阅读说明：本技术 一种降低氢气对管道材料性能劣化的方法 (Method for reducing performance deterioration of pipeline material caused by hydrogen ) 是由 刘娟 徐俊辉 陈留平 朱旭初 王卫东 于 2021-08-25 设计创作，主要内容包括：本发明涉及氢能源利用技术领域,尤其涉及一种降低氢气对管道材料性能劣化的方法,包括以下步骤：S1、向氢气储存容器中先加入缓蚀气体,所述氢气储存容器由金属材料及金属合金制成；S2、将氢气储存容器静置,使得缓蚀气体与容器充分接触并且渗透到容器内部；S3、抽出容器内的部分缓蚀气体,余下部分缓蚀气体留在容器中；S4、向氢气储存容器中充入氢气,然后将容器密封,通过缓蚀气体降低氢气对氢气储存容器的腐蚀速率。本发明的一种降低氢气对管道材料性能劣化的方法,通过向氢气储存器中加入缓蚀气体,将容器静置一端时间,可以降低氢气对金属的腐蚀作用,从而提高氢气储存器的使用寿命,避免氢气泄露发生安全事故。(The invention relates to the technical field of hydrogen energy utilization, in particular to a method for reducing the performance deterioration of a pipeline material caused by hydrogen, which comprises the following steps: s1, adding corrosion inhibition gas into a hydrogen storage container, wherein the hydrogen storage container is made of metal materials and metal alloys; s2, standing the hydrogen storage container to enable the corrosion inhibition gas to be in full contact with the container and permeate into the container; s3, extracting part of corrosion inhibition gas in the container, and leaving the rest part of corrosion inhibition gas in the container; and S4, filling hydrogen into the hydrogen storage container, sealing the container, and reducing the corrosion rate of the hydrogen to the hydrogen storage container through corrosion inhibition gas. According to the method for reducing the performance deterioration of the hydrogen on the pipeline material, the corrosion inhibition gas is added into the hydrogen storage device, the container is kept still for a period of time, the corrosion effect of the hydrogen on the metal can be reduced, the service life of the hydrogen storage device is prolonged, and safety accidents caused by hydrogen leakage are avoided.)

1. A method for reducing the performance deterioration of a pipeline material caused by hydrogen is characterized by comprising the following steps: the method comprises the following steps:

s1, adding corrosion inhibition gas into a hydrogen storage container, wherein the hydrogen storage container is made of metal materials and metal alloys;

s2, standing the hydrogen storage container to enable the corrosion inhibition gas to be in full contact with the container and permeate into the container;

s3, extracting part of corrosion inhibition gas in the container, and leaving the rest part of corrosion inhibition gas in the container;

and S4, filling hydrogen into the hydrogen storage container, sealing the container, and reducing the corrosion rate of the hydrogen to the hydrogen storage container through corrosion inhibition gas.

2. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: the hydrogen storage container includes: and constructing an underground hydrogen gas storage reservoir by using a high-pressure storage tank, a pipeline, a depleted oil-gas field, an underground aquifer, a saline rock stratum or a waste mine.

3. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: the filling pressure condition of the corrosion inhibition gas filled in the step S1 is 0.1 MPa-2 MPa.

4. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 3, wherein: the corrosion inhibiting gas may be oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂One or two or more gases selected from O) and argon (Ar) in the presence of oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂O and argon (Ar) are added in sequence.

5. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: the standing time of the hydrogen storage container in the step S2 is 3-5 hours.

6. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: the amount of the residual corrosion inhibition gas in the step S3 is 10-1000 ppm.

7. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: in step S4, the purity of the hydrogen gas charged is 80.0% to 99.999%.

8. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: the metal material includes carbon steel, stainless steel, copper alloy, aluminum alloy, and brass material.

9. A method of reducing degradation of the material properties of a pipe by hydrogen gas as claimed in claim 1, wherein: grades of the carbon steel include X42-X70 pipeline steel.

Technical Field

The invention relates to the technical field of hydrogen energy utilization, in particular to a method for reducing the performance degradation of hydrogen on pipeline materials, which can effectively improve the durability of metal materials in the process of pipeline transportation, storage tanks and underground storage reservoirs.

Background

With the climate change and the sign of Paris' agreement, global energy is advancing toward high-efficiency, clean, low-carbon and diversified characteristic directions. The energy transformation development of all countries in the world mainly focuses on renewable energy sources such as solar energy, wind energy, water and electricity and the like, and aims to improve the energy safety and reduce the carbon emission. However, the production of renewable energy sources is unstable and difficult to store, so that hydrogen energy which can solve the peak regulation problem of the renewable energy sources rises rapidly, and the renewable energy sources have the characteristics of high hydrogen-electricity conversion rate, storage, high heat value per unit mass, wide combustion limit and the like, and are considered as important energy carriers in the future.

At present, the international widely held is that the 'hydrogen-doped natural gas technology' is one of effective ways for solving the problem of 'wind and light abandonment'. The technology uses part of electric energy converted from wind energy/light energy for hydrogen production by water electrolysis, mixes hydrogen into natural gas in a certain proportion to form hydrogen-mixed natural gas, and then utilizes a newly-built pipe network or an in-service natural gas pipe network to convey the hydrogen-mixed natural gas to a user terminal, a gas station, a gas storage warehouse and the like, so that the functions of energy storage and peak load clipping and valley filling of electric power load can be achieved, and high construction cost required by newly-built hydrogen conveying pipelines is avoided. Foreign research shows that the cost of the hydrogen pipeline is more than 2 times of that of the natural gas pipeline. On the other hand, underground hydrogen gas storage reservoirs can be constructed by using depleted oil and gas fields, underground aquifers, saline rock formations or waste mines.

Research shows that the metal material has the possibility of hydrogen embrittlement under the hydrogen environment. Compared with the air environment, the strength of the material in the hydrogen-containing environment is not greatly changed, but the ductility, the fatigue performance and the fracture toughness are obviously degraded. The deterioration degree of the tensile property of the pipeline steel increases with the increase of the three axial degrees of loading rate, hydrogen pressure and stress. The fatigue performance is related to hydrogen pressure, stress ratio, loading frequency, microstructure and the like, and the fatigue crack propagation rate is accelerated due to the increase of the pressure, the increase of the stress ratio and the decrease of the loading frequency. Fracture toughness is related to various factors such as loading rate, hydrogen pressure, grain size, martensite/austenite content, etc., and a decrease in loading rate and an increase in hydrogen pressure generally result in a decrease in fracture toughness. Therefore, whether the hydrogen is transported through a pipeline or stored by a salt cavern or a storage tank of steel material, the problem of the degradation of the performance of the pipeline material by the hydrogen must be considered.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the invention provides a method for reducing the performance deterioration of hydrogen on a pipeline material, aiming at solving the technical problem that the metal material is easy to deteriorate in the processes of pipeline transportation, storage tanks and underground storage reservoirs in the prior art.

The technical scheme adopted by the invention for solving the technical problems is as follows: a method of reducing degradation of the properties of a pipe material by hydrogen gas, comprising the steps of:

s1, adding corrosion inhibition gas into a hydrogen storage container, wherein the hydrogen storage container is made of metal materials and metal alloys;

s2, standing the hydrogen storage container to enable the corrosion inhibition gas to be in full contact with the container and permeate into the container;

s3, extracting part of corrosion inhibition gas in the container, and leaving the rest part of corrosion inhibition gas in the container;

and S4, filling hydrogen into the hydrogen storage container, sealing the container, and reducing the corrosion rate of the hydrogen to the hydrogen storage container through corrosion inhibition gas.

According to the method for reducing the performance degradation of the pipeline material caused by the hydrogen, the corrosion inhibition gas is added into the hydrogen storage device, the container is kept still for a period of time, so that gas molecules of the corrosion inhibition gas are diffused into the metal through the wall of the container and fully contact with the metal, and a protective layer is formed on the surface of the metal, so that the corrosion effect of the hydrogen on the metal can be reduced, the service life of the hydrogen storage device is prolonged, the hydrogen leakage caused by hydrogen cracking of the hydrogen storage device is avoided, and the safety accident is avoided.

Further, the hydrogen storage container includes: and constructing an underground hydrogen gas storage reservoir by using a high-pressure storage tank, a pipeline, a depleted oil-gas field, an underground aquifer, a saline rock stratum or a waste mine.

Further, the filling pressure condition of the corrosion inhibition gas filled in the step S1 is 0.1 MPa-2 MPa.

Further, the corrosion inhibiting gas may be oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂One or two or more gases selected from O) and argon (Ar) in the presence of oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂O and argon (Ar) are added in sequence.

Further, the standing time of the hydrogen storage container in the step S2 is 3 to 5 hours.

Further, the amount of the residual corrosion inhibiting gas used in step S3 is 10 to 1000 ppm. The residual corrosion inhibition gas in the hydrogen storage device can reduce the fatigue crack propagation rate of the metal material of the hydrogen storage device, but the fatigue crack propagation rate of the metal material tends to be increased due to excessive residual corrosion inhibition gas, and the purpose of delaying the corrosion of hydrogen to the metal material cannot be achieved due to excessive residual corrosion inhibition gas.

Further, in step S4, the purity of the hydrogen gas charged is 80.0% to 99.999%.

Further, the metal material includes carbon steel, stainless steel, copper alloy, aluminum alloy, and brass material.

Further, the grades of carbon steel include X42-X70 pipeline steel.

The method for reducing the performance deterioration of the hydrogen to the pipeline material has the advantages that the corrosion inhibition gas with strong diffusivity is added into the container for storing the hydrogen, the initially introduced corrosion inhibition gas can fully contact with the inner wall of the metal, then part of the gas permeates into the inner wall of the metal to generate a protective layer on the inner wall of the metal, so that the corrosion action of the hydrogen to the metal can be reduced, the integrity and the durability of the metal material are improved in the process of storing and transporting the hydrogen, the service life of a hydrogen storage device or a hydrogen transportation pipeline is prolonged, the used corrosion inhibition gas has proper price and low cost, the used corrosion inhibition gas cannot pollute the environment, the energy is saved, the environment is protected, and the service performance and the safety performance of the metal material are greatly improved, the service life of the hydrogen storage device and the conveying pipeline is prolonged, and the safety of hydrogen storage is also improved.

Drawings

The invention is further illustrated with reference to the following figures and examples.

FIG. 1 is a flow diagram of a method of reducing hydrogen degradation to pipe material performance in accordance with a preferred embodiment of the present invention.

Fig. 2 is a fracture map image of X70 pipeline steel.

Detailed Description

To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1: referring to fig. 1, a method for reducing hydrogen degradation to pipe material performance according to a preferred embodiment of the present invention comprises the following steps:

s1, adding corrosion inhibition gas into a hydrogen storage container, wherein the hydrogen storage container is made of metal materials and metal alloys;

s2, standing the hydrogen storage container to enable the corrosion inhibition gas to be in full contact with the container and permeate into the container;

s3, extracting part of corrosion inhibition gas in the container, and leaving the rest part of corrosion inhibition gas in the container;

and S4, filling hydrogen into the hydrogen storage container, sealing the container, and reducing the corrosion rate of the hydrogen to the hydrogen storage container through corrosion inhibition gas.

Further embodiments of the invention are: the hydrogen storage container includes: and constructing an underground hydrogen gas storage reservoir by using a high-pressure storage tank, a pipeline, a depleted oil-gas field, an underground aquifer, a saline rock stratum or a waste mine.

Further embodiments of the invention are: the filling pressure condition of the corrosion inhibition gas filled in the step S1 is 0.1 MPa-2 MPa.

Further embodiments of the invention are: the corrosion inhibiting gas is oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂One or two or more gases selected from O) and argon (Ar), wherein the gases are not mixed but added in a certain order when the two or more gases are added, and the gases are added according to oxygen (O) when the two or more gases are added₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂O and argon (Ar) are added in sequence.

Further embodiments of the invention are: the standing time of the hydrogen storage container in the step S2 is 3-5 hours.

Further embodiments of the invention are: the amount of the residual corrosion inhibition gas in the step S3 is 10-1000 ppm.

Further embodiments of the invention are: the source of the hydrogen gas charged in the step S4 is not limited, and the purity of the charged hydrogen gas is 80.0% -99.999%.

Further embodiments of the invention are: the metal material includes carbon steel, stainless steel, copper alloy, aluminum alloy, and brass material.

Further embodiments of the invention are: grades of carbon steel include X42-X70 pipeline steel.

The effects of different gases on the hydrogen storage vessel were compared by a fatigue crack growth rate test, the test method being referred to astm e647, i.e. using a compact tensile specimen, the specimen was first precracked in air: and (3) applying a cyclic load to the sample by adopting a sinusoidal loading waveform with a stress ratio of 0.1, wherein the loading frequency is 5Hz, the initial force value range is 25kN, and the loading is stopped until the crack length is increased by about 3 mm. And then filling high-purity hydrogen into the sample, adding corrosion inhibition gas, standing for a period of time, adopting a sinusoidal loading waveform with a stress ratio of 0.1 during testing, keeping the force value range unchanged at 19kN, reducing the loading frequency to 1Hz, obtaining the change relation between the crack propagation length and the stress intensity factor along with the load cycle number in the test process, and finally calculating to obtain the fatigue crack propagation rate of the sample.

Testing in a hydrogen environment of 10MPa at normal temperature, firstly filling hydrogen with the purity of 100% into a No. 1 alloy steel container to serve as a blank sample, respectively filling corrosion inhibition gas into No. 2 to No. 11 alloy steel containers under the pressure condition of 0.1MPa for detecting the sample, and respectively filling oxygen (O) into the corrosion inhibition gas filled into the No. 2 to No. 11 alloy steel containers₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Sulfur dioxide (SO)₂) Water vapor (H)₂O), argon (Ar), methyl mercaptan (CH)₃SH), hydrogen sulfide (H)₂S), standing for 3 hours, pumping out the corrosion inhibition gas to ensure that the content of the residual corrosion inhibition gas is 0.1%, then filling hydrogen with the purity of 100%, standing for a period of time, and testing the fatigue crack propagation rate according to the method, wherein the test data are shown in Table 1.

TABLE 1 comparison of the effects of different gases on the fatigue crack growth Rate

As can be seen from Table 1, when the crack growth rate of hydrogen is used as blank data and the same volume content of the gas remaining in each container is used, sulfur dioxide (SO) is obtained₂) Methyl mercaptan (CH)₃SH), hydrogen sulfide (H)₂S) the three gases have no delaying effect on the crack propagation rate, but play a promoting role, accelerate the corrosion of the alloy steel, and cannot be used as corrosion inhibition gases. The gas having a retarding effect on the crack propagation rate is oxygen (O)₂) Carbon monoxide (CO), methane (CH)₄) Nitrogen (N)₂) Carbon dioxide (CO)₂) Water vapor (H)₂O) and argon (Ar), so the corrosion of the hydrogen alloy steel can be inhibited by adding the gases, the service performance and the safety performance of the metal material are improved, and the service life of the metal material is prolonged.

Example 2

The material is subjected to a mechanical property test, the test method refers to standard ASTMG142, a smooth round bar sample is adopted to fill hydrogen with certain purity, corrosion inhibition gas is added at the same time, after the sample is placed for a period of time, uniaxial stretching is carried out on the sample at a constant speed in a displacement control mode until the sample is broken. The maximum stress value to which the sample is subjected before breaking in this process is the tensile strength. And the maximum force corresponding to the elastic deformation of the sample is the yield strength. The ratio of the elongation length to the original length in the stretch-break process is the elongation at break.

The method comprises the steps of testing in a 10MPa hydrogen environment at normal temperature, firstly filling 100% hydrogen into a plurality of steel containers of different grades to serve as blank samples, respectively filling corrosion inhibition gas into the steel containers of the different grades under the pressure condition of 1MPa for the test samples, standing for 4 hours, then pumping out the corrosion inhibition gas to enable the content of the residual corrosion inhibition gas to be 1%, then filling the hydrogen with the purity of 100%, standing for a period of time, detecting the mechanical properties of the steel containers of the different grades according to the method, and comparing the influences of the different corrosion inhibition gases on the mechanical properties of the steel containers of the different grades. The data are shown in the following table:

TABLE 2 influence of different gases on mechanical properties of different grades of steel

As shown in table 2, from the yield strength data, when the alloy steel material is filled with hydrogen, elastic deformation occurs, when the alloy steel material is stretched by external force, the material enters into the plastic deformation period to be deformed, and after corrosion inhibition gas is added, the elasticity of the material is improved, and the possibility of deformation is reduced.

From the data of tensile strength, after the alloy steel material is filled with hydrogen, the tensile strength of the alloy steel material is reduced, which shows that the anti-fracture capability of the alloy steel material is reduced, and after the corrosion inhibition gas is added, the tensile strength of the alloy steel material is increased, and the resistance to plastic deformation is also increased, so that the anti-fracture capability of the alloy steel material is improved.

From the data of the elongation at break, the elongation at break after filling hydrogen gas is compared with the elongation at break of the material before filling hydrogen gas at normal temperature and normal pressure, which shows that the percentage content is reduced, and the percentage content of the value after adding the corrosion inhibition gas is increased compared with the value after filling hydrogen gas only shows that the elasticity performance of the material corroded by hydrogen can be increased by adding the corrosion inhibition gas.

Therefore, the corrosion inhibition gas is added, so that the corrosion of the hydrogen to the metal material can be reduced, and the service performance and the safety performance of the metal material are improved. FIG. 2 is a fracture diagram image of X70 pipeline steel, (a) is a 10MPa hydrogen environment with 1% oxygen added; it can be seen from the fracture of the sample that after the corrosion inhibition gas is added, the plastic deformation degree of the material is reduced, and the crack characteristics are not obvious; (b) in a pure hydrogen environment of 10MPa, it can be seen that the material is locally subjected to plastic deformation, and a plurality of cracks with different degrees and even fracture phenomena are generated. Comparing the two graphs of the graph (a) and the graph (b), the corrosion situation of the metal material after the corrosion inhibition gas is added is greatly improved, and the influence of hydrogen on hydrogen corrosion embrittlement and hydrogen induced cracking of the metal material can be obviously reduced.

Example 3

The test is carried out in a hydrogen environment of 10MPa at normal temperature, the steel pipe grades X42 and X70 are selected for the test, firstly, hydrogen with the concentration of 100% is filled into steel containers of two different grades to be used as blank samples, the test samples are that oxygen and carbon monoxide are respectively filled into the two steel containers under the pressure condition of 2MPa, the oxygen and the carbon monoxide are respectively extracted after the two steel containers are stood for 5 hours, the residual contents of the two gases are respectively 10ppm, 500ppm, 1000ppm and 2000ppm, then, the hydrogen with the purity of 100% is filled, and after the steel containers are stood for a period of time, the fatigue crack propagation rate of the test samples is tested according to the method of the embodiment 1. The data are as follows:

TABLE 3 comparison of the effects of different gases on the fatigue crack growth Rate

As can be seen from Table 3, the fatigue crack growth rate can be reduced by adding oxygen and carbon monoxide, and gradually decreases with increasing addition amount until the fatigue crack growth rate is ignored, but the more the addition amount is, the better the fatigue crack growth rate is, and when the addition amount reaches 2000ppm, the fatigue crack growth rate rather tends to increase, so the optimal amount of the corrosion inhibiting gas is 10-1000 ppm.

In summary, the method for reducing the degradation of the performance of the pipeline material by the hydrogen has the following effects: the corrosion inhibition gas used in the invention has proper price and low cost, and the used corrosion inhibition gas does not cause pollution to the environment, is energy-saving and environment-friendly, greatly improves the service performance and safety performance of the metal material, prolongs the service life of the hydrogen storage device or the hydrogen conveying pipeline, and also improves the safety of hydrogen storage.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined by the scope of the claims.