CN115161085A - Hydrogen-resistant reconstruction method for hydrogen pipeline by using natural gas additive based on competitive adsorption - Google Patents
Hydrogen-resistant reconstruction method for hydrogen pipeline by using natural gas additive based on competitive adsorption Download PDFInfo
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- CN115161085A CN115161085A CN202210921380.7A CN202210921380A CN115161085A CN 115161085 A CN115161085 A CN 115161085A CN 202210921380 A CN202210921380 A CN 202210921380A CN 115161085 A CN115161085 A CN 115161085A
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- hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D3/00—Arrangements for supervising or controlling working operations
- F17D3/12—Arrangements for supervising or controlling working operations for injecting a composition into the line
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a hydrogen-resistant reconstruction method for a hydrogen pipeline by using a natural gas additive based on competitive adsorption, belonging to the technical field of natural gas hydrogen-doped pipeline transportation. The additive is injected into the hydrogen pipeline, so that the hydrogen-resistant reconstruction of the hydrogen pipeline can be realized, the used additive is any one of alkane, alkene or a compound containing three elements of C, H and O, the concentration of hydrogen molecules on the surface of the hydrogen pipeline can be reduced, the possibility of tube body failure caused by hydrogen permeation and hydrogen induced cracking in a metal matrix of a tube wall is reduced, the hydrogen pipeline is protected, the problems of high construction cost, difficult construction and poor applicability of the hydrogen pipeline in the hydrogen-resistant reconstruction of the natural gas pipeline are solved, and the flexibility of hydrogen energy transmission is improved.
Description
Technical Field
The invention relates to the technical field of natural gas hydrogen-loading pipe transportation, in particular to a hydrogen-resistant reconstruction method for a hydrogen pipeline by using a natural gas additive based on competitive adsorption.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
As an effective way for solving the problem of renewable energy consumption such as 'wind and light abandonment' and the like, the main problem of the development of the natural gas hydrogen-doped pipe transportation process is the problem of hydrogen embrittlement of pipeline steel, and the pipeline steel is more susceptible to hydrogen when the strength is higher, so that the mechanical property is degraded, and accidents such as pipeline brittle failure, leakage and the like are caused.
At present, two methods of steel modification and surface modification can be used for improving the hydrogen embrittlement resistance of the hydrogen steel. The steel material modification cannot be used for the built natural gas pipeline, even if a newly-built natural gas pipeline is subjected to high-strength hydrogen-resistant stainless steel, the construction cost is overhigh, and the low-strength pipeline steel limits the design pressure of the pipeline and reduces the conveying efficiency; for surface modification, various hydrogen-resistant coating products are applied to high-pressure hydrogen storage equipment, but compared with a hydrogen storage container, a long-distance large-pipe-diameter high-pressure natural gas pipeline has a larger coating area, and the problems of high use cost of the coating, difficult repair after falling off and difficult coating exist.
In view of this, in order to overcome the defects in the prior art, a hydrogen-resistant modification method for a large-scale long-distance high-pressure and high-hydrogen-doping-ratio natural gas transmission pipeline is provided, which is a technical problem to be solved in the field urgently.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a hydrogen-resistant reforming method for a hydrogen pipeline by using a natural gas additive based on competitive adsorption. The additive injection method is used for injecting the natural gas additive based on competitive adsorption into the hydrogen pipeline by adopting an additive injection mode aiming at the hydrogen pipeline or the natural gas hydrogen-doped pipeline made of metal, so that the concentration of hydrogen molecules on the surface of the hydrogen pipeline is reduced, the possibility of failure of a pipe body caused by hydrogen permeation and hydrogen induced cracking in a metal matrix of the pipe wall is reduced, and the protection of the hydrogen pipeline is realized.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the natural gas additive based on competitive adsorption is applied to the protection of a hydrogen pipeline, wherein the additive is any one of alkane, olefin or a compound containing three elements of C, H and O, preferably one of alcohols and ether organic matters, and further preferably one of methanol, ethanol, propanol and diethyl ether.
On the other hand, the natural gas additive based on competitive adsorption is injected into the hydrogen pipeline by using the natural gas additive based on competitive adsorption, so that the hydrogen molecule concentration on the surface of the pipeline is reduced, the possibility of failure of the pipeline body caused by hydrogen permeation and hydrogen induced cracking in the pipeline wall matrix is reduced, and the hydrogen pipeline is protected; the natural gas additive based on competitive adsorption is any one of alkane, alkene or a compound containing three elements of C, H and O; preferably, the organic substance is one of alcohols and ethers.
The invention has the beneficial effects that:
1. in the method for protecting the pipeline in the presence of hydrogen, the natural gas additive based on competitive adsorption can be injected in stages, so that the defects of high one-time cost and high investment in replacing steel and coating an inner coating are overcome.
2. In the method for protecting the pipeline in the presence of hydrogen, the process of injecting the natural gas additive based on competitive adsorption into the pipeline in the presence of hydrogen is simple, and the injection of a drag reducer and a corrosion inhibitor in the natural gas pipeline can be used for reference, so that the problems of expensive coating equipment, complex coating process, difficult guarantee of coating quality and the like in the pipeline in the presence of hydrogen are solved.
3. In the method for protecting the hydrogen pipeline, the natural gas additive based on competitive adsorption has wide application range, and both hydrogen-doped or pure hydrogen conveying pipelines can be used. For pipelines which are not coated with an inner coating in service, small-caliber low-pressure short-distance gas transmission pipelines, pipelines with coatings falling off and the like, the hydrogen-resistant transformation can be realized by injecting additives.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram showing the dimensions of a hydrogen-charged tensile specimen in Experimental example 1 of the present invention;
FIG. 2 shows 7MPa CH in Experimental example 1 of the present invention 4 +3MPa H 2 And (3) comparing the mechanical tensile stress-strain curve of the sample after hydrogen charging under the condition of ethanol and the sample under the air condition.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned above, the prior art is difficult to reform the natural gas pipeline in hydrogen resistance, and the problems of high investment cost, difficult construction and poor applicability exist in both steel replacement and inner coating. In view of the above, the invention provides a hydrogen-resistant reforming method for a hydrogen pipeline based on competitive adsorption, which solves the problems of high construction cost, difficult construction and poor applicability of the hydrogen pipeline in hydrogen-resistant reforming of a natural gas pipeline, and increases the flexibility of hydrogen energy transmission.
The invention provides an application of a natural gas additive based on competitive adsorption in the protection of a hydrogen pipeline, wherein the additive is any one of alkane, olefin or a compound containing three elements of C, H and O; preferably one of alcohols and ethers; more preferably one of methanol, ethanol, propanol and diethyl ether.
The action principle of the natural gas additive based on competitive adsorption is as follows: and the hydrogen molecule concentration on the metal surface is reduced. The method specifically comprises the following steps: the competitive adsorption of methane and hydrogen is intensified on the metal surface of the hydrogen pipeline, so that the beneficial effect of reducing the hydrogen molecule concentration on the metal surface is achieved; or the natural gas additive components based on competitive adsorption and hydrogen have competitive adsorption, so that the beneficial effect of reducing the hydrogen molecule concentration on the metal surface is achieved, the hydrogen embrittlement coefficient of the pipeline steel is finally reduced, and the hydrogen embrittlement resistance is provided for the pipeline steel.
In another exemplary embodiment of the present invention, a method for protecting a pipeline in hydrogen using a natural gas additive based on competitive adsorption is provided, in which the natural gas additive based on competitive adsorption is injected into the pipeline in hydrogen, so as to reduce the concentration of hydrogen molecules on the inner surface of the pipeline, reduce the possibility of failure of the pipeline body caused by hydrogen permeation and hydrogen induced cracking in the matrix of the pipeline wall, and protect the pipeline in hydrogen; the natural gas additive based on competitive adsorption is any one of alkane, alkene or a compound containing three elements of C, H and O; preferably one of alcohols and ethers; more preferably one of methanol, ethanol, propanol and diethyl ether.
In some embodiments of this embodiment, the hydrogen pipeline is a hydrogen pipeline or a natural gas-loaded hydrogen pipeline made of metal.
The implantation method of the present invention is not particularly limited, and in some embodiments, the implantation method is: injecting a natural gas additive based on competitive adsorption into a hydrogen pipeline in an injection mode; in some embodiments, the spray injection is carried out by means of atomization injection, and the spray injection can be selected automatically according to working conditions.
In some embodiments of this embodiment, the injection is performed by atomizing injection, the additive is atomized into tiny droplets by a high-pressure pump and an atomizing nozzle installed at the inlet of the pipeline, and the atomized droplets of the additive are carried by the high-speed airflow into the hydrogen pipeline. The additive liquid drops which are fully atomized uniformly float in the natural gas transported by the pipe, flow along with the flow of the hydrogen, uniformly strike the pipe wall or a layer close to the pipe wall by means of the turbulent diffusion effect when the high-pressure gas in the pipeline flows, and finally attach to the surface of the pipe wall to play the role of reducing the hydrogen concentration on the surface of the pipe wall.
In some embodiments of the embodiment, the additive is injected in an optional and staged mode, so that the defect of high investment cost for replacing steel and coating the inner coating at one time is overcome.
In some examples of this embodiment, the competitive adsorption-based natural gas additive is essentially characterized by: under the condition of the operating temperature along the hydrogen pipeline, the saturated vapor pressure of the natural gas additive based on competitive adsorption is not higher than the operating pressure along the pipeline, so that the film forming process and the film forming state of the additive on the surface of the pipeline are ensured; for additives that do not separate from the transport gas at the end of the pipeline in which hydrogen is present, a combustion chemical reaction can occur with the air to remove the added natural gas additive based on competitive adsorption by combustion; and the separated natural gas additive based on competitive adsorption is recycled and injected into the hydrogen pipeline again to play a role.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1:
the natural gas additive based on competitive adsorption is applied to the protection of a hydrogen pipeline, and the natural gas additive based on competitive adsorption is ethanol.
The additive can be added into a hydrogen pipeline, so that the concentration of hydrogen molecules on the surface of the hydrogen pipeline is reduced, the possibility of failure of a pipe body caused by hydrogen permeation and hydrogen induced cracking in a metal matrix of a pipe wall is reduced, and the hydrogen pipeline is protected.
Experimental example 1:
in order to verify whether the additive in the embodiment 1 of the invention has the effect of reducing the possibility of tube body failure caused by hydrogen permeation and hydrogen induced cracking in the metal matrix of the tube wall, the following test verification is specially made:
the principle is as follows: the change of the hydrogen brittleness sensitivity of the metal sample after hydrogen filling under the condition of no additive is tested by experiments to judge whether the additive in the embodiment 1 has the effect of reducing the possibility of tube body failure caused by hydrogen permeation and hydrogen induced cracking in the metal matrix of the tube wall.
(1) Processing X80 steel into a bar sample with the shape and the size as shown in figure 1, polishing a test area by using sand paper to remove processing traces, washing and degreasing, and then putting into a reaction kettle for sealing;
(2) After the sample is packaged, repeatedly purging the reaction kettle for three times by adopting 1MPa nitrogen, and replacing the air in the kettle;
(3) Filling 3MPa hydrogen, filling 7MPa methane, and filling hydrogen for 24 hours in the sample under the condition of 10MPa mixed gas and room temperature;
(4) And taking out the sample from the reaction kettle after the specified hydrogen charging time, immediately performing a mechanical tensile experiment at a tensile rate of 2mm/min, recording the load and deformation borne by the sample in real time, and calculating to obtain a stress-strain curve according to the load and deformation.
Ethanol is used as an additive, the ethanol is fully atomized and sprayed on the surface of the bar before sealing in the experimental process, and the ethanol which does not exceed the gauge length section of the bar is added into the reaction kettle, so that the stress-strain curve is obtained after the experiment is finished, and is shown in figure 2.
As can be seen from FIG. 2, due to the existence of ethanol, the H is 3MPa 2 +7MPa CH 4 The stress-strain curve of the sample with hydrogen embrittlement under the environment is closer to that of the steel directly stretched in the air. The elongation after fracture of the bar under the condition of mixed gas, the condition of mixed gas and ethanol and the air is respectively 20.03%, 25.20% and 24.48%, so that the ethanol is used as an additive to be injected into the hydrogen pipeline, the hydrogen embrittlement sensitivity of the pipeline steel under the hydrogen-doped natural gas is reduced, the mechanical property of the pipeline steel is improved, the hydrogen resistance of the hydrogen pipeline is improved, and the protection of the hydrogen pipeline is realized.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The application of the natural gas additive based on competitive adsorption in the protection of the hydrogen pipeline is characterized in that the additive is any one of alkane, alkene or a compound containing three elements of C, H and O.
2. The use of claim 1, wherein the additive is one of an alcohol and an ether organic.
3. The use of claim 1, wherein the additive is one of methanol, ethanol, propanol, and diethyl ether.
4. The use according to claim 1 wherein the additive has a saturated vapour pressure not higher than the operating pressure along the conduit at the operating temperature along the conduit in the presence of hydrogen.
5. A hydrogen-resistant reconstruction method for a hydrogen pipeline by using a natural gas additive based on competitive adsorption is characterized in that the natural gas additive based on competitive adsorption is injected into the hydrogen pipeline, the concentration of hydrogen molecules on the inner surface of the pipeline is reduced, the possibility of failure of a pipe body caused by hydrogen permeation and hydrogen induced cracking in a pipe wall matrix is reduced, and the hydrogen pipeline is protected;
the natural gas additive based on competitive adsorption is any one of alkane, alkene or a compound containing three elements of C, H and O; preferably one of alcohols and ethers; more preferably one of methanol, ethanol, propanol and diethyl ether.
6. The method of claim 5, wherein the pipeline is a metal pipeline for transporting hydrogen or natural gas.
7. The method of claim 5, wherein the injection comprises: and injecting the natural gas additive based on competitive adsorption into the hydrogen pipeline in an injection mode.
8. The method of claim 7, wherein the injection comprises: the additive is sprayed in an atomizing injection mode, the additive is atomized into tiny droplets through a high-pressure pump and an atomizing nozzle arranged at the inlet of a pipeline, and the atomized additive droplets are carried by high-speed airflow and enter a hydrogen-contacting pipeline.
9. The method of hydrogen pipeline hydrogen withstand retrofit of claim 5 wherein the injecting is staged.
10. The hydrogen tolerant reforming process of claim 5 wherein the natural gas additive based on competitive adsorption has a saturated vapor pressure not higher than the operating pressure along the pipeline at the operating temperature along the pipeline.
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