transition temperature is obtained according to the change relation of the Raman peak frequency shift along with the temperature, so that the accuracy of measuring the alpha-beta phase transition boundary line of quartz can be further improved.
Some embodiments
The difference from example 1 was only that the salinity of the NaCl solution used was different, and the specific measurement results are shown in Table 1.
Table 1:
test example 1
Isovolumetric line calculation formulas proposed by Zhang and Frantz (1987) are specifically shown as formula (1):
P＝A 1 +A 2 ·T (1)
wherein P in the formula (1) is pressure (unit: bar), T is temperature (. Degree. C.), and coefficient A 1 And A 2 The calculation formula of (2) is shown as formula (2) and (3):
A 1 ＝0.0061+(0.2385-a 1 )·Th—(0.002855+a 2 )·Th 2 —(a 3 ·Th+a 4 ·Th 2 )·m (2)
A 2 ＝a 1 +a 2 ·Th+9.888·10 -6 ·Th 2 +(a 3 +a 4 ·Th)·m (3)；
wherein in the formulae (2) and (3), T h At a uniform temperature (. Degree.C.), m is the molar concentration (mol/kg) of the NaCl solution, a 1 、a 2 、a 3 And a 4 As parameters, the values were determined by fitting isovolumetric experimental data.
The experimental data of different salinity obtained by all the examples of the invention are used to re-simulate the parameter a of the formula (3) 1 、a 2 、a 3 And a 4 (see Table 2 for specific results).
Table 2:
| a 1 | a 2 | a 3 | a 4 | |
| NaCl-H 2 O | 27.21 | -0.05956 | -0.3095 | 0.003232 |
substituting the new parameters shown in table 2 into formulas (1) - (3) to obtain an isovolumetric line calculation formula under certain uniform temperature and salinity, comparing the value of the pressure P or the temperature T obtained by calculation with the formula with the measured actual experimental data, finding that the calculated value is basically consistent with the actual measured data (the average calculation error of the slope of the isovolumetric line obtained by the formula is 4.6%), and calculating by using the formula to obtain the pressure P or the temperature T consistent with the pressure P or the temperature T obtained by the isovolumetric line of the NaCl aqueous solution obtained by the measuring method of the isovolumetric line of the saline system.
Test example 2
The new parameters shown in Table 2 obtained in test example 1 were used to substitute the above formulas (1) - (3), and a series of different salinity and uniform temperature T were used h Substituting the values into (1) - (3) to obtain a series of isovolumetric line calculation formulas of NaCl solutions with different salinity at different uniform temperatures, and then fitting the isovolumetric line calculation formulas into isovolumetric lines respectively (as shown in figure 4);
comparing the isovolumetric line obtained by fitting with the isovolumetric line obtained by fitting by other existing methods (as shown in fig. 4), wherein the other existing methods are as follows: bodnar and Vityk (1994)The isovolumetric line measuring method of the brine system can be based on the calculation software HOKIEFLINCS_H 2 O-NACL (online version doi: 10.1016/j.cageo.2012.01.022) is drawn directly; isovolumetric line measurement of brine systems as proposed by Mao et al (2015), see article A predictive model for the pvtx properties of CO 2 –H 2 O–NaCl fluidmixture up to high temperature and high pressure.Applied Geochemistry,54,54–64。
As can be seen from fig. 4, the present invention is substantially identical to the isovolumetric lines drawn by other conventional methods when the pressure is less than 600MPa, but the errors of the isovolumetric lines obtained by the saline system isovolumetric line measurement method proposed by Bodnar and Vityk (1994) and the saline system isovolumetric line measurement method proposed by Mao et al (2015) are gradually increased when the pressure exceeds 600MPa, wherein the errors of the isovolumetric lines obtained by the saline system isovolumetric line measurement method proposed by Bodnar and Vityk (1994) are the largest, and the isovolumetric lines obtained by the saline system isovolumetric line measurement method proposed by Mao et al (2015) are the next. Therefore, compared with other prior art, the isovolumetric line obtained by the method for measuring the isovolumetric line of the saline water system can be suitable for a higher temperature and pressure range, wherein the temperature can reach 860 ℃ and the pressure can reach 1.2Gpa. Moreover, in the higher pressure range, the isovolumetric line precision of the brine system of the invention is still kept at a higher level.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (4)
1. A method for measuring isovolumetric line of a brine system, comprising the steps of:
acquiring quartz alpha-beta phase transition temperature Ttr, and calculating Dan Ying-beta phase transition pressure Ptr corresponding to the Dan Ying-beta phase transition temperature Ttr according to a relation Ptr (+ -5.6 MPa) =0.0008.Ttr2+2.8056.Ttr-1877.5;
obtaining uniform temperature Th and freezing point temperature Tm of a salt water system, and calculating uniform pressure Ph of the salt water system;
fitting by taking the Dan Ying-beta phase transition temperature Ttr and the uniform temperature Th of the salt water system as abscissa and taking the Dan Ying-beta phase transition pressure Ptr and the uniform pressure Ph of the salt water system as ordinate to obtain an isovolumetric line of the salt water system;
wherein, the Dan Ying-beta phase transition temperature Ttr is the temperature when the characteristic peak of quartz at the peak position of 128cm < -1 > reaches stability; and the Dan Ying-beta phase transition temperature Ttr is measured by combining a hot liquid diamond pressure cavity with a laser Raman spectrometer, and specifically comprises the following steps of:
s1, placing deionized water and a quartz sample or a saline aqueous solution and a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
s2, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, heating, recording bubble disappearance temperature Th1 in the sample cavity, observing that a characteristic peak of a quartz sample at a 128cm-1 Raman peak position continuously deviates in a direction of small wave number in the heating process, and recording temperature Ttr1 when the characteristic peak does not continuously deviate in the direction of small wave number;
s3, suspending heating and slowly cooling, and recording the reappearance bubble disappearance temperature Th2 when the reappearance of bubbles in the sample cavity is observed; meanwhile, the characteristic peak of the quartz sample at the 128cm-1 Raman peak position continuously deviates to the direction with small wave number in the heating process, and the temperature Ttr2 when the characteristic peak does not continuously deviate to the direction with small wave number is recorded;
s4, comparing the bubble disappearing temperature Th1 with the bubble disappearing temperature Th2, and performing the following steps a or b;
a. when the bubble vanishing temperature Th1 and the bubble vanishing temperature Th2 are the same or differ by less than or equal to 2 ℃, the temperature Ttr2 is Dan Ying-beta phase transition temperature Ttr;
b. repeating steps S1-S4 when the bubble disappearing temperature Th1 and the bubble disappearing temperature Th2 differ by more than 2 ℃;
the method for obtaining the uniform temperature Th of the salt water system specifically comprises the following steps:
(1) Placing a sample of a salt water system into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
(2) Connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, heating, recording bubble disappearance temperature Th1 in the sample cavity, then suspending heating, cooling, and recording the re-occurring bubble disappearance temperature Th2 when the re-occurrence of the bubbles in the sample cavity is observed, and slowly heating again;
(3) Comparing the bubble disappearing temperature Th1 and the bubble disappearing temperature Th2, and performing the following steps a or b:
a. when the bubble disappearing temperature Th2 is equal to or less than or equal to 2 ℃ than the bubble disappearing temperature Th1, the Th2 is considered to be uniform temperature Th;
b. and (3) repeating the steps (1) - (3) when the bubble disappearing temperature Th2 and the bubble disappearing temperature Th1 are different by more than 2 ℃.
2. The method according to claim 1, wherein the method for obtaining the freezing temperature Tm of the brine system comprises the following steps:
and placing a sample of the salt water system into a sample cavity of the hydrothermal diamond pressure cavity, sealing the sample cavity, placing the hydrothermal diamond pressure cavity into a cooling platform, reducing the temperature to be lower than-90 ℃, slowly heating, and recording the temperature as the freezing point temperature Tm of the salt water system by observing the melting temperature of the last ice crystal in the sample of the salt water system.
3. The assay of claim 1 wherein the hydrothermal diamond plenum is a Bassett hydrothermal diamond plenum; the laser Raman is a microscopic confocal Raman spectrometer.
4. The measurement method according to claim 1, wherein the temperature increase process of step S2 or step S3 comprises the steps of:
the temperature is increased at a rate of 20-30 ℃/min in a temperature range from room temperature to 300 ℃; a temperature range of 300-500 ℃ adopts a heating rate of 10-15 ℃/min; the temperature rising rate of 5-8 ℃/min is adopted above 500 ℃, and the temperature rising rate is 1-4 ℃/min when the alpha-beta phase transition point of quartz is heated.
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