CN116858917B - For supercritical CO 2 Hydrogen permeation testing device for pipeline steel in conveying environment - Google Patents
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- CN116858917B CN116858917B CN202310746794.5A CN202310746794A CN116858917B CN 116858917 B CN116858917 B CN 116858917B CN 202310746794 A CN202310746794 A CN 202310746794A CN 116858917 B CN116858917 B CN 116858917B
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 207
- 239000001257 hydrogen Substances 0.000 title claims abstract description 207
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 238000012360 testing method Methods 0.000 title claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 24
- 239000010959 steel Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000010438 heat treatment Methods 0.000 claims abstract description 84
- 238000005259 measurement Methods 0.000 claims abstract description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000007613 environmental effect Effects 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 230000006835 compression Effects 0.000 claims description 20
- 238000007906 compression Methods 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000005056 compaction Methods 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WABPQHHGFIMREM-NJFSPNSNSA-N lead-209 Chemical compound [209Pb] WABPQHHGFIMREM-NJFSPNSNSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4162—Systems investigating the composition of gases, by the influence exerted on ionic conductivity in a liquid
Abstract
The invention provides a method for supercritical CO 2 Hydrogen permeation testing device for pipeline steel in conveying environment, high-temperature high-pressure environment hydrogen charging kettle for containing supercritical CO 2 Fluid, simulated impurity-containing supercritical CO 2 Delivering environmental conditions; the normal pressure hydrogen measurement electrolytic cell is used for containing sodium hydroxide solution, so that hydrogen atoms permeated into the hydrogen measurement electrolytic cell from the hydrogen charging kettle are oxidized to form hydrogen permeation current; the circulating water heating device is used for providing a constant-temperature heat source for the normal-pressure hydrogen measurement electrolytic cell and heating sodium hydroxide solution in the hydrogen measurement electrolytic cell so as to ensure that the temperature of the normal-pressure hydrogen measurement electrolytic cell is the same as the temperature of the hydrogen charging kettle in a high-temperature high-pressure environment. The invention can be applied to the supercritical CO 2 The in-situ hydrogen permeation measurement of metal in any high-pressure moisture environment with temperature in the conveying environment is realized, hydrogen charging in the high-pressure moisture environment and hydrogen measurement in the normal-pressure environment are realized, the test difficulty and the test cost are reduced, the temperature consistency of the two sides of the hydrogen charging and the hydrogen measurement can be ensured, and the accuracy of the test result is ensured.
Description
Technical Field
The invention provides a method for supercritical CO 2 A hydrogen permeation testing device for pipeline steel in a conveying environment belongs to the technical field of carbon capture.
Background
In carbon capture, utilization and sequestration (CCUS) engineering applications, the captured CO 2 Compression to supercritical state (pressure>7.38MPa, temperature>31.1 ℃ C. And collectedThe carbon steel pipeline transportation is used for realizing large-scale CO 2 The most economical way of efficient transport. Supercritical CO 2 The fluid inevitably contains a certain amount of H 2 O and O 2 、H 2 S、SO x 、NO x The components of the impurities (ppm level), especially the impurities, can undergo complex chemical reactions to promote strong acidic substances (such as H 2 SO 4 、HNO 3 Etc.), which exposes the pipeline steel to a strongly acidic corrosive environment. In the pipeline steel corrosion process, hydrogen atoms generated by cathodic hydrogen evolution reaction are adsorbed on the surface of steel and permeate into the steel, so that the pipeline steel is damaged by hydrogen, and then the pipeline steel is broken and fails. Investigation of supercritical CO 2 The hydrogen permeation behavior of pipeline steel in a conveying environment is an important link for researching the environment fracture sensitivity and mechanism of the pipeline steel.
At present, the hydrogen permeation testing device is mainly designed based on the Devanathan-Stachurski double-electrolytic cell principle, is composed of a hydrogen charging electrolytic cell, a hydrogen measuring electrolytic cell and a testing sample between the hydrogen charging electrolytic cell and the hydrogen measuring electrolytic cell, and is mainly applied to an atmospheric pressure aqueous solution medium environment. Is applicable to supercritical CO 2 Hydrogen permeation testing devices that deliver special environments are very limited. Supercritical CO 2 The conveying pipeline operates under high pressure and low temperature, and the conveyed fluid is treated by supercritical CO 2 Is the main body, a small amount of H 2 O、O 2 、SO x 、NO x 、H 2 S and other impurity components as solute and dissolved or distributed in CO 2 Is a kind of medium. This environment is essentially a high pressure, humid environment, which is significantly different from an environment that is primarily aqueous. Therefore, the conventional hydrogen permeation testing device widely applied to the aqueous medium environment cannot be directly applied to the high-pressure moisture environment. Notably, for small amounts of H 2 Supercritical CO of O 2 In terms of conveying environment, H 2 O is dissolved in supercritical CO 2 Of which only H 2 O precipitates and condenses on the surface of pipeline steel to cause corrosion and subsequent hydrogen permeation problems. Therefore, if there is a temperature difference between the hydrogen charging side and the hydrogen measuring side devices, H 2 O can condense on the sample surface on the hydrogen-filled side due to temperature differences, which can exacerbate sample corrosion and cause hydrogen permeation testing errors. Thus, for superCritical CO 2 The development and design of hydrogen permeation testing devices in a delivery environment requires full consideration of the above-described problems. In view of this, it is necessary to design a set of supercritical CO-compatible devices 2 Hydrogen permeation testing device of conveying environment for supercritical CO 2 Technical support is provided for the basic scientific research of conveying pipeline corrosion.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for supercritical CO 2 A hydrogen permeation testing device for pipeline steel in a conveying environment. The device can realize hydrogen charging in a high-pressure wet gas environment and hydrogen measurement in a normal-pressure environment, and reduces the testing difficulty and the testing cost; meanwhile, the hydrogen permeation test of the high-pressure moisture environment at different temperatures can be realized, the temperature equality of the two sides of hydrogen charging and hydrogen measurement can be ensured, and the problem of inaccurate test results caused by water condensation due to the temperature difference of the two sides is solved.
The invention adopts the following technical scheme:
for supercritical CO 2 The hydrogen permeation testing device of pipeline steel in a conveying environment comprises a high-temperature high-pressure environment hydrogen charging kettle, a normal-pressure hydrogen testing electrolytic cell and a circulating water heating device;
high-temperature high-pressure environment hydrogen charging kettle for holding supercritical CO 2 Fluid, simulated impurity-containing supercritical CO 2 Delivering environmental conditions.
The normal pressure hydrogen measuring electrolytic cell is used for containing sodium hydroxide solution with a certain concentration, so that hydrogen atoms permeated into the hydrogen measuring electrolytic cell from the hydrogen charging kettle are oxidized, and hydrogen permeation current is formed.
The circulating water heating device is used for providing a constant-temperature heat source for the normal-pressure hydrogen measurement electrolytic cell and heating sodium hydroxide solution in the hydrogen measurement electrolytic cell so as to ensure that the temperature of the normal-pressure hydrogen measurement electrolytic cell is the same as the temperature of the hydrogen charging kettle in a high-temperature high-pressure environment.
The water outlet of the heating box of the circulating water heating device is connected with the water inlet of the normal pressure hydrogen measuring electrolytic cell through a pipeline, and the water outlet of the normal pressure hydrogen measuring electrolytic cell is connected with the water inlet of the heating box of the circulating water heating device through a pipeline; the normal pressure hydrogen measurement electrolytic cell is communicated with the high temperature and high pressure environment hydrogen charging kettle through a fastening bolt, a compression block and a sample clamp are arranged at the joint of the normal pressure hydrogen measurement electrolytic cell and the high temperature and high pressure environment hydrogen charging kettle, and a test sample is placed in the sample clamp. One side of the compaction block is contacted with the normal pressure hydrogen measurement electrolytic cell, and the other side is contacted with the test sample and the sample clamp. One side of the sample clamp is contacted with the compaction block, and the other side is contacted with the hydrogen charging kettle body in the high-temperature high-pressure environment.
The circulating water heating device comprises a constant temperature heating box body, water, a circulating water pump, a heating box water outlet and a heating box water inlet. The constant temperature heating box body is used for heating water to a set temperature and maintaining a constant temperature state. The circulating water pump is arranged in the constant temperature heating box body and is connected with a water outlet of the heating box on the constant temperature heating box body through a pipeline, and is used for sucking and pumping water in the constant temperature heating box body. The water outlet of the heating box at the upper part of the constant temperature heating box body is connected with a pipeline through an adapter and is used for providing constant temperature water for the constant pressure hydrogen measurement electrolytic cell. The water inlet of the heating box at the upper part of the constant temperature heating box body is connected with a pipeline through an adapter and is used for recovering water discharged by the constant pressure hydrogen measurement electrolytic cell.
The normal pressure hydrogen measurement electrolytic cell is a hydrogen measurement side and is used for measuring hydrogen permeation current. Comprising the following steps: the device comprises an inner cavity, an inner cavity wall, an outer cavity wall, a connecting plate, an electrolytic cell water inlet and an electrolytic cell water outlet. The inner cavity is used for containing sodium hydroxide solution with a certain concentration, the outer cavity is used for flowing constant-temperature circulating water, the inner cavity wall is used for isolating the inner cavity and the outer cavity, and the outer cavity wall is used for preserving heat. The inner cavity wall and one side of the outer cavity wall are connected with the connecting plate, through holes are formed in the edges of the connecting plate and used for installing fastening bolts, the center of the connecting plate is provided with holes and connected with a cylindrical hollow tube, through holes are formed in the upper tube wall of the cylindrical hollow tube and used for inserting working electrode wires connected with samples, and the side face of the cylindrical hollow tube is contacted with the compressing block and used for compressing the compressing block. An electrolytic cell water inlet is arranged below the normal pressure hydrogen measurement electrolytic cell, is communicated with the outer cavity and is connected with a pipeline through an adapter, and the normal pressure hydrogen measurement electrolytic cell is used for receiving constant temperature water provided by the circulating water heating device. An electrolytic cell water outlet is arranged above the normal pressure hydrogen measurement electrolytic cell, is communicated with the outer cavity and is connected with a pipeline through an adapter for discharging circulating water to the circulating water heating device. The upper inner cavity wall and the outer cavity wall of the normal pressure hydrogen measurement electrolytic cell are provided with three conical holes for placing a rubber plug, and the center of the rubber plug is provided with a through hole for respectively installing a working electrode lead, a reference electrode and a counter electrode. The working electrode wire is used for connecting a test sample, the lower end of the reference electrode is connected with the Rujin capillary, and the tail end of the Rujin capillary is close to the surface of the test sample. And connecting the working electrode lead, the counter electrode and the reference electrode with an electrochemical workstation to realize hydrogen permeation current measurement.
The high-temperature high-pressure environment hydrogen charging kettle is a hydrogen charging side and is used for simulating a high-pressure moisture environment and providing environmental conditions for corrosion of a test sample and generation of hydrogen. Comprises a kettle cover, a kettle body, a controller, a heating resistance wire, a thermocouple, a pressure gauge, an air inlet, an air outlet, a water filling port and a heat preservation sleeve. The kettle cover is connected with the kettle body through a fastening bolt; a through hole is formed in the kettle wall at one side of the kettle body and is used for installing a test sample and is connected with a connecting plate of the normal-pressure hydrogen measurement electrolytic cell through a fastening bolt; a heating resistance wire is arranged in the kettle wall, a thermocouple is arranged on the kettle cover, and the heating resistance wire and the thermocouple are connected with a controller through wires and used for heating and adjusting the temperature in the kettle; the kettle cover is provided with a pressure gauge which is connected with the controller through a lead and used for monitoring the pressure in the kettle body; the kettle cover is provided with a water filling port for filling trace water required by a test environment into the kettle; the kettle cover is provided with an air inlet for introducing gas required by the test into the kettle body; the kettle cover is provided with an exhaust port for exhausting gas in the kettle body.
A sealing part is designed between the normal pressure hydrogen measurement electrolytic cell and the high temperature and high pressure environment hydrogen charging kettle, a first O-shaped sealing ring is arranged on the outer side of the compression block, and a through hole is formed in the upper wall and used for inserting a working electrode wire connected with a sample. One side of the compaction block is contacted with the side surface of a cylindrical hollow tube on the connecting plate of the normal pressure hydrogen measuring electrolytic cell, and the other side is contacted with the test sample and the sample clamp. And a second O-shaped sealing ring is arranged on the outer side of the sample clamp, one side of the sample clamp is contacted with the compression block, and the other side of the sample clamp is contacted with the hydrogen charging kettle body in the high-temperature and high-pressure environment. When tightening the fastening bolt connected between the normal pressure hydrogen measurement electrolytic cell and the high-temperature high-pressure environment hydrogen charging kettle, the cylindrical hollow tube on the connecting plate of the normal pressure hydrogen measurement electrolytic cell extrudes the compression block, the compression block extrudes the test sample and the sample clamp, and the sample clamp extrudes the kettle body wall, so that the sealing among the normal pressure hydrogen measurement electrolytic cell, the test sample and the high-temperature high-pressure environment hydrogen charging kettle is realized.
The technical scheme of the invention has the technical effects that:
1. can be applied to supercritical CO 2 In situ hydrogen permeation measurement of metals in any hot, high pressure, humid environment, including the transport environment.
2. The method realizes hydrogen charging in a high-pressure wet gas environment and hydrogen measurement in a normal-pressure environment, and reduces the test difficulty and the test cost.
3. The method can ensure that the temperature of the two sides of hydrogen charging and hydrogen measurement is consistent, avoid the problem of condensation of water in the high-pressure moisture environment caused by the temperature difference of the two sides, and further ensure that the test result can truly reflect the hydrogen permeation behavior of the high-pressure moisture environment.
Drawings
FIG. 1 is a schematic view of a hydrogen permeation testing device according to the present invention;
FIG. 2 is a schematic view of the circulating water heating apparatus of the present invention;
FIG. 3 is a schematic view of the structure of the normal pressure hydrogen measuring electrolytic cell of the present invention;
FIG. 4 is a schematic diagram of the structure of the high-temperature high-pressure environment hydrogen charging kettle of the invention;
FIG. 5 is a schematic view of the seal member structure of the present invention;
FIG. 6 is a graph of supercritical CO at example water saturation concentration 2 And supercritical CO 2 -SO 2 Hydrogen permeation curve of X65 pipeline steel in environment (8 MPa,50 ℃);
FIG. 7 (a) is a graph showing supercritical CO at the saturation concentration of example water 2 Macroscopic corrosion morphology (8 MPa,50 ℃) of the X65 steel surface after hydrogen permeation test in the environment;
FIG. 7 (b) is a graph showing supercritical CO at the saturation concentration of example water 2 -SO 2 Macroscopic corrosion morphology (8 MPa,50 ℃) of the X65 steel surface after hydrogen permeation test in the environment.
Detailed Description
The specific technical scheme of the invention is described with reference to the accompanying drawings.
As shown in fig. 1, the hydrogen permeation testing device mainly comprises three parts of a high-temperature and high-pressure environment hydrogen charging kettle 100, an atmospheric pressure hydrogen measuring electrolytic cell 200 and a circulating water heating device 300.
The functions of each part are as follows:
(1) High temperature and high pressure environment hydrogen charging kettle 100 for holding supercritical CO 2 Fluid, simulated impurity-containing supercritical CO 2 Delivering environmental conditions.
(2) The normal pressure hydrogen measuring electrolytic cell 200 is used for containing sodium hydroxide solution with a certain concentration, so that hydrogen atoms permeated into the hydrogen measuring electrolytic cell from the hydrogen charging kettle are oxidized, and hydrogen permeation current is formed.
(3) The circulating water heating device 300 is used for providing a constant temperature heat source for the normal pressure hydrogen measuring electrolytic cell 200 and heating the sodium hydroxide solution in the hydrogen measuring electrolytic cell, so as to ensure that the temperature of the normal pressure hydrogen measuring electrolytic cell 200 is the same as the temperature of the hydrogen charging kettle 100 in the high temperature and high pressure environment.
The main connection relationships between the various parts are as follows:
as shown in fig. 1, the water outlet 304 of the heating box of the circulating water heating device 300 is connected with the water inlet 206 of the electrolysis cell 200 of the normal pressure hydrogen measurement electrolytic cell through a pipeline, the water outlet 207 of the electrolysis cell of the normal pressure hydrogen measurement electrolytic cell 200 is connected with the water inlet 303 of the heating box of the circulating water heating device 300 through a pipeline, and an adapter is arranged between the pipeline and the water inlet/outlet for connection between the pipeline and the water inlet/outlet. The normal pressure hydrogen measuring electrolytic cell 200 is communicated with the high temperature and high pressure environment hydrogen charging kettle 100 through a fastening bolt, a compression block 600 and a sample clamp 500 are arranged at the joint of the two, and a test sample 400 is arranged in the sample clamp 500. One side of the pressing block 600 is in contact with the normal pressure hydrogen measuring cell 200, and the other side is in contact with the test sample 400 and the sample holder 500. One side of the sample fixture 500 is contacted with the compaction block 600, and the other side is contacted with the hydrogen charging kettle 100 body in the high-temperature high-pressure environment. The assembly relation is used for ensuring good tightness of the device and ensuring that no air leakage is generated in the high-pressure hydrogen charging and normal-pressure hydrogen measuring processes.
As shown in fig. 2, the circulating water heating apparatus 300 functions to provide constant temperature water heating of the normal pressure hydrogen measuring electrolytic cell 200, ensuring that the normal pressure hydrogen measuring electrolytic cell 200 is at the same temperature as the high temperature and high pressure environment hydrogen charging tank 100. The circulating water heating apparatus 300 comprises a constant temperature heating box 301, water, a circulating water pump 302, a heating box water outlet 304 and a heating box water inlet 303. The constant temperature heating cabinet 301 is used to heat water to a set temperature and maintain a constant temperature state. The circulating water pump 302 is arranged in the constant temperature heating box 301 and connected with a water outlet 304 of the heating box on the constant temperature heating box 301 through a pipeline, and is used for sucking and pumping water in the constant temperature heating box 301. The heating box water outlet 304 at the upper part of the constant temperature heating box 301 is connected with a pipeline through an adapter and is used for providing constant temperature water for the constant pressure hydrogen measuring electrolytic cell 200. The water inlet 303 of the heating box at the upper part of the constant temperature heating box 301 is connected with a pipeline through an adapter and is used for recycling water discharged by the constant pressure hydrogen measuring electrolytic cell 200. Through the above-mentioned action relationship, the water circulation function is realized.
As shown in fig. 3, the normal pressure hydrogen measuring cell 200 is a hydrogen measuring side for measuring a hydrogen permeation current. Comprising the following steps: an inner cavity 201, an inner cavity wall 202, an outer cavity 203, an outer cavity wall 204, a connection plate 205, an electrolytic cell water inlet 206 and an electrolytic cell water outlet 207. The inner cavity 201 is used for containing sodium hydroxide solution with a certain concentration, the outer cavity 203 is used for flowing constant-temperature circulating water, the inner cavity wall 202 is used for isolating the inner cavity 201 from the outer cavity 203, and the outer cavity wall 204 is used for heat preservation. One side of the inner cavity wall 202 and one side of the outer cavity wall 204 are connected with the connecting plate 205, through holes are formed in the edge of the connecting plate 205 and used for installing fastening bolts, the center of the connecting plate 205 is provided with a hole and is connected with the cylindrical hollow tube 208, through holes are formed in the upper tube wall of the cylindrical hollow tube 208 and used for inserting the working electrode wires 209 connected with samples, and the side face of the cylindrical hollow tube 208 is contacted with the compression block 600 and used for compressing the compression block 600. An electrolytic cell water inlet 206 is arranged below the normal pressure hydrogen measurement electrolytic cell 200, and the electrolytic cell water inlet 206 is communicated with the outer cavity 203 and is connected with a pipeline through an adapter for receiving constant temperature water provided by the circulating water heating device 300. An electrolytic cell water outlet 207 is arranged above the normal pressure hydrogen measuring electrolytic cell 200, and the electrolytic cell water outlet 207 is communicated with the outer cavity 203 and is connected with a pipeline through an adapter for discharging circulating water to the circulating water heating device 300. The upper inner cavity wall 202 and the outer cavity wall 204 of the normal pressure hydrogen measuring electrolytic cell 200 are provided with three conical holes for placing a rubber plug 212, and the center of the rubber plug 212 is provided with a through hole for respectively installing a working electrode lead 209, a reference electrode 210 and a counter electrode 211. The working electrode wire 209 is used for connecting the test sample 400, the lower end of the reference electrode 210 is connected with the Rugold capillary 213, and the tail end of the Rugold capillary 213 is close to the surface of the test sample 400. The hydrogen permeation current measurement can be achieved by connecting the working electrode lead 209, the counter electrode 211, and the reference electrode 210 to an electrochemical workstation.
As shown in fig. 4, the high temperature and high pressure environment hydrogen filling tank 100 is a hydrogen filling side for simulating a high pressure moisture environment and providing environmental conditions for corrosion and hydrogen generation of the test sample 400. Comprises a kettle cover 101, a kettle body 102, a controller 103, a heating resistance wire 104, a thermocouple 105, a pressure gauge 106, an air inlet 107, an air outlet 108, a water injection port 109 and a thermal insulation sleeve 110. The kettle cover 101 is connected with the kettle body 102 through a fastening bolt; a through hole is formed on one side of the kettle body 102 and used for installing the test sample 400, and the through hole is connected with the connecting plate 205 of the normal pressure hydrogen measuring electrolytic cell 200 through a fastening bolt; a heating resistance wire 104 is arranged in the wall of the kettle body 102, a thermocouple 105 is arranged on the kettle cover 101, and the heating resistance wire and the thermocouple are connected with the controller 103 through wires and used for heating and adjusting the temperature in the kettle; the kettle cover 101 is provided with a pressure gauge 106, and the pressure gauge 106 is connected with the controller 103 through a wire and is used for monitoring the pressure in the kettle body 102; the kettle cover 101 is provided with a water filling port 109 for filling trace water required by a test environment into the kettle; the kettle cover 101 is provided with an air inlet 107 for introducing gas required by test into the kettle body 102; the tank cover 101 is provided with an exhaust port 108 for exhausting the gas in the tank body 102.
As shown in fig. 5, a sealing member including a pressing block 600, a sample holder 500 and an O-ring is provided between the normal pressure hydrogen measuring cell 200 and the high temperature and high pressure environment hydrogen charging tank 100. The first O-ring 501 is installed on the outer side of the compression block 600, and a through hole is formed in the upper wall for inserting the working electrode wire 209 connected with the sample. One side of the compression block 600 is contacted with the side surface of the cylindrical hollow tube 208 on the connecting plate 205 of the normal pressure hydrogen measuring electrolytic cell 200, and the other side is contacted with the test sample 400 and the sample clamp 500. A second O-ring 502 is installed on the outer side of the sample clamp 500, one side of the sample clamp 500 is in contact with the compression block 600, and the other side is in contact with the body of the high-temperature and high-pressure environment hydrogen charging kettle 100. When tightening the fastening bolts connected between the normal pressure hydrogen measuring electrolytic cell 200 and the high-temperature high-pressure environment hydrogen charging kettle 100, the cylindrical hollow tube 208 on the connecting plate 205 of the normal pressure hydrogen measuring electrolytic cell 200 extrudes the compression block 600, the compression block 600 extrudes the test sample 400 and the sample clamp 500, and the sample clamp 500 extrudes the wall of the kettle body 102, so that the sealing among the normal pressure hydrogen measuring electrolytic cell 200, the test sample 400 and the high-temperature high-pressure environment hydrogen charging kettle 100 is realized.
In situ hydrogen permeation test method:
s1, placing a sample of the single-sided electroplated nickel coating on a sample clamp 500, wherein one side of the sample nickel coating faces to the normal pressure hydrogen measurement electrolytic cell 200, and the exposed surface of the other side faces to the high-temperature high-pressure environment hydrogen charging kettle 100. The sample clamp 500 is placed in a through hole on one side wall of the kettle body 102 of the high-temperature high-pressure environment hydrogen charging kettle 100, and the compacting block 600 is placed. Then the normal pressure hydrogen measuring electrolytic cell 200 is connected with the high temperature and high pressure environment hydrogen charging kettle 100 through fastening bolts.
S2, adding sodium hydroxide solution with a certain concentration into the inner cavity 201 of the normal pressure hydrogen measurement electrolytic cell 200, mounting a rubber plug 212, a working electrode lead 209, a counter electrode 211, a reference electrode 210 and a Rujin capillary 213, and connecting with an electrochemical workstation. The surface of the nickel-plated sample exposed to one side of the normal pressure hydrogen measuring electrolytic cell 200 is passivated by applying a potentiostatic polarizing potential thereto by an electrochemical workstation to reduce the background current to 0.1. Mu.A/cm 2 The following is given.
S3, closing the high-temperature high-pressure environment hydrogen charging kettle 100, opening an exhaust port 108 valve, and introducing high-purity CO 2 The gas was allowed to flow for at least 2 hours to remove residual air from the kettle. The hydrogen charging kettle 100 and the heating device 300 of the heat circulating water in the high-temperature and high-pressure environment are respectively heated, meanwhile, the circulating water pump 302 is turned on, constant-temperature circulating water is introduced into the outer cavity 203 of the normal-pressure hydrogen measuring electrolytic cell 200, and then the solution in the inner cavity 201 is heated. After the temperature reaches the set temperature, the required water quantity is added into the high-temperature high-pressure environment hydrogen charging kettle 100 through the water filling port 109, and the supercritical CO is added into the high-temperature high-pressure environment hydrogen charging kettle 100 through the air inlet 107 2 O and O 2 、SO x 、NO x 、H 2 S and other impurity components to the required pressure.
S4, recording the change of the current density of one side of the normal pressure hydrogen measurement electrolytic cell 200 along with time in real time through an electrochemical workstation. When the sample surface at the hydrogen charging side of the high-temperature and high-pressure environment is corroded, hydrogen generated by corrosion permeates through the sample and reaches the sample surface at the side of the normal-pressure hydrogen measuring electrolytic cell 200, hydrogen atoms are oxidized under the action of constant-potential polarization applied by an electrochemical workstation to form oxidation current, and then a hydrogen permeation curve is obtained.
FIG. 6 shows supercritical CO at saturated concentration of water measured using the apparatus of the present invention 2 And supercritical CO 2 -SO 2 Hydrogen permeation curve of X65 pipeline steel in the environment. Fig. 7 (a) and 7 (b) are macroscopic corrosion profiles of the X65 steel surface after hydrogen permeation testing. In water saturation supercritical CO 2 The corrosion of the X65 steel in the environment is very slight, as in fig. 7 (a), with a hydrogen permeation current density of substantially 0 (fig. 6), indicating that no hydrogen permeation occurs in this environment. While in water saturated supercritical CO 2 -SO 2 The significant hydrogen permeation current (fig. 6) was detected in the environment where the corrosion of the X65 steel was severe, as in fig. 7 (b), indicating that hydrogen permeation could occur. It can be seen that SO 2 The presence of impurities can significantly promote hydrogen permeation. The above examples demonstrate the feasibility of the device of the invention.
Supercritical CO according to the invention 2 The device and method of the present invention can be used in both a delivery environment, but not limited to, a related test under such an environment, a high temperature, high pressure, humidity environment, and an aqueous medium environment.
Claims (2)
1. For supercritical CO 2 The hydrogen permeation testing device for pipeline steel in a conveying environment is characterized by comprising a high-temperature high-pressure environment hydrogen charging kettle (100), a normal-pressure hydrogen measuring electrolytic cell (200) and a circulating water heating device (300);
high temperature and high pressure environment hydrogen charging kettle (100) for holding supercritical CO 2 Fluid, simulated impurity-containing supercritical CO 2 Delivering environmental conditions;
a normal pressure hydrogen measuring electrolytic cell (200) for holding sodium hydroxide solution with a certain concentration, so that hydrogen atoms permeated into the hydrogen measuring electrolytic cell from the hydrogen charging kettle are oxidized to form hydrogen permeation current;
the circulating water heating device (300) is used for providing a constant-temperature heat source for the normal-pressure hydrogen measurement electrolytic cell (200) and heating sodium hydroxide solution in the hydrogen measurement electrolytic cell to ensure that the temperature of the normal-pressure hydrogen measurement electrolytic cell (200) is the same as the temperature of the high-temperature high-pressure environment hydrogen charging kettle (100);
the water outlet (304) of the heating box of the circulating water heating device (300) is connected with the water inlet (206) of the electrolysis cell of the normal pressure hydrogen measurement electrolysis cell (200) through a pipeline, and the water outlet (207) of the electrolysis cell of the normal pressure hydrogen measurement electrolysis cell (200) is connected with the water inlet (303) of the heating box of the circulating water heating device (300) through a pipeline; the normal pressure hydrogen measurement electrolytic cell (200) is communicated with the high temperature and high pressure environment hydrogen charging kettle (100) through a fastening bolt, a compression block (600) and a sample clamp (500) are arranged at the joint of the two, and a test sample (400) is arranged in the sample clamp (500); one side of the compaction block (600) is contacted with the normal pressure hydrogen measuring electrolytic cell (200), and the other side is contacted with the test sample (400) and the sample clamp (500); one side of the sample clamp (500) is contacted with the compaction block (600), and the other side is contacted with the body of the high-temperature high-pressure environment hydrogen charging kettle (100);
the circulating water heating device (300) comprises a constant-temperature heating box body (301), water, a circulating water pump (302), a heating box water outlet (304) and a heating box water inlet (303); the constant temperature heating box body (301) is used for heating water to a set temperature and maintaining a constant temperature state; the circulating water pump (302) is arranged in the constant-temperature heating box body (301) and is connected with a heating box water outlet (304) on the constant-temperature heating box body (301) through a pipeline, and is used for sucking and pumping water in the constant-temperature heating box body (301); a water outlet (304) of the heating box at the upper part of the constant temperature heating box body (301) is connected with a pipeline through an adapter and is used for providing warm water for the normal pressure hydrogen measurement electrolytic cell (200); a water inlet (303) of the heating box at the upper part of the constant temperature heating box body (301) is connected with a pipeline through an adapter and is used for recovering water discharged by the normal pressure hydrogen measuring electrolytic cell (200);
the normal pressure hydrogen measurement electrolytic cell (200) is a hydrogen measurement side and is used for measuring hydrogen permeation current; comprising the following steps: an inner cavity (201), an inner cavity wall (202), an outer cavity (203), an outer cavity wall (204), a connecting plate (205), an electrolytic cell water inlet (206) and an electrolytic cell water outlet (207); the inner cavity (201) is used for containing sodium hydroxide solution with a certain concentration, the outer cavity (203) is used for flowing constant-temperature circulating water, the inner cavity wall (202) is used for isolating the inner cavity (201) and the outer cavity (203), and the outer cavity wall (204) is used for preserving heat; one side of the inner cavity wall (202) and one side of the outer cavity wall (204) are connected with a connecting plate (205), through holes are formed in the edges of the connecting plate (205) and are used for installing fastening bolts, the center of the connecting plate (205) is provided with a hole and is connected with a cylindrical hollow pipe (208), through holes are formed in the upper pipe wall of the cylindrical hollow pipe (208) and are used for inserting a working electrode wire (209) connected with a sample, and the side face of the cylindrical hollow pipe (208) is contacted with a compression block (600) and used for compressing the compression block (600); an electrolytic cell water inlet (206) is arranged below the normal pressure hydrogen measurement electrolytic cell (200), the electrolytic cell water inlet (206) is communicated with the outer cavity (203) and is connected with a pipeline through an adapter for receiving the hot water provided by the circulating water heating device (300); an electrolytic cell water outlet (207) is arranged above the normal pressure hydrogen measurement electrolytic cell (200), the electrolytic cell water outlet (207) is communicated with the outer cavity (203) and is connected with a pipeline through an adapter for discharging circulating water to the circulating water heating device (300); three conical holes are formed in an inner cavity wall (202) and an outer cavity wall (204) at the upper part of the normal-pressure hydrogen measurement electrolytic cell (200) and are used for placing a rubber plug (212), and a through hole is formed in the center of the rubber plug (212) and is used for respectively installing a working electrode lead (209), a reference electrode (210) and a counter electrode (211); the working electrode lead (209) is used for connecting a test sample (400), the lower end of the reference electrode (210) is connected with the Rujin capillary (213), and the tail end of the Rujin capillary (213) is close to the surface of the test sample (400); connecting a working electrode lead (209), a counter electrode (211) and a reference electrode (210) to an electrochemical workstation to realize hydrogen permeation current measurement;
the high-temperature high-pressure environment hydrogen charging kettle (100) is a hydrogen charging side and is used for simulating a high-pressure moisture environment and providing environmental conditions for corrosion of a test sample (400) and hydrogen generation; the device comprises a kettle cover (101), a kettle body (102), a controller (103), a heating resistance wire (104), a thermocouple (105), a pressure gauge (106), an air inlet (107), an air outlet (108), a water injection port (109) and a heat preservation sleeve (110); the kettle cover (101) is connected with the kettle body (102) through a fastening bolt; a through hole is formed on the kettle wall at one side of the kettle body (102) and is used for installing a test sample (400) and is connected with a connecting plate (205) of the normal pressure hydrogen measuring electrolytic cell (200) through a fastening bolt; a heating resistance wire (104) is arranged in the wall of the kettle body (102), a thermocouple (105) is arranged on the kettle cover (101), and the heating resistance wire and the thermocouple are connected with a controller (103) through wires and used for heating and adjusting the temperature in the kettle; the kettle cover (101) is provided with a pressure gauge (106), and the pressure gauge (106) is connected with the controller (103) through a wire and is used for monitoring the pressure in the kettle body (102); the kettle cover (101) is provided with a water filling port (109) for filling trace water required by a test environment into the kettle; the kettle cover (101) is provided with an air inlet (107) for introducing gas required by test into the kettle body (102); the kettle cover (101) is provided with an exhaust port (108) for exhausting the gas in the kettle body (102).
2. A process for supercritical CO according to claim 1 2 The hydrogen permeation testing device for pipeline steel in a conveying environment is characterized in that a sealing part is designed between a normal pressure hydrogen measuring electrolytic cell (200) and a high temperature and high pressure environment hydrogen charging kettle (100), a first O-shaped sealing ring (501) is arranged on the outer side of a compression block (600), and a through hole is formed in the upper wall and used for inserting a working electrode lead (209) connected with a sample; one side of the compaction block (600) is contacted with the side surface of a cylindrical hollow tube (208) on a connecting plate (205) of the normal pressure hydrogen measuring electrolytic cell (200), and the other side is contacted with the test sample (400) and the sample clamp (500); a second O-shaped sealing ring (502) is arranged on the outer side of the sample clamp (500), one side of the sample clamp (500) is contacted with the compaction block (600), and the other side is contacted with the body of the high-temperature and high-pressure environment hydrogen charging kettle (100); when tightening the fastening bolt connected between the normal pressure hydrogen measurement electrolytic cell (200) and the high-temperature high-pressure environment hydrogen charging kettle (100), the cylindrical hollow pipe (208) on the connecting plate (205) of the normal pressure hydrogen measurement electrolytic cell (200) extrudes the compression block (600), the compression block (600) extrudes the test sample (400) and the sample clamp (500), the sample clamp (500) extrudes the wall of the kettle body (102), and the sealing among the normal pressure hydrogen measurement electrolytic cell (200), the test sample (400) and the high-temperature high-pressure environment hydrogen charging kettle (100) is realized.
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