In-situ hydrogen permeation and corrosion coupling autoclave

Abstract

The application discloses an in-situ hydrogen permeation and corrosion coupling autoclave, which comprises a hydrogen permeation autoclave for containing high-pressure hydrogen, a side wall of the hydrogen permeation autoclave being provided with a first single window; a corrosion autoclave provided with a three-electrode system, the three-electrode system extending into the corrosion autoclave, a side wall of the corrosion autoclave being provided with a second single window, the first single window and the second single window being sealingly connected, the first single window and the second single window both being hollow structures, the hydrogen permeation autoclave and the corrosion autoclave being communicated with each other through the first single window and the second single window; a sample clamp arranged between the first single window and the second single window and realized sealing through bolts, the sample clamp being used for clamping and fixing a sample to be tested, so that two sides of the sample to be tested are exposed to environments of the hydrogen permeation autoclave and the corrosion autoclave respectively; the sample to be tested and a working electrode connecting joint in the three-electrode system are connected through wires to form the working electrode.

Description

Technical Field

[0001] This invention relates to the technical field of hydrogen permeation testing equipment and corrosion testing equipment, and particularly to an in-situ hydrogen permeation and corrosion coupled high-pressure reactor. Background Technology

[0002] The statements herein provide only background information in relation to this invention and do not necessarily constitute prior art.

[0003] Hydrogen energy is a crucial link in promoting the clean and efficient utilization of traditional fossil fuels and supporting the large-scale development of renewable energy. With increasing energy demand and stricter environmental requirements, the proportion of renewable energy installed capacity will continue to rise in the future. However, due to the limited peak-shaving capacity of the current power system, the phenomenon of "wind and solar curtailment" is severe, hindering the development of renewable energy to some extent. Hydrogen production through water electrolysis enables large-scale energy storage and peak-shaving coupling with the power grid, increasing the flexibility of the power system, helping to improve the utilization rate of renewable energy, forming a flexible and efficient multi-energy complementary system, and promoting the development of clean energy. Pipeline hydrogen transportation is an important way to achieve large-scale hydrogen transport. Currently, pure hydrogen pipelines and hydrogen-blended natural gas pipelines have received widespread attention and are being vigorously developed both domestically and internationally.

[0004] However, the pipeline transportation of hydrogen still faces many challenges. On one hand, hydrogen molecules adsorb onto the surface of the pipeline steel, dissociate to form hydrogen atoms, and penetrate into the pipeline metal, reducing the plasticity and toughness of the matrix and leading to deterioration of the pipeline's mechanical properties. Simultaneously, the hydrogen atoms inside the pipeline exacerbate corrosion. On the other hand, for hydrogen-blended natural gas pipelines, the transported components contain carbon dioxide and water, causing internal corrosion. Furthermore, in real-world conditions such as buried and subsea pipelines, corrosive substances also damage the outer wall of the pipeline. Both internal and external corrosion further affect the hydrogen atom penetration process. Therefore, studying the effects of hydrogen penetration and corrosion on pipe materials, along with the influence of corrosive factors, is particularly important for hydrogen-blended natural gas pipelines and pure hydrogen pipelines. Existing hydrogen permeation autoclaves can only test the degree of hydrogen permeation under ideal, corrosion-free conditions. They cannot achieve in-situ measurement of the corrosion degree under real-world pipeline transportation conditions (such as buried and subsea pipelines) where hydrogen permeation and corrosion occur simultaneously and synergistically. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide an in-situ hydrogen permeation and corrosion coupled high-pressure reactor.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] An in-situ hydrogen permeation and corrosion coupled autoclave, comprising:

[0008] A hydrogen permeation reactor, used to hold high-pressure hydrogen, has a first single viewing window extending through its side wall;

[0009] The corrosion vessel is equipped with a three-electrode system that extends into the corrosion vessel. A second single window is provided through its side wall. The first and second single windows are sealed together. Both the first and second single windows are hollow structures. The hydrogen permeation vessel and the corrosion vessel are interconnected through the first and second single windows.

[0010] The sample clamp is located between the first single window and the second single window and is sealed by bolts. The sample clamp is used to clamp and fix the sample to be tested, so that its two sides are exposed to the environments of the hydrogen permeation reactor and the corrosion reactor, respectively.

[0011] The test sample is connected to the working electrode in the three-electrode system via a wire to form the working electrode.

[0012] The three-electrode system consists of a working electrode. 、 Reference electrode 、 The electrode composition is as follows: the sample serves as the working electrode and is connected to the working electrode connector via a wire; the reference electrode is a high-temperature and high-pressure reference electrode.

[0013] In some embodiments, both the first single window and the second single window are three-tiered structures. The first and third tiers are hollow cylinders, and the second tier is a trumpet-shaped structure with its large-diameter end connected to the end of the third tier and its small-diameter end connected to the end of the first tier.

[0014] Preferably, the sample fixture includes a large pressure cap, and a clamping part is provided inside the large pressure cap. The first single window and the second single window are pressed together by bolts to fix the large pressure cap.

[0015] More preferably, the large pressure cap has a cylindrical structure, and the interior of the large pressure cap has a hollow two-tier structure, with the inner diameters of the first and second tiers increasing sequentially.

[0016] In a further preferred embodiment, the large pressure cap is tightly fitted with the three-tiered structure of the first single window and the second single window, and a sealing element is provided between the large pressure cap and the first single window.

[0017] More preferably, the inner wall of the second stage of the large pressure cap is provided with a first clamping part and a second clamping part for clamping the sample. The clamping force between the first clamping part and the second clamping part is maintained by the bolt.

[0018] In some embodiments, the corrosion vessel includes a corrosion vessel body and a corrosion vessel cover, which are connected by bolts, and a sealing element is provided between the corrosion vessel body and the corrosion vessel cover.

[0019] Preferably, the corrosion vessel lid is provided with a gas channel, and the outer end of the gas channel is used to connect to a valve.

[0020] In some embodiments, the hydrogen permeation reactor includes a reactor body and a reactor cover, which are connected by bolts, and a sealing element is provided between the reactor body and the reactor cover.

[0021] The hydrogen permeation reactor lid is equipped with a gas channel, and the outer end of the gas channel is used to connect to a valve.

[0022] The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:

[0023] (1) This invention couples two reactors, allowing both sides of the sample to undergo hydrogen permeation and corrosion tests simultaneously under high pressure. The three-electrode system can quantitatively measure the degree of corrosion under the coupled effects of hydrogen permeation and corrosion using electrochemical methods in situ. This solves the problem that existing hydrogen permeation autoclaves can only test the degree of hydrogen permeation under ideal, corrosion-free conditions, and cannot achieve in-situ measurement of corrosion under real pipeline transportation conditions (such as buried pipelines, subsea pipelines, etc.) where hydrogen permeation and corrosion occur simultaneously and promote each other. Compared with existing autoclaves that can only simulate corrosion-free conditions, the simulation test results of this invention are more accurate and closer to the actual situation.

[0024] (2) The present invention provides a sealing structure between the single window of the permeation vessel and the pressure cap, between the single window of the corrosion vessel and the pressure cap, and between the clamping part and the sample; and uses a bolt structure to connect the single window of the permeation vessel and the single window of the corrosion vessel to prevent hydrogen from leaking out of the high pressure vessel, and ensure that the pressure inside the two vessels is maintained at a certain value during the coupling stage, thus ensuring the safety of the test environment.

[0025] (3) When the corrosion vessel and the hydrogen permeation vessel of this invention are coupled, they are connected as a whole by bolts. After the bolts are removed, the corrosion vessel can be equipped with a conical plug to conduct high-temperature and high-pressure corrosion tests independently; the hydrogen permeation vessel can be equipped with an electrolytic cell to conduct hydrogen permeation tests independently. Thus, one vessel can be used for multiple purposes, making the device functionally diversified and maximizing its value. Attached Figure Description

[0026] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0027] Figure 1 An isometric view of an in-situ hydrogen permeation and corrosion coupled autoclave in an embodiment of the present invention is shown;

[0028] Figure 2A front view of the in-situ hydrogen permeation and corrosion coupled high-pressure vessel in an embodiment of the present invention is shown;

[0029] Figure 3 A top view of an in-situ hydrogen permeation and corrosion coupled autoclave is shown in an embodiment of the present invention;

[0030] Figure 4 A cross-sectional view of an in-situ hydrogen permeation and corrosion coupled high-pressure vessel is shown in an embodiment of the present invention.

[0031] In the diagram, 1. Hydrogen permeation reactor cover; 2. Hydrogen permeation reactor body; 3. Corrosion reactor cover; 4. Corrosion reactor body; 5. Working electrode connection connector; 6. Reference electrode; 7. Counter electrode; 8. Large pressure cap; 9. First clamping part; 10. Second clamping part; 11. First single viewing window; 12. Sample (working electrode); 13. Large bolt; 14. Small bolt; 15. Second single viewing window; 16. Inlet channel; 17. Exhaust channel; 18. Explosion valve connection channel; 19. Instrument interface. Detailed Implementation

[0032] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0033] The present invention will be further described below with reference to the embodiments.

[0034] like Figures 1-4 As shown, this embodiment provides an in-situ hydrogen permeation and corrosion coupled autoclave, including a hydrogen permeation vessel, a corrosion vessel, and a sample holder. Both the hydrogen permeation vessel body 2 and the corrosion vessel body 4 are autoclaves. The hydrogen permeation vessel can be filled with high-pressure hydrogen gas, and the corrosion vessel can be filled with a corrosive solution and high-pressure gas. The sample holder is used to hold the sample (working electrode) 12. One side of the sample (working electrode) 12 is in contact with the hydrogen gas inside the hydrogen permeation vessel body 2, and the other side of the sample (working electrode) 12 is connected to the working electrode connector 5 via a wire and is in contact with the corrosive solution. A three-electrode system is formed inside the corrosion vessel to monitor the corrosion electrochemical signal of the sample (working electrode) 12 under the influence of hydrogen permeation and corrosion coupling in real time, thereby calculating the degree of corrosion.

[0035] like Figures 1-4 As shown, the hydrogen permeation reactor body 2 has a first single viewing window 11, and the corrosion reactor body 4 has a second single viewing window 15. Both the hydrogen permeation reactor cover 1 and the corrosion reactor cover 3 are equipped with an air inlet channel 16, an exhaust channel 17, a rupture valve connection channel 18, and an instrument interface 19. The corrosion reactor cover 3 is also equipped with a three-electrode system, which consists of a sample (working electrode) 12. 、 Reference electrode 6 、The electrode 7 is composed of a sample (working electrode) 12 with a lead wire connected to the working electrode connector 5, and the reference electrode 6 is a high-temperature and high-pressure reference electrode.

[0036] The hydrogen permeation vessel cover 1 and the hydrogen permeation vessel body 2, and the corrosion vessel cover 3 and the corrosion vessel body 4 are all connected by large bolts 13. The first single viewing window and the second single viewing window are connected by small bolts 14, thereby pressing the two large pressure caps 8 together, and then clamping the clamping part to fix the sample (working electrode) 12.

[0037] This embodiment couples a hydrogen permeation reactor with a corrosion reactor to simulate the simultaneous hydrogen permeation and corrosion of a pipeline, and enables in-situ measurement of the degree of corrosion. Compared with existing high-pressure reactors that can only simulate hydrogen permeation under ideal, corrosion-free conditions, the simulation is more accurate and closer to reality.

[0038] like Figure 2 and Figure 3 As shown, the single viewing window 11 is located on the side wall of the vessel body and is welded to the vessel body to form a whole. It is a hollow shell structure. The single viewing window has a three-stage structure. The first stage and the third stage are cylindrical. The first stage is connected to the side wall of the vessel body and its diameter is smaller than that of the other stages. The third stage has a larger diameter. The second stage is trumpet-shaped and connects the first stage and the third stage.

[0039] like Figure 4 As shown, the sample fixture consists of a large pressure cap 8, a first clamping part 9, and a second clamping part 10. After assembly, the sample fixture is installed between the single viewing window 11 of the hydrogen permeation reactor body 2 and the single viewing window 15 of the corrosion reactor body 4. The single viewing window 11 of the hydrogen permeation reactor body 2 and the single viewing window 15 of the corrosion reactor body 4 are then connected by small bolts 14 to achieve coupling between the hydrogen permeation reactor and the corrosion reactor.

[0040] The large pressure cap 8 has a cylindrical structure, and the interior of the large pressure cap has a hollow two-stage structure, with the inner diameter of the first stage and the second stage increasing sequentially.

[0041] The inner second stage of the large pressure cap 8 is provided with a first clamping part 9 and a second clamping part 10 for clamping the sample (working electrode) 12. The first clamping part 9 is a second-order hollow cylinder. A cylinder with a larger diameter and a predetermined depth is cut into the bottom, and a rectangular groove is carved to accommodate an O-ring seal. A cylinder with a smaller diameter and a predetermined depth is cut into the top, together forming a through hole. The second clamping part 10 is a third-order hollow cylinder. The outer diameter of the second, third, and first orders increases sequentially. A through hole is drilled inside, and a rectangular groove is carved into the top to accommodate an O-ring seal.

[0042] The sample (working electrode) 12 is a circular thin sheet, which is fixed by the first clamping part 9 and the second clamping part 10, and the high-pressure hydrogen gas is sealed by the O-ring. The sample is fixed by the small bolt 14, and the clamping force between the first clamping part 9 and the second clamping part 10 is maintained by the small bolt 14.

[0043] To prevent high-pressure gas from escaping from the single viewing window 11, the connection between the three-electrode structure and the valve cover inside the autoclave, the sample holder is sealed to the single viewing window 11, and the sample area and the connection between the three electrodes and the valve cover are also sealed. Four O-rings are used. The four O-rings are located between the first clamping part 9 and the sample (working electrode) 12, between the second clamping part 10 and the sample (working electrode) 12, between the large pressure cap 8 and the third step of the first single viewing window 11 of the high-pressure hydrogen permeation autoclave body 2, and between the large pressure cap 8 and the third step of the second single viewing window 15 of the high-pressure corrosion autoclave body 4.

[0044] The sample clamp is a hollow structure used to hold the sample (working electrode) 12, so that one side of the sample (working electrode) 12 is in contact with the hydrogen gas in the hydrogen permeation vessel, and the other side of the sample (working electrode) 12 is connected to the working electrode connector 5 through a wire and is in contact with the medium in the corrosion vessel.

[0045] The entire vessel body is made of Hastelloy, a nickel-based corrosion-resistant alloy with excellent corrosion resistance, hydrogen embrittlement resistance, and thermal stability, ensuring the stability of the vessel body and the safety of the test.

[0046] During the assembly of the coupling high-pressure vessel, the hydrogen permeation vessel cover 1 and the single-viewing-window vessel body 2 of the hydrogen permeation vessel are connected by large bolts 13; the O-ring seal is placed in the two rectangular grooves of the first clamping part 9 and the second clamping part 10, and the sample (working electrode) 12 is fixed by the first clamping part 9 and the second clamping part 10; the first clamping part 9 and the second clamping part 10 are placed between the second-stage hollow cylinders of the two large pressure caps, and the sample (working electrode) 12 is clamped tightly.

[0047] Connect the working electrode to connector 5 、 Reference electrode 6 、 The counter electrode 7 is integrated with the corrosion vessel cover 3 via threads. The corrosion vessel cover 3 is connected to the corrosion vessel single-view window body 4 via large bolts 13. The lead wire of the working electrode connector 5 in the three-electrode system is connected to the rear end of the sample (working electrode) 12. The single-view window 11 of the hydrogen permeation vessel body 2 and the single-view window 15 of the corrosion vessel body 4 are connected via small bolts 14, thereby fixing the sample (working electrode) 12 and achieving coupling between the hydrogen permeation vessel and the corrosion vessel. The installation is then complete.

[0048] During use, both the hydrogen permeation reactor and the corrosion reactor are first purged of residual gas inside with nitrogen, repeating this process three times. After the current stabilizes, the required test substances are filled in, and relevant tests are conducted.

[0049] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An in-situ hydrogen permeation and corrosion coupled high-pressure vessel, characterized in that: include: A hydrogen permeation reactor, used to hold high-pressure hydrogen, has a first single viewing window extending through its side wall; The corrosion vessel is equipped with a three-electrode system that extends into the vessel. A second single-viewing window is provided through its side wall. The first and second single-viewing windows are sealed together. Both the first and second single-viewing windows are hollow structures. The hydrogen permeation vessel and the corrosion vessel are interconnected through the first and second single-viewing windows. Both the first and second single-viewing windows have a three-tiered structure. The first and third tiers are hollow cylinders, and the second tier is a trumpet-shaped structure. Its large-diameter end is connected to the end of the third tier, and its small-diameter end is connected to the end of the first tier. A sample clamp is positioned between the first single-view window and the second single-view window and is sealed by bolts. The sample clamp is used to clamp and fix the sample to be tested, exposing its two sides to the environments of the hydrogen permeation reactor and the corrosion reactor, respectively. The sample clamp includes a large pressure cap, and a clamping part is provided inside the large pressure cap. The first single-view window and the second single-view window are pressed together by bolts to fix the large pressure cap. The large pressure cap has a cylindrical structure and a hollow two-tier structure inside, with the inner diameters of the first and second tiers increasing sequentially. The large pressure cap fits tightly with the three-tier structure of the first and second single windows, and a sealing element is provided between the large pressure cap and the first single window. The inner wall of the second tier inside the large pressure cap is provided with a first clamping part and a second clamping part for clamping the sample. The test sample is connected to the working electrode in the three-electrode system via a wire to form the working electrode.

2. The in-situ hydrogen permeation and corrosion coupled autoclave according to claim 1, characterized in that: The corrosion vessel includes a corrosion vessel body and a corrosion vessel cover, which are connected by bolts, and a sealing element is provided between the corrosion vessel body and the corrosion vessel cover.

3. The in-situ hydrogen permeation and corrosion coupled autoclave according to claim 2, characterized in that: The corrosion vessel lid is provided with a gas channel, and the outer end of the gas channel is used to connect to a valve.

4. The in-situ hydrogen permeation and corrosion coupled autoclave according to claim 1, characterized in that: The hydrogen permeation reactor includes a reactor body and a reactor cover, which are connected by bolts, and a sealing element is provided between the reactor body and the reactor cover.

5. The in-situ hydrogen permeation and corrosion coupled autoclave according to claim 4, characterized in that: The hydrogen permeation reactor lid is equipped with a gas channel, and the outer end of the gas channel is used to connect to a valve.

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