Ultrahigh-temperature autoclave system for supercritical water oxidation test and test method thereof

Abstract

This invention relates to an ultra-high temperature and high pressure autoclave system and its testing method for supercritical water oxidation experiments. The autoclave module of the system includes a horizontal tubular autoclave body and a split cylindrical heater. The split cylindrical heater is fitted outside the horizontal tubular autoclave body. The steam inlet end of the horizontal tubular autoclave body is an integrated bottom, including an inner layer with small holes and an outer layer with steam inlet holes. A steam inlet cavity is formed between the outer and inner layers. The steam outlet end of the horizontal tubular autoclave body is sealed by a sealing pipe plug and a cylindrical flange. A steam outlet hole is opened on the sealing pipe plug, which communicates with the cavity of the horizontal tubular autoclave body. A central threaded hole coaxial with the steam outlet hole is opened on the cylindrical flange. A water treatment module, a water chemistry quality monitoring module, a liquid injection module, and a preheating module are connected to the steam inlet end of the horizontal tubular autoclave body through pipelines. The steam outlet end of the horizontal tubular autoclave body is connected to an explosion-proof module through a steam outlet hole. A temperature and pressure monitoring and regulation module is used to control the temperature and pressure at the steam inlet end.

Description

Technical Field

[0001] This invention relates to supercritical water oxidation test equipment, specifically to an ultra-high temperature and high pressure autoclave system and its test method for supercritical water oxidation tests. Background Technology

[0002] Developing high-parameter ultra-supercritical coal-fired power generation technology is of great strategic significance and practical application value for my country's energy conservation, pollution reduction, and carbon dioxide emission reduction. Over the past two decades, my country's domestically produced coal-fired power generating units have gradually progressed from subcritical and supercritical to ultra-supercritical at the 620℃ level. Compared with existing 600℃–620℃ ultra-supercritical power generation technology, the structural differences in power generation equipment for higher-parameter (650℃, 700℃) ultra-supercritical power generation technologies are not significant. The key to improving steam parameters lies in developing or selecting suitable materials for critical high-temperature components (such as high-temperature boiler tubes, headers, main steam pipes, turbine rotors, blades, cylinders, high-temperature valves, etc.). Practice shows that due to the strong oxidizing properties of supercritical water, related components often undergo severe oxidation during operation, posing a significant threat to the safe operation of the unit. Therefore, the oxidation resistance of candidate materials in supercritical water is a crucial evaluation indicator.

[0003] To investigate the antioxidant properties of candidate materials in supercritical water, researchers both domestically and internationally have conducted extensive work. However, due to limitations in experimental equipment, it remains impossible to truly test the oxidation performance of materials under near-realistic conditions (dynamic supercritical water) at temperatures of 650℃–750℃ and pressures of 35MPa–45MPa. This is because, under current technological conditions, achieving a sealed environment under ultra-high temperature and pressure conditions is extremely difficult; and when external water is continuously pumped into the autoclave and the supercritical water after the reaction is continuously discharged, the temperature and pressure within the autoclave cavity fluctuate significantly. Furthermore, the safety of the equipment under ultra-high temperature and pressure conditions is also a challenge. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides an ultra-high temperature and high pressure reactor system and its testing method for supercritical water oxidation experiments. The system is reasonably designed, has a simple structure, good sealing performance, precise temperature and pressure control, is safe and reliable, and occupies a small area.

[0005] This invention is achieved through the following technical solution:

[0006] The ultra-high temperature and high pressure autoclave system for supercritical water oxidation experiments includes a water treatment module, a water chemistry quality monitoring module, a liquid injection module, a preheating module, an autoclave module, an explosion-proof module, and a temperature and pressure monitoring and control module.

[0007] The autoclave module includes a horizontal tubular autoclave body and a split cylindrical heating furnace; the split cylindrical heating furnace is fitted outside the horizontal tubular autoclave body.

[0008] The steam inlet end of the horizontal tubular high-pressure reactor body is an integrated reactor bottom, comprising an inner layer with small holes and an outer layer with steam inlet holes; a steam inlet cavity is formed between the outer layer and the inner layer; the steam outlet end of the horizontal tubular high-pressure reactor body is sealed by a sealing pipe plug and a cylindrical flange; a steam outlet hole is opened on the sealing pipe plug and communicates with the reactor cavity of the horizontal tubular high-pressure reactor body; a central threaded hole coaxial with the steam outlet hole is opened on the cylindrical flange;

[0009] The water treatment module, water chemistry quality monitoring module, liquid injection module, and preheating module are sequentially connected to the steam inlet end of the horizontal tubular high-pressure reactor body through pipelines. The steam outlet end of the horizontal tubular high-pressure reactor body is connected to the explosion-proof module through the steam outlet hole, forming a medium flow loop.

[0010] The temperature and pressure monitoring and regulation module is used to control the temperature and pressure at the steam inlet and to regulate the temperature and pressure inside the vessel cavity of the horizontal tubular high-pressure autoclave.

[0011] Furthermore, the horizontal tubular autoclave body has thermocouple placement holes on the inner and outer layers of the steam inlet end, and a cavity thermocouple is fixedly installed in the thermocouple placement hole, extending into the cavity of the autoclave body; the small holes in the inner layer are evenly distributed, and the inner walls of the small holes are coated with a ceramic coating; the output end of the cavity thermocouple is connected to the control end of the split cylindrical heating furnace; the steam outlet end of the horizontal tubular autoclave body is provided with several threads, and a boss and a groove are provided inside; the inner diameter of the cylindrical flange is equal to the outer diameter of the horizontal tubular autoclave body, and several bolts are evenly arranged along the circumference of the bottom surface; the tail of the sealing plug is provided with a handle, and the end is provided with a boss and a groove that match the groove and boss of the steam outlet end of the horizontal tubular autoclave body; the center of the handle is a cylindrical pipe, which passes through the central screw hole of the cylindrical flange and is fixedly and sealed to the cylindrical flange by threads.

[0012] Furthermore, the temperature and pressure monitoring and regulation module includes a first PID temperature controller, a second PID temperature controller, a pressure regulator control device, and a back pressure valve; the first PID temperature controller is connected to the preheating module; the second PID temperature controller is connected to the split cylindrical furnace; the pressure regulator control device includes a pressure regulator, a first pressure sensor, and a first pressure gauge; the pressure regulator is installed on the pipeline between the liquid injection module and the preheating module, and the first pressure sensor and the first pressure gauge are installed at the inlet of the pressure regulator; the back pressure valve is installed on the steam outlet pipeline of the horizontal tubular high-pressure reactor body.

[0013] Furthermore, the preheating module includes a preheating furnace with a serpentine coil inside and a preheating temperature measuring thermocouple connected to the preheating furnace; the inlet end of the serpentine coil of the preheating furnace is connected to the outlet of the pressure regulator, and the outlet end is connected to the steam inlet end of the horizontal tubular high-pressure vessel; the output end of the preheating temperature measuring thermocouple is connected to the control end of the preheating furnace.

[0014] Furthermore, the explosion-proof module includes a check valve and a first rupture valve sequentially arranged on the steam outlet pipeline of the horizontal tubular autoclave body. A second rupture valve and a safety valve are arranged in parallel on the output pipeline of the first rupture valve. A second pressure sensor and a second pressure gauge are arranged on the check valve and the steam outlet pipeline of the horizontal tubular autoclave body. The back pressure valve is arranged on another pipeline at the outlet end of the check valve.

[0015] Furthermore, it also includes a condenser and a circulating water tank that are sequentially installed at the outlet of the back pressure valve.

[0016] Furthermore, the water treatment module includes an ultrapure water preparation device, an automatic dosing device, and a water storage tank; the water storage tank is equipped with an automatic dosing device, the inlet pipe is connected to the ultrapure water preparation device, and the outlet pipe is equipped with a four-way valve and an electromagnetic relief valve in sequence.

[0017] Furthermore, the water chemistry quality monitoring module includes an online dissolved oxygen meter, an ion concentration meter, and an online pH meter connected in parallel on the pipeline between the water treatment module and the liquid injection module.

[0018] Furthermore, the liquid injection module includes a high-pressure metering pump; the inlet of the high-pressure metering pump is connected to the outlet pipeline of the water chemical quality monitoring module.

[0019] The test methods for the ultra-high temperature and high pressure reactor system used in supercritical water oxidation experiments include,

[0020] Metal materials are placed inside the horizontal tubular autoclave, and the steam outlet of the autoclave is sealed by a sealing plug and a cylindrical flange.

[0021] Tap water is preheated and treated sequentially through a water treatment module, a water chemistry quality monitoring module, a liquid injection module, and a preheating module. It is then fed into the cavity of the horizontal tubular high-pressure reactor through the steam inlet. The temperature and pressure at the steam inlet are controlled by a temperature and pressure monitoring and adjustment module, regulating the temperature and pressure within the reactor cavity. The oxidation performance of metallic materials in dynamic supercritical water at 650℃~750℃ and 35MPa~45MPa pressure is then tested using a split-type cylindrical heating furnace.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects:

[0023] This invention utilizes a horizontal tubular autoclave as the primary material for testing the oxidation performance of metallic materials. The steam inlet of the autoclave is integrated into a single bottom. Tap water, supplied sequentially from a water treatment module, a water chemistry quality monitoring module, a liquid injection module, and a preheating module connected to the steam inlet, is fed into the autoclave cavity through a steam inlet hole on the outer layer and small holes on the inner layer. The small holes ensure even distribution of the water within the cavity, thus improving the accuracy and reliability of the metal oxidation performance test. Simultaneously, the steam outlet of the autoclave is sealed. The sealing effect is effectively improved by using a plug and a cylindrical flange with a steam outlet. The special horizontal tubular autoclave body structure design, combined with the temperature and pressure monitoring and regulation module, the thermocouple connected to the autoclave body and the explosion-proof module set at the steam outlet, can effectively ensure the sealing effect while providing more precise and stable control of the temperature and pressure inside the autoclave. The overall system is safe and reliable, and can complete the testing of the oxidation performance of metal materials in dynamic supercritical water at a temperature of 650℃~750℃ and a pressure of 35MPa~45MPa.

[0024] Furthermore, the system of this invention employs thermocouple placement holes on the outer and inner layers of the horizontal tubular autoclave. The thermocouples for measuring the autoclave cavity are inserted into the cavity through these holes, effectively measuring the temperature within the cavity. A ceramic coating on the inner wall of the uniformly distributed small holes effectively prevents oxidation and subsequent clogging of the holes in high-temperature, high-pressure environments. A sealing plug is installed between the steam outlet of the horizontal tubular autoclave and the cylindrical flange, with matching bosses and grooves on both to achieve a complete seal. A high-temperature anti-seize agent is applied between the two to prevent seizing and improve safety and reliability.

[0025] Furthermore, the system of this invention controls the temperature of the preheating module by setting a first PID temperature controller on the preheating module, and sets a second PID temperature controller on the split cylindrical heating furnace to set the heating / cooling rate, test temperature, and holding time in segments, so that the temperature fluctuation in the cavity of the horizontal tubular autoclave meets the test requirements. At the same time, a pressure regulator is set in series with the high-pressure metering pump at the steam inlet end. Using a first pressure gauge, a first pressure sensor, and a pressure regulator with PID control, the pressure of the pumped liquid is monitored in real time and adjusted according to the pressure feedback. In addition, a back pressure valve is set at the steam outlet end of the system to regulate and stabilize the pressure in the circuit. Combined with the pressure regulator control system, the pressure fluctuation in the cavity meets the test requirements.

[0026] Furthermore, the system of the present invention adopts a preheating furnace with a built-in serpentine coil, connects the inlet of the serpentine coil to the outlet of the pressure regulator, and then connects the outlet of the serpentine coil to the steam inlet of the horizontal tubular high-pressure vessel to form a passage. Combined with the preheating temperature measuring thermocouple connected to the preheating furnace, the temperature inside the preheating furnace is monitored and adjusted in real time.

[0027] Furthermore, the system of the present invention employs a second pressure sensor placed on the steam outlet pipeline at the steam outlet end of the horizontal tubular autoclave body, and feeds back the pressure information to the second pressure gauge in real time. Based on the steam pressure value in the pipeline, the first rupture valve or safety valve can be automatically opened in an emergency as needed, ensuring the safety and reliability of the entire system.

[0028] Furthermore, the system of the present invention converts the high-temperature and high-pressure water after the reaction into normal-temperature and normal-pressure water by placing the condenser and the circulating water tank in sequence on the pipeline at the outlet of the back pressure valve, and collects it in the circulating water tank. It is environmentally friendly, efficient, economical and reliable.

[0029] Furthermore, the system of this invention uses an automatic dosing device to quantitatively add the deoxygenating agent to the water storage tank, which is efficient, convenient, safe and reliable. At the same time, an ultrapure water preparation device is installed on the inlet pipe of the water storage tank to ensure the quality of the test water and improve the accuracy of the test results. In addition, a four-way valve is set on the outlet pipe to facilitate the connection of subsequent treatment equipment, which is safe and efficient.

[0030] Furthermore, the system of the present invention connects the online dissolved oxygen meter, the ion concentration meter, and the pH online detector in parallel through pipelines to the pipeline between the water treatment module and the liquid injection module, thereby realizing the monitoring of the quality of the treated water.

[0031] Furthermore, the system of the present invention, by setting a high-pressure metering pump on the outlet pipeline of the water chemical quality monitoring module, can pump the deoxygenated water into the preheating module. After the steam temperature reaches the set temperature, it enters the autoclave module through the pipeline, which can effectively improve the efficiency of test. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the system described in an embodiment of the present invention.

[0033] Figure 2 This is a schematic diagram of the structure of the horizontal tubular high-pressure reactor body described in this embodiment of the invention.

[0034] Figure 3 This is a schematic diagram of the inner layer of the steam inlet end of the horizontal tubular high-pressure reactor body in an embodiment of the present invention.

[0035] The system includes: 1. Ultrapure water preparation system; 2. Automatic dosing system; 3. Water storage tank; 4. Dissolved oxygen meter; 5. pH meter; 6. Ion concentration meter; 7. Electromagnetic relief valve; 8. High-pressure metering pump; 9. Voltage regulator; 10. Preheating furnace; 11. First PID temperature controller; 12. Preheating temperature measuring thermocouple; 13. Steam inlet; 14. Horizontal tubular autoclave body; 15. Metal sample; 16. Split-type cylindrical heating furnace; 17. Cylindrical flange; 18. 19. Steam outlet, 20. Bolt, 21. First pressure sensor, 22. First pressure gauge, 23. First burst valve, 24. Safety valve, 25. Check valve, 26. Back pressure valve, 27. Condenser, 28. Circulating water tank, 29. Sealing plug, 30. Inner layer, 31. Thermocouple placement hole, 32. Small hole, 33. Thermocouple for vessel cavity, 34. Second PID temperature controller, 35. Second burst valve, 36. Second pressure sensor, 37. Second pressure gauge. Detailed Implementation

[0036] The present invention will be further described in detail below with reference to specific embodiments. These descriptions are for explanation purposes only and are not intended to limit the scope of the invention.

[0037] The ultra-high temperature and high pressure autoclave system for supercritical water oxidation experiments provided by this invention mainly includes a water treatment module, a water chemical quality monitoring module, a liquid injection module, a preheating module, a high pressure autoclave module, a temperature and pressure monitoring and regulation module, an explosion-proof module, and a condenser 26. The modules are connected by pipelines to form a media flow loop. Figure 1 As shown, the specific structure is as follows:

[0038] The water treatment module includes an ultrapure water preparation device 1, an automatic dosing device 2, and a water storage tank 3 equipped with a dosing port, a monitoring port, and an electromagnetic relief valve 7, all three connected by pipelines. The ultrapure water preparation device 1 is used to treat tap water. The automatic dosing device 2 can quantitatively add deoxygenating agent to the water storage tank 3 through the dosing port. The monitoring port of the water storage tank 3 is connected in sequence to the water chemistry monitoring module and the liquid injection module via pipelines. The electromagnetic relief valve 7 is installed on the pipeline between the water chemistry monitoring module and the liquid injection module.

[0039] The water chemical quality monitoring module includes a dissolved oxygen meter 4, a pH meter 5, and an ion concentration meter 6. These are connected to the pipeline after the monitoring hole of the water storage tank 3 via a four-way valve to realize real-time monitoring of water quality. After the water quality meets the test requirements, it is injected into the liquid injection module via the electromagnetic relief valve 7.

[0040] The liquid injection module includes a high-pressure metering pump 8; the inlet of the high-pressure metering pump 8 is connected to the electromagnetic relief valve 7 on the water storage tank 3 through a pipeline, and the outlet is connected to the preheating module through a heat-resistant steel pipeline; the high-pressure metering pump 8 pumps the deoxygenated water into the preheating module, and after the steam temperature reaches the set temperature, it enters the high-pressure autoclave module through a pipeline.

[0041] The preheating module includes a preheating furnace 10 and a preheating temperature measuring thermocouple 12. The preheating furnace 10 is equipped with a serpentine coil. The inlet end of the serpentine coil is connected to the outlet of the voltage regulator 9 through a pipeline, and the outlet end is connected to the steam inlet of the high-pressure reactor module through a pipeline. The probe end of the preheating temperature measuring thermocouple 12 extends into the preheating furnace 10, and the output end is connected to the control terminal of the preheating furnace 10 for real-time measurement of the furnace temperature. The preheating furnace 10 can preheat the deoxygenated water to a set temperature before sending it into the high-pressure reactor module.

[0042] The autoclave module includes a horizontal tubular autoclave body 14 and a split cylindrical heating furnace 16 arranged around the horizontal tubular autoclave body 14.

[0043] The horizontal tubular autoclave body 14 is made of a super high-temperature high-strength nickel-based alloy, with an outer diameter of 100-120 mm and a wall thickness of 5-10 mm.

[0044] The steam inlet end of the horizontal tubular high-pressure reactor body 14 is an integrated reactor bottom, adopting a double-layer structure similar to a shower head. The outer layer has a steam inlet hole 13 and a temperature measuring thermocouple placement hole; for example... Figure 3 As shown, the inner layer 29 has evenly distributed small holes 31 and thermocouple placement holes 30. The diameter of the small holes 31 is 1-3 mm. The inner wall of the small holes 31 is coated with a ceramic coating to prevent the diameter of the small holes 31 from shrinking or even becoming blocked due to oxidation in a high-temperature and high-pressure environment. The thermocouple 32 of the vessel cavity passes through two thermocouple placement holes on the inner and outer layers of the integrated vessel bottom and is inserted into the vessel cavity of the horizontal tubular high-pressure vessel body 14. It is fixed to the integrated vessel bottom by welding. Its output end is connected to the control end of the split cylindrical heating furnace 16 to feed back the temperature in the vessel cavity of the horizontal tubular high-pressure vessel body 14 to the temperature and pressure monitoring and adjustment module in real time.

[0045] The steam outlet end of the horizontal tubular autoclave 14 is externally threaded with multiple turns of thread, and internally has a boss and a groove. The surface of the boss is flush with the outermost thread surface, and it is fixedly and sealed to a cylindrical flange 17 with an inner diameter equal to the outer diameter of the horizontal tubular autoclave 14 via threads; Figure 2As shown, the bottom surface of the cylindrical flange 17 has a steam outlet 18, a central screw hole, and multiple bolts 19 evenly distributed along the circumference. Between the horizontal tubular autoclave body 14 and the cylindrical flange 17, a sealing plug 28 with a handle at the tail and a boss and groove at the head is provided. Its boss and groove cooperate with the groove and boss at the steam outlet end of the horizontal tubular autoclave body 14 to achieve a seal. At the same time, a high-temperature anti-seize agent is coated between the two to prevent seizing. The handle of the sealing plug 28 has a cylindrical pipeline inside, which is fixedly connected to the cylindrical flange 17 by a central bolt. An explosion-proof module, a condenser 26, and a circulating water tank 27 are respectively installed on the pipeline at the steam outlet end of the horizontal tubular autoclave body 14.

[0046] The temperature and pressure monitoring and regulation module includes a first PID temperature controller 11, a second PID temperature controller 33, a voltage regulator pressure control device, and a back pressure valve 25.

[0047] Specifically, based on the temperature information monitored and fed back in real time by the preheating temperature measuring thermocouple 12, the temperature of the preheating furnace 10 is set and automatically adjusted by the first PID temperature controller 11; at the same time, the second PID temperature controller 33 can realize the segmented setting of the heating / cooling rate, test temperature and holding time of the split cylindrical heating furnace 16, and automatically adjust the split cylindrical heating furnace 16 based on the temperature information monitored and fed back in real time by the reactor cavity temperature measuring thermocouple 32, so that the temperature fluctuation in the reactor cavity of the horizontal tubular high pressure vessel 14 does not exceed the set temperature ±0.5℃;

[0048] The pressure regulator control device includes a first pressure sensor 20, a first pressure gauge 21, and a pressure regulator 9 using PID control. The pressure regulator 9 is located at the steam inlet of the entire system, that is, it is connected in series with the high-pressure metering pump 8 at the steam inlet of the preheating furnace 10, and monitors the pressure of the pumped liquid in real time and adjusts it according to the pressure feedback. The first pressure sensor 20 and the first pressure gauge 21 are installed on the pipeline between the high-pressure metering pump 8 and the pressure regulator 9.

[0049] The back pressure valve 25 is located at the steam outlet end of the horizontal tubular high pressure vessel 14, which is the steam outlet end of the entire system, and is used to regulate and stabilize the pressure in the circuit. The pressure regulator and the back pressure valve 25 work together to ensure that the pressure fluctuation in the vessel cavity of the horizontal tubular high pressure vessel 14 does not exceed ±0.5MPa.

[0050] The explosion-proof module includes a second pressure sensor 35, a second pressure gauge 36, a check valve 24, a first rupture valve 22, a second rupture valve 34, and a safety valve 23. The second pressure sensor 35 and the second pressure gauge 36 are placed on the pipeline at the steam outlet of the horizontal tubular autoclave body 14 and feed back the pressure information to the pressure gauge 21 in real time. The first rupture valve 22 and the check valve 24 are connected in series and placed on the pipeline after the check valve 24. The second rupture valve 34 and the safety valve 23 are connected in parallel on the pipeline after the first rupture valve 22.

[0051] The condenser 26 and the circulating water tank 27 are placed sequentially on the pipeline at the steam outlet of the horizontal tubular autoclave body 14. The condenser 26 converts the high-temperature and high-pressure water after the reaction into normal-temperature and normal-pressure water and discharges it into the circulating water tank 27.

[0052] In practical applications, the metal sample 15 is placed in the cavity of the horizontal tubular autoclave body 14. Tap water is treated by the ultrapure water preparation system 1 and then injected into the water storage tank 3. The automatic dosing system 2 adds oxygen scavengers such as hydrazine into the water storage tank 3 through the dosing hole. Subsequently, the water in the water storage tank 3 is monitored in real time by the dissolved oxygen meter 4, the pH meter 5 and the ion concentration meter 6 through the monitoring holes. After the water quality meets the test requirements, it is injected into the high-pressure metering pump 8 through the electromagnetic relief valve 7.

[0053] The high-pressure metering pump 8 then pumps the deoxygenated water into the serpentine coil of the preheating furnace 10. The pressure of the pumped liquid is monitored in real time by the pressure regulator 9 and adjusted according to the pressure feedback. The deoxygenated water is preheated to the set temperature by the first PID temperature controller 11 and the preheating temperature measuring thermocouple 12 and then sent into the steam inlet hole 13 on the outer layer of the steam inlet end of the horizontal tubular high pressure vessel body 14.

[0054] Water from the steam inlet 13 enters the cavity of the horizontal tubular autoclave 14 through the uniformly distributed small holes 31 on the inner layer 29, reacting with the metal sample 15. The temperature information monitored and fed back in real time by the thermocouple 32 in the cavity automatically adjusts the split cylindrical heating furnace 16. According to the second PID temperature controller 33, the heating / cooling rate, test temperature, and holding time of the split cylindrical heating furnace 16 can be set in segments, ensuring that the temperature fluctuation within the cavity of the horizontal tubular autoclave 14 does not exceed the set temperature ±0.5℃. Simultaneously, the pressure control system and back pressure valve 25 work together to ensure that the pressure fluctuation within the cavity of the horizontal tubular autoclave 14 does not exceed ±0.5MPa. The high-temperature, high-pressure water generated by the test reaction is discharged from the steam outlet of the horizontal tubular autoclave 14.

[0055] The discharged high-temperature and high-pressure water is condensed by condenser 26 and transformed into room temperature and normal pressure water, which is then collected in circulating water tank 27 to finally complete the test of the oxidation performance of metal sample 15.

[0056] During the above test, the pressure information of the pipeline at the steam outlet of the horizontal tubular autoclave 14 can be fed back to the second pressure gauge 36 in real time through the second pressure sensor 35. When the steam pressure in the pipeline exceeds the specified value by a small amount, the first rupture valve 22 automatically opens to discharge steam to the outside of the system to ensure the safe operation of the equipment. When the steam pressure in the pipeline exceeds the specified value by a large amount, the safety valve 23 automatically opens in an emergency.

[0057] The system of this invention can test the oxidation performance of metallic materials in dynamic supercritical water at a temperature of 650℃~750℃ and a pressure of 35MPa~45MPa. It has a small footprint and low environmental requirements, making it particularly suitable for supercritical water engineering experiments and scientific research in the laboratory.

[0058] Based on any of the above systems, the present invention also provides a test method for an ultra-high temperature and high pressure vessel system for supercritical water oxidation experiments, including,

[0059] Metal material is placed inside the body 14 of the horizontal tubular autoclave, and the steam outlet of the body 14 of the horizontal tubular autoclave is sealed by the sealing plug 28 and the cylindrical flange 17.

[0060] Tap water is treated and preheated sequentially through a water treatment module, a water chemical quality monitoring module, a liquid injection module, and a preheating module. It is then fed into the cavity of the horizontal tubular high-pressure reactor 14 through the steam inlet. The temperature and pressure at the steam inlet are controlled by the temperature and pressure monitoring and adjustment module, which regulates the temperature and pressure inside the cavity of the horizontal tubular high-pressure reactor 14. The oxidation performance of the metal material is tested by heating with a split cylindrical heating furnace 16.

Claims

1. An ultra-high temperature autoclave system for supercritical water oxidation testing, characterized by, The water treatment module, the water chemical quality monitoring module, the liquid injection module, the preheating module, the autoclave module, the explosion-proof module and the temperature and pressure monitoring and adjusting module are connected in sequence through pipelines at the steam inlet end of the horizontal tubular autoclave body (14), and the steam outlet end of the horizontal tubular autoclave body (14) is connected to the explosion-proof module through the steam outlet hole (18) to form a medium flow loop. The autoclave module comprises a horizontal tubular autoclave body (14) and a split cylindrical heating furnace (16); the split cylindrical heating furnace (16) is sleeved outside the horizontal tubular autoclave body (14). The steam inlet end of the horizontal tubular autoclave body (14) is an integrated autoclave bottom comprising an inner layer (29) provided with small holes (31) and an outer layer provided with a steam inlet hole (13); a steam cavity is formed between the outer layer and the inner layer (29); the small holes (31) of the inner layer (29) are uniformly distributed, and the inner walls of the small holes (31) are coated with a ceramic coating. The steam outlet end of the horizontal tubular autoclave body (14) is sealed by a sealing pipe plug (28) and a cylindrical flange (17); the sealing pipe plug (28) is provided with a steam outlet hole (18) coaxial with the steam outlet hole (18) and communicating with the autoclave cavity of the horizontal tubular autoclave body (14); the cylindrical flange (17) is provided with a central threaded hole coaxial with the steam outlet hole (18); the end of the sealing pipe plug (28) is provided with a boss and a groove matching the groove and the boss of the steam outlet end of the horizontal tubular autoclave body (14), and a high-temperature anti-seizure agent is coated between the two. The water treatment module, the water chemical quality monitoring module, the liquid injection module and the preheating module are connected in sequence through pipelines at the steam inlet end of the horizontal tubular autoclave body (14), and the steam outlet end of the horizontal tubular autoclave body (14) is connected to the explosion-proof module through the steam outlet hole (18) to form a medium flow loop. The temperature and pressure monitoring and adjusting module is used to control the temperature and pressure at the steam inlet end and adjust the temperature and pressure in the autoclave cavity of the horizontal tubular autoclave body (14). The temperature and pressure monitoring and adjusting module comprises a first PID temperature controller (11), a second PID temperature controller (33), a pressure stabilizer pressure control device and a back pressure valve (25); the first PID temperature controller (11) is connected to the preheating module; the second PID temperature controller (33) is connected to the split cylindrical heating furnace (16), and the pressure stabilizer pressure control system and the back pressure valve (25) work together to make the pressure fluctuation in the autoclave cavity of the horizontal tubular autoclave body not higher than ±0.5MPa. The explosion-proof module comprises a check valve (24) and a first burst valve (22) arranged in sequence on the pipeline at the steam outlet end of the horizontal tubular autoclave body (14), a second burst valve (34) and a safety valve (23) are arranged in parallel on the output pipeline of the first burst valve (22); a second pressure sensor (35) and a second pressure gauge (36) are arranged on the pipeline at the steam outlet end of the horizontal tubular autoclave body (14) and the check valve (24); and the back pressure valve (25) is arranged on another pipeline at the outlet end of the check valve (24).

2. The super-high-temperature and high-pressure autoclave system for supercritical water oxidation experiments according to claim 1, wherein The temperature measuring thermocouple placement hole (30) is arranged in the steam inlet end of the horizontal tube type autoclave body (14), and the autoclave cavity temperature measuring thermocouple (32) extending into the autoclave cavity of the horizontal tube type autoclave body (14) is fixedly arranged in the temperature measuring thermocouple placement hole (30); the output end of the autoclave cavity temperature measuring thermocouple (32) is connected to the control end of the split cylindrical heating furnace (16); the steam outlet end of the horizontal tube type autoclave body (14) is provided with a plurality of threads, and the inside is provided with a boss and a groove; the inner diameter of the cylindrical flange (17) is equal to the outer diameter of the horizontal tube type autoclave body (14), and a plurality of bolts (19) are uniformly arranged on the bottom surface along the bottom surface circumference; the tail of the sealing pipe plug (28) is provided with a handle, and the end is provided with a boss and a groove which are consistent with the groove and the boss of the steam outlet end of the horizontal tube type autoclave body (14); the center of the handle is a cylindrical pipeline, which passes through the center threaded hole of the cylindrical flange (17) and is fixed and sealed with the cylindrical flange (17) through threads.

3. The ultra-high temperature autoclave system for supercritical water oxidation test according to claim 1, characterized by, The pressure control device of the pressure stabilizer comprises a pressure stabilizer (9), a first pressure sensor (20) and a first pressure gauge (21); the pressure stabilizer (9) is arranged on the pipeline between the liquid injection module and the preheating module, and the first pressure sensor (20) and the first pressure gauge (21) are arranged at the inlet of the pressure stabilizer (9).

4. The ultra-high temperature autoclave system for supercritical water oxidation test according to claim 3, characterized by, The preheating module comprises a preheating furnace (10) provided with a serpentine coil inside and a preheating temperature measuring thermocouple (12) connected to the preheating furnace (10); the inlet end of the serpentine coil of the preheating furnace (10) is connected to the outlet of the pressure stabilizer (9), and the outlet end is connected to the steam inlet end of the horizontal tube type autoclave body (14); the output end of the preheating temperature measuring thermocouple (12) is connected to the control end of the preheating furnace (10).

5. The ultra-high temperature autoclave system for supercritical water oxidation test according to claim 1, characterized by, A condenser (26) and a circulating water tank (27) are further arranged in sequence at the outlet of the back pressure valve (25).

6. The ultra-high temperature autoclave system for supercritical water oxidation testing of claim 1, wherein, The water treatment module comprises an ultrapure water preparation device (1), an automatic dosing device (2) and a water storage tank (3); the automatic dosing device (2) is arranged on the water storage tank (3), the ultrapure water preparation device (1) is connected to the water inlet pipeline, and a four-way valve and an electromagnetic relief valve (7) are arranged in sequence on the water outlet pipeline.

7. The ultra-high-temperature high-pressure autoclave system for supercritical water oxidation test according to claim 1, characterized by, The water chemical quality monitoring module comprises an online dissolved oxygen tester (4), an ion concentration tester (6) and a PH online tester (5) connected in parallel and then connected to the pipeline between the water treatment module and the liquid injection module.

8. The ultra-high temperature autoclave system for supercritical water oxidation testing of claim 1, wherein, The liquid injection module comprises a high-pressure metering pump (8); the inlet of the high-pressure metering pump (8) is connected to the water outlet pipeline of the water chemical quality monitoring module.

9. A test method for a super-high-temperature high-pressure autoclave system for supercritical water oxidation tests, characterized by, The system according to any one of claims 1-8, comprising, The metal material is placed in the horizontal tube type autoclave body (14), and the outlet end of the horizontal tube type autoclave body (14) is sealed by the sealing pipe plug (28) and the cylindrical flange (17). The tap water is treated and preheated by the water treatment module, the water chemical quality monitoring module, the liquid injection module and the preheating module in turn, and then is sent into the horizontal tube autoclave body (14) through the steam inlet end of the horizontal tube autoclave body (14), the temperature and pressure of the steam inlet end are controlled by the temperature and pressure monitoring and adjusting module, the temperature and pressure in the autoclave cavity of the horizontal tube autoclave body (14) are adjusted, and the oxidation performance test of the metal material in the dynamic supercritical water with the temperature of 650-750 DEG C and the pressure of 35-45 MPa is completed by using the split cylindrical heating furnace (16).

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