阅读说明：本技术 一种流动式高温高压溶解度在线测定装置及其测定方法 (Flow type high-temperature high-pressure solubility online measuring device and measuring method thereof ) 是由 方涛 刘博� 丁鑫 姜召 王斌 王玉琪 于 2020-05-30 设计创作，主要内容包括：本发明公开了一种流动式高温高压溶解度在线测定装置及其测定方法,该系统包括进料系统、平衡釜、采样系统和压力控制系统；采用Hastelloy C276材料作为平衡釜体,可以耐受823K的高温和35MPa的高压,保证可以在较大的温度压力范围内获得稳定的相平衡状态；合理的进料系统保证进入平衡釜的试剂组成一致混合均匀；精准的温度和压力控制系统以及机械搅拌装置保证平衡釜内流体相达到充分平衡；合理的采样系统保证采样过程不影响流动体系的相平衡,高压电导率检测池可以在线检测样品的电导率,进一步得到流体的溶解度数据。(The invention discloses a flow type high-temperature high-pressure solubility online measuring device and a measuring method thereof, wherein the system comprises a feeding system, a balance kettle, a sampling system and a pressure control system; the Hastelloy C276 material is adopted as a balance kettle body, so that 823K high temperature and 35MPa high pressure can be resisted, and a stable phase balance state can be obtained in a larger temperature and pressure range; a reasonable feeding system ensures that the components of the reagents entering the balance kettle are consistent and uniformly mixed; the accurate temperature and pressure control system and the mechanical stirring device ensure that the fluid phase in the balance kettle is fully balanced; the reasonable sampling system ensures that the phase balance of the flow system is not influenced in the sampling process, and the high-pressure conductivity detection pool can detect the conductivity of the sample on line so as to further obtain the solubility data of the fluid.)

1. A flow type high-temperature high-pressure solubility online measuring device is characterized by comprising a feeding system, a balance kettle (10), a sampling system and a pressure control system;

the balance space at the center of the balance kettle (10) is formed by surrounding a balance kettle body; stirring the fluid in the balance kettle (10) by a mechanical stirring device (8);

the outlet of the feeding system, namely the outlet of the feeding pipe (20), is arranged at the bottom of the balance kettle (10); the outlet is immersed in the fluid in the balance kettle;

the sampling system is connected with an outlet of the discharge pipe (27), and an inlet of the discharge pipe (27) is communicated with an opening on the inner side of the kettle cover of the balance kettle (10); an opening on the inner side of the kettle cover is communicated with a balance space in the balance kettle (10);

the pressure control system is connected with the feeding system through a tee joint (6), and the temperature control device (9) is directly connected with the balance kettle (10).

2. The on-line measuring device of claim 1, characterized in that the feeding system comprises a raw material solution bottle (1), a feeding pump (3), a one-way valve (5) and a tee (6); the outlet of the raw material liquid reagent bottle (1) is connected to the inlet of the feeding pump (3), the outlet of the feeding pump (3) is connected with one end of a one-way valve (5), the other end of the one-way valve (5) is connected to the first interface of a tee joint (6), the second interface of the tee joint (6) is connected with a feeding pipe (20), and the raw material liquid is fed into the balance kettle (10); the pressure control system is connected to the feeding system, the third interface of tee joint (6) is connected with one end of first filter (131), the other end of first filter (131) is connected with one end of back pressure valve (4), and the other end of back pressure valve (4) is connected with waste liquid recovery bottle (2).

3. The on-line measuring device for the solubility at high temperature and high pressure of the flowing type according to claim 1, characterized in that the equilibrium still (10) adopts Hastelloy C276 alloy as the material of the equilibrium still body.

4. The on-line measuring device of the solubility at high temperature and high pressure of claim 1, wherein the equilibrium space in the equilibrium still (10) is cylindrical, the exterior of the equilibrium still body is covered by an asbestos jacket (30), the exterior of the asbestos jacket (30) is covered by a ceramic electric heating ring (31), the exterior of the ceramic electric heating ring (31) is a stainless steel shell (29), and the equilibrium still (10), the asbestos jacket (30), the ceramic electric heating ring (31) and the stainless steel shell (29) are integrally formed into the equilibrium device; the part of the mechanical stirring device (8) inserted into the balance kettle (10) is a mechanical stirring paddle (81), and the part of the mechanical stirring device (8) positioned outside the balance kettle (10) is provided with a cooling circulating water inlet (23) and a cooling circulating water outlet (22); the uppermost layer of the balancing device is a kettle cover (24); a layer of stainless steel pipe (21) is wrapped on the outer layer of the upstream section before the feeding pipe (20) is communicated with the kettle cover (24), and a layer of stainless steel pipe (21) is also wrapped on the outer layer of the downstream section after the discharging pipe (27) leaves the kettle cover (24); a screw rod (25) and a nut (26) for fixing are arranged on the kettle cover (24); a fixing device hoop (28) is arranged between the kettle cover (24) and the stainless steel shell (29).

5. The on-line flowing high-temperature high-pressure solubility measuring device as claimed in claim 1, wherein the sampling system comprises a safety valve (11) arranged at the outlet of the discharge pipe (27), a second filter (132), a cooling device (14), a third filter (133), a ball valve (15), a high-pressure conductivity detection pool (16), a stop valve (17) and a sampling bottle (18) which are sequentially communicated with the outlet of the discharge pipe (27), and the sampling bottle (18) is immersed in an ice water bath (19); the balanced feed liquid leaves the balance kettle (10) through the discharge pipe (27), and then sequentially passes through the second filter (132), the cooling device (14), the third filter (133), the ball valve (15), the high-pressure conductivity detection pool (16) and the stop valve (17) to enter the sampling bottle (18).

6. The on-line measuring device for the solubility at high temperature and high pressure of claim 1, wherein the thermocouple (7) of the temperature control device (9) is inserted into the balance kettle (10); a pressure gauge (12) is arranged on the balance kettle (10).

7. The on-line measuring device for the solubility at high temperature and high pressure of claim 1, wherein the maximum temperature resistance of the autoclave (10) is 823K, and the maximum pressure resistance thereof is 35 MPa.

8. The method for measuring the flowing type high-temperature high-pressure solubility online measuring device in any one of claims 1 to 7, which is characterized by comprising the following steps:

step one, preparing a standard curve of conductivity-solubility, which comprises the following steps:

(1) the method comprises the steps of filling a system solution to be measured into a raw material liquid reagent bottle (1), continuously feeding the system solution to be measured into a balance kettle (10) through a feeding pump (3), allowing the system solution to be measured to stay in the balance kettle (10) for a period of time, flowing out of a discharge pipe (27), sequentially filtering and cooling through a second filter (132), a cooling device (14) and a third filter (133), flowing out of a measuring device after flowing through a high-pressure conductivity detection pool (16), and measuring the conductivity value of the solution in real time through the high-pressure conductivity detection pool (16); part of the raw material liquid flows out from a pipeline of the pressure control system, and the waste liquid is collected in a waste liquid recovery bottle (2);

(2) heating the balance kettle (10) to a required temperature by using an electric heating system, and adjusting the pressure of a measuring device to a required pressure through a back pressure valve (4); when the temperature fluctuation of the balance kettle (10) measured by the temperature control device (9) is not more than +/-1K, and the pressure fluctuation of the balance kettle (10) measured by the pressure gauge (12) is not more than +/-0.1 MPa, continuously balancing for a period of time;

(3) the system solution to be measured is balanced in a balance kettle (10), and when the conductivity of the solution measured by the high-pressure conductivity detection cell (16) is stable, the conductivity value at the moment is recorded;

(4) sampling from a sampling system to a sampling bottle (18) immersed in an ice water bath (19), and measuring the ion concentration in the sample by using an inductively coupled plasma emission spectrometer to obtain a solubility value;

(5) changing the temperature and the pressure of a measuring device, repeating the steps (3) and (4) in the first step to obtain a plurality of groups of conductivity values and corresponding solubility values of the solution under different temperature and pressure conditions, and fitting by MATLAB software to obtain a conductivity-solubility standard curve;

step two, on-line measurement of mobile high-temperature high-pressure solubility

The same conductivity values of the system solution to be measured are measured by repeating the steps (1) to (3) in the step one, and the corresponding solubilities under different conductivity values can be obtained through the conductivity-solubility standard curve obtained in the step one (5); when the on-line conductivity data drifts, is unstable, or is outside the standard curve range, a calibration is performed by sampling to determine the solubility data.

9. The method according to claim 8, wherein the system solution to be measured is a mixture of an inorganic salt and water, and the molar concentration of the inorganic salt is 0.5 mol/L.

10. The assay of claim 8, wherein the feed rate of the feed system is 4-5 mL/min.

Technical Field

The invention relates to the technical field of solubility determination, in particular to a flow type high-temperature high-pressure solubility online determination device and a determination method thereof.

Background

In the energy structure of China, coal is still one of main energy sources for a long time. The coking wastewater is organic wastewater generated in the processes of coke making from coal, gas purification and coking product recovery, contains a large amount of compounds (such as thiocyanate, chloride, sulfate, ammonium salt, phenols, polycyclic aromatic hydrocarbon and the like), is one of the most toxic industrial wastewater which must be treated before discharge, and accounts for about 2 percent of the total discharge amount of national industrial wastewater. Supercritical Water Oxidation (SCWO) is used as an efficient green chemical technology and is suitable for treating stubborn wastes such as aromatic hydrocarbons, polycyclic organic compounds and the like. Usually within minutes, most of the organic matter is decomposed to H₂O、CO₂、N₂And the like. Since the introduction of industrial application by the company MODAR in the united states in 1980, SCWO plants of commercial scale were established in approximately 30 enterprises, but only 2-3 plants were still in operation until now. The reason is that the key problems of serious corrosion, salt deposition and blockage, high operation cost and the like exist in the actual wastewater treatment process.

In the last decade, the research on corrosion and crystallization mechanisms in the SCWO process has been focused, but the phase equilibrium closely related to the reaction system has not been paid enough attention. The applicant believes that: phase equilibrium research can provide solutions and basic data for the three problems: first, inorganic salts are a significant cause of corrosion of equipment under high temperature, high pressure and oxygen-rich conditions, especially chloride and sulfate salts. The research on corrosion necessarily requires the solubility of salts in high-temperature and high-pressure water, which is one of the basic data that phase equilibrium research can provide; then, supercritical water and nonpolar organic matters are well mutually soluble, and the solubility of inorganic salt in the supercritical water is very low, so that the SCWO technology is applied to the common problems of pipeline blockage and the like caused by salt deposition in a reactor. Starting from phase equilibrium studies, it is possible to guide the setting of the pretreatment (preheating and separation functions) process parameters in order to separate the inorganic salts to the greatest possible extent before the reaction.

The inorganic salts in the coking wastewater are mainly chloride (50-3000mg/L), sulfate (30-2000mg/L) and ammonium salt (250-750 mg/L). The binary and multi-phase behaviors of the components in water are systematically researched in a wide temperature and pressure range (covering the sub/supercritical state of water), which is the most challenging basic scientific problem related to the supercritical water oxidation technology.

In order to obtain basic data of phase equilibrium research, experimental equipment capable of measuring phase equilibrium data under the condition of simultaneous existence of high temperature and high pressure is indispensable, however, at present, the research on the phase equilibrium of inorganic salt and water is rarely carried out in China.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a flow type high-temperature high-pressure solubility online measuring device capable of working under a high-temperature high-pressure environment and a measuring method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a flow type high-temperature high-pressure solubility online measuring device comprises a feeding system, a balance kettle, a sampling system and a pressure control system; the balance space at the center of the balance kettle is formed by surrounding a balance kettle body; stirring the fluid in the balance kettle by a mechanical stirring device; an outlet of the feeding system, namely an outlet of the feeding pipe, is arranged at the bottom of the balance kettle; the outlet is immersed in the fluid in the balance kettle; the sampling system is connected with an outlet of the discharge pipe, and an inlet of the discharge pipe is communicated with an opening on the inner side of the kettle cover of the balance kettle; an opening on the inner side of the kettle cover is communicated with a balance space in the balance kettle; the pressure control system is connected with the feeding system through a tee joint, and the temperature control device is directly connected with the balance kettle.

The invention further improves the following steps: the feeding system comprises a raw material liquid reagent bottle, a feeding pump, a one-way valve and a tee joint; the outlet of the raw material liquid reagent bottle is connected to the inlet of the feeding pump, the outlet of the feeding pump is connected with one end of a one-way valve, the other end of the one-way valve is connected to a first interface of a tee joint, and a second interface of the tee joint is connected with a feeding pipe to feed the raw material liquid into the balance kettle; the pressure control system is connected to the feeding system, a third interface of the tee joint is connected with one end of the first filter, the other end of the first filter is connected with one end of the back pressure valve, and the other end of the back pressure valve is connected with the waste liquid recovery bottle.

The invention further improves the following steps: the balance kettle adopts Hastelloy C276 alloy as a balance kettle body material.

The invention further improves the following steps: the balance space in the balance kettle is cylindrical, the inner diameter is 40mm, the height is 100mm, and the volume is 125 mL; the outer layer of the balance kettle body is wrapped with an asbestos jacket, the outer layer of the asbestos jacket is wrapped with a ceramic electric heating ring, the outer layer of the ceramic electric heating ring is a stainless steel shell, and the balance kettle, the asbestos jacket, the ceramic electric heating ring and the stainless steel shell form a balance device integrally; the part of the mechanical stirring device inserted into the balance kettle is a mechanical stirring paddle, and a cooling circulating water channel is arranged on the part of the mechanical stirring device positioned outside the balance kettle; the uppermost layer of the balancing device is a kettle cover; a layer of stainless steel pipe is wrapped on the outer layer of the upstream section before the feeding pipe is communicated with the kettle cover, and a layer of stainless steel pipe is also wrapped on the outer layer of the downstream section after the discharging pipe leaves the kettle cover; a screw and a nut for fixing are arranged on the kettle cover; a fixing device hoop is arranged between the kettle cover and the stainless steel shell.

The invention further improves the following steps: the sampling system comprises a safety valve arranged at the outlet of the discharge pipe, a second filter, a cooling device, a third filter, a ball valve, a high-pressure conductivity detection pool, a stop valve and a sampling bottle which are sequentially communicated with the outlet of the discharge pipe, and the sampling bottle is immersed in an ice-water bath; and the balanced feed liquid leaves the balance kettle through the discharge pipe and then enters the sampling bottle through the second filter, the cooling device, the third filter, the ball valve, the high-pressure conductivity detection pool and the stop valve in sequence.

The invention further improves the following steps: a thermocouple of the temperature control device is inserted into the balance kettle; the pressure gauge is arranged on the balance kettle.

The invention further improves the following steps: the maximum tolerance temperature of the balance kettle is 823K, and the maximum tolerance pressure is 35 MPa.

The invention further improves the following steps: the connecting pipeline between each part is a 316L stainless steel pipe, the inner diameter is 1mm, and the outer diameter is 3 mm.

The measuring method of the flow type high-temperature high-pressure solubility online measuring device comprises the following steps:

step one, preparing a standard curve of conductivity-solubility, which comprises the following steps:

(1) the method comprises the following steps of (1) filling a system solution to be measured in a raw material liquid reagent bottle, continuously feeding the system solution to be measured into a balance kettle through a feeding pump, allowing the system solution to be measured to stay in the balance kettle for a period of time, flowing out of a discharge pipe, filtering and cooling through a filter and a cooling device in sequence, flowing out of a measuring device after flowing through a high-pressure conductivity detection pool, and measuring the conductivity value of the solution in real time through the high-pressure conductivity detection pool; part of the raw material liquid flows out from a pipeline of the pressure control system, and the waste liquid is collected in a waste liquid recovery bottle;

(2) heating the balance kettle to a required temperature by using an electric heating system, and adjusting the pressure of the measuring device to a required pressure by using a back pressure valve; when the temperature fluctuation of the balance kettle measured by the temperature control device is not more than +/-1K and the pressure fluctuation of the balance kettle measured by the pressure gauge is not more than +/-0.1 MPa, continuously balancing for a period of time;

(3) balancing the system solution to be measured in a balance kettle, when the conductivity of the solution measured by the high-pressure conductivity detection cell is stable, indicating that a dynamic balance state is achieved, and recording the conductivity value at the moment;

(4) sampling from a sampling system to a sampling bottle immersed in an ice water bath, and measuring the ion concentration in the sample by using an inductively coupled plasma emission spectrometer to obtain a solubility value;

(5) changing the temperature and the pressure of a measuring device, repeating the steps (3) and (4) in the first step, obtaining 20 groups of conductivity values and corresponding solubility values of the solution under different temperature and pressure conditions, and fitting by MATLAB software to obtain a conductivity-solubility standard curve;

step two, on-line measurement of mobile high-temperature high-pressure solubility

Measuring the same conductivity value of the system solution to be measured by repeating the steps (1) to (3) in the step one, and obtaining the solubility corresponding to different conductivity values through the conductivity-solubility standard curve obtained in the step one (5); when the on-line conductivity data drifts, is unstable, or is outside the standard curve range, a calibration is performed by sampling to determine the solubility data.

The invention further improves the following steps: the system solution to be measured is a mixture of inorganic salt and water, wherein the molar concentration of the inorganic salt is 0.5 mol/L.

The invention further improves the following steps: the feed rate of the feed system was 4-5 mL/min.

The invention further improves the following steps: the stirring rate was 600 r/min.

Compared with the prior art, the invention has the following advantages:

(1) the reasonable feeding system ensures that the components of the reagent entering the balance kettle are uniformly mixed.

(2) The reasonable sampling system ensures that the sampling process does not influence the phase balance of the flow system, and the sampling process actually samples the flowing liquid, which is the advantage of the flow detection device.

(3) A reasonable temperature and pressure control system ensures that stable temperature and pressure conditions required for the experiment are provided.

(4) The high-pressure conductivity detection pool can detect the conductivity value of a sample on line, further calculates the solubility value of the solution according to a conductivity-solubility standard curve, facilitates data acquisition, and simultaneously is compared with sample data obtained by sampling, so that the accuracy and reliability of the data are ensured.

(5) The mechanical stirring device is adopted, so that the heat distribution in the balance kettle is ensured to be uniform, the sufficient deposition of solid substances is promoted, the fluid substances can be fully mixed in the balance kettle, and the complete dynamic balance state is achieved.

(6) The reactor body is made of Hastelloy C276 alloy, so that the highest tolerance temperature of the whole device reaches 823K, the highest tolerance pressure reaches 35MPa, and a stable phase equilibrium state can be obtained in a larger temperature and pressure range.

Drawings

FIG. 1 is a schematic structural diagram of a flow-type high-temperature high-pressure solubility online measurement device according to the present invention.

FIG. 2 is a view showing the structure of an equilibrium reactor.

Wherein: 1 is a raw material solution reagent bottle; 2 is a waste liquid recovery bottle; 3 is a feed pump; 4 is a back pressure valve; 5 is a one-way valve; 6 is a tee joint; 7 is a thermocouple; 8 is a mechanical stirring device; 9 is a temperature control device; 10 is a balance kettle; 11 is a safety valve; 12 is a pressure gauge; 14 is a cooling device; 15 is a ball valve; 16 is a high-pressure conductivity detection cell; 17 is a stop valve; 18 is a sampling bottle; 19, ice water bath; 20 is a feed pipe; 21 is a stainless steel tube; 22 is a cooling circulating water outlet; 23 is a cooling circulating water inlet; 24 is a kettle cover; 25 is a screw; 26 is a nut; 27 is a discharge pipe; 28 is a hoop; 29 is a stainless steel shell; 30 is an asbestos jacket; 31 is a ceramic electric heating ring; 131 is a first filter; 132 is a second filter; numeral 133 denotes a third filter; 81 is a mechanical stirring paddle; 201 is a feed probe tube.

Detailed Description

The invention is described in further detail below with reference to the figures and specific examples.

As shown in fig. 1 and fig. 2, the present invention provides a flow-type online measuring apparatus for high-temperature and high-pressure solubility, which comprises a feeding system, a high-temperature and high-pressure equilibrium kettle 10, a sampling system and a pressure control system;

the feeding system comprises a raw material liquid reagent bottle 1, a feeding pump 3, a one-way valve 5 and a tee joint 6; the outlet of the raw material liquid reagent bottle 1 is connected to the inlet of the feed pump 3, the outlet of the feed pump 3 is connected with one end of a one-way valve 5, the other end of the one-way valve 5 is connected to the first interface of a three-way valve 6, the second interface of the three-way valve 6 is connected with a feed pipe 20, and the raw material liquid is fed into the balance kettle 10; the feed liquid is initially placed in a raw material liquid reagent bottle 1, the feed pump 3 pumps the feed liquid to the balance kettle 10, the feed liquid enters a tee joint 6 through a one-way valve 5, and the feed liquid in the middle of the feed liquid is introduced into the bottom of the balance kettle 10 through a feed pipe 20; the mouth of feed probe 201 is submerged in the fluid in the tank.

The balance kettle 10 adopts Hastelloy C276 alloy as a balance kettle body material, connecting pipelines among all parts adopt 316L stainless steel pipes, the inner diameter is 1mm, the outer diameter is 3mm, the highest tolerance temperature of the whole system is 823K, and the highest tolerance pressure is 35 MPa; the equilibrium space in the equilibrium reactor 10 had a cylindrical shape with an inner diameter of 40mm, an inner height of 100mm and a volume of 125 mL.

The balance space at the center of the balance kettle 10 is formed by surrounding a balance kettle body; a mechanical stirring device 8 is arranged in the balance kettle 10; the outer layer of the balance kettle body is wrapped with a layer of asbestos jacket 30 for preventing heat loss, the outer layer of the asbestos jacket 30 is wrapped with a layer of ceramic electric heating ring 31, and the balance kettle 10 of the flow type high-temperature high-pressure solubility online measuring device is heated by an electric heating system; the outer layer of the ceramic electric heating ring 31 is a stainless steel shell 29, and the balance kettle 10, the asbestos jacket 30, the ceramic electric heating ring 31 and the stainless steel shell 29 form a balance device integrally; the part of the mechanical stirring device 8 inserted into the balance kettle 10 is a mechanical stirring paddle 81, and the part of the mechanical stirring device 8 positioned outside the balance kettle 10 is provided with a cooling circulating water inlet 23 and a cooling circulating water outlet 22; the uppermost layer of the balancing device is a kettle cover 24; a layer of stainless steel pipe 21 is wrapped on the outer layer of the upstream section before the feeding pipe 20 is communicated with the kettle cover 24, and a layer of stainless steel pipe 21 is also wrapped on the outer layer of the downstream section after the discharging pipe 27 leaves the kettle cover 24; a screw 25 and a nut 26 for fixing are arranged on the kettle cover 24; a fixing device hoop 28 is arranged between the kettle cover 24 and the stainless steel shell 29.

The balance kettle 10 is additionally provided with the mechanical stirring device 8, so that the heat distribution in the balance kettle 10 is ensured to be uniform, the full deposition of solid matters is promoted, the fluid substances can be fully mixed in the balance kettle 10 to reach a complete dynamic balance state, and credible solubility data can be obtained during sampling; and a cooling circulation system is additionally arranged on the part, positioned outside the balance kettle 10, above the mechanical stirring device 8 so as to reduce the temperature of the mechanical stirring device 8 and prevent the device from being damaged.

The sampling system comprises a safety valve 11, a second filter 132, a cooling device 14, a third filter 133, a ball valve 15, a high-pressure conductivity detection cell 16, a stop valve 17, a sampling bottle 18 and an ice-water bath 19; an inlet of the sampling system, namely an inlet of the discharge pipe is communicated with an opening on the inner side of the kettle cover of the balance kettle 10; an opening on the inner side of the kettle cover is communicated with a balance space in the balance kettle 10; a safety valve 11 is arranged at the outlet of the balance kettle 10; after the balanced feed liquid leaves the balance kettle 10 through the discharge pipe 27, the feed liquid sequentially passes through the second filter 132, the cooling device 14, the third filter 133, the ball valve 15, the high-pressure conductivity detection pool 16 and the stop valve 17 and enters the sampling bottle 18; the sampling bottle 18 is immersed in an ice-water bath 19; the conductivity of the solution is detected on line by a high-pressure conductivity detection cell 16; the solution is balanced in the balance kettle 10, when the conductivity of the solution is stable, the temperature fluctuation of the balance kettle 10 measured by the temperature control device 9 is not more than +/-1K, and the pressure fluctuation of the balance kettle 10 measured by the pressure gauge 12 is not more than +/-0.1 MPa, the sample is taken from the sampling system to the sampling bottle 18 immersed in the ice water bath 19, the effluent liquid is actually sampled in the sampling process, and the phase balance state of a flow system is not influenced in the sampling process, which is the advantage of the flow detection device; the collected sample is rapidly cooled to a liquid state, so that the composition of the obtained sample is consistent with that in the balance kettle 10; the sampling system can accurately control the sampling flow rate, and the adverse effect on the system balance caused by the over-high flow rate is prevented; the sampling bottle 18 is immersed in an ice-water bath 19 to ensure that the sample is rapidly condensed into a liquid state after being collected, and the obtained sample has the same composition with the corresponding phase state.

The pressure control system is connected with the feeding system; the third interface of the tee joint 6 is connected with one end of a first filter 131, the other end of the first filter 131 is connected with one end of a back pressure valve 4, the other end of the back pressure valve 4 is connected with a waste liquid recovery bottle 2, and the back pressure valve is mainly used for controlling the pressure of the system; the temperature control device 9 is directly connected with the balance kettle 10, and the thermocouple 7 of the temperature control device 9 is inserted into the balance kettle 10; the temperature measured by the thermocouple 7 is directly fed back into the temperature control device 9, and the control system directly adjusts the output heat so as to control the temperature, so as to ensure that the overall temperature of the system meets the experimental requirements; the balance kettle 10 is provided with a pressure gauge 12.

The invention relates to a measuring method of a flow type high-temperature high-pressure solubility online measuring device, which comprises the following steps:

step one, preparing a standard curve of conductivity-solubility

(1) Firstly, filling a system solution to be measured into a raw material solution reagent bottle 1, pumping the solution by using a feed pump 3 (with the maximum flow rate of 10mL/min), and feeding the solution into a balance kettle 10 from a feed pipe 20 through a one-way valve 5 and a tee joint 6; the balanced fluid flows out from the discharge pipe 27, passes through the second filter 132, reaches the cooling device 14 for cooling, and then flows out through the third filter 133, the ball valve 15, the high-pressure conductivity detection cell 16 and the stop valve 17; detecting the conductivity of the solution in real time through a high-pressure conductivity detection cell 16; part of the raw material liquid flows into the waste liquid recovery bottle 2 through the first filter 131 and the back pressure valve 4;

(2) setting balance temperature 473-823K and balance pressure 8-35 MPa; the backpressure valve 4 is adjusted to control the pressure of the whole system, and the ball valve 15 is adjusted to cooperatively control the pressure of the system; the thermocouple 7 monitors the temperature of the system in real time and feeds the temperature back to the temperature control device 9, and the temperature control device 9 controls the temperature of the system; the mechanical stirring device 8 ensures that the heat in the balance kettle 10 is uniformly distributed, promotes the full deposition of solid matters, and ensures that fluid matters can be fully mixed in the balance kettle 10 to achieve a complete dynamic balance state; the pressure gauge 12 monitors the system pressure; the safety valve 11 relieves the pressure of the device when the system pressure exceeds the safety pressure; when the temperature and the pressure of the system reach a set value (the temperature fluctuation of the system does not exceed +/-1K, and the pressure fluctuation does not exceed +/-0.1 MPa), continuing balancing for a sufficient time;

(3) when the conductivity of the solution is stable, indicating that the system reaches a dynamic equilibrium state, and recording the conductivity value at the moment;

(4) sampling from a sampling system to a sampling bottle 18 immersed in an ice water bath 19, and determining the composition of the collected sample by using an inductively coupled plasma emission spectrometer to obtain a solubility value;

(5) changing the temperature and the pressure of a measuring device, repeating the steps (3) and (4) in the step one, obtaining 20 groups of conductivity values and corresponding solubility values of the solution under different temperature and pressure conditions, and fitting by MATLAB software to obtain a conductivity-solubility standard curve;

step two: flow type high-temperature high-pressure solubility on-line determination

The same conductivity values of the system solution to be measured are measured by repeating the steps (1) to (3) in the step one, and the corresponding solubilities under different conductivity values can be obtained through the conductivity-solubility standard curve obtained in the step one (5); when the on-line conductivity data drifts, is unstable, or is outside the standard curve range, a calibration is performed by sampling to determine the solubility data.