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 adsorptionDownload PDFInfo
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- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- 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
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
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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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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明涉及天然气掺氢管输技术领域，尤其涉及一种利用基于竞争吸附的天然气添加剂的临氢管道耐氢改造方法。The invention relates to the technical field of natural gas hydrogen-mixed pipeline transportation, in particular to a hydrogen-resistant transformation method of a hydrogen-adjacent pipeline using a natural gas additive based on competitive adsorption.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
作为解决“弃风弃光”等可再生能源消纳问题的有效途径，天然气掺氢管输工艺发展面临的主要问题为管道钢氢脆问题，且管道钢强度越高越易受氢影响，进而力学性能退化，造成管道脆断、泄漏等事故。As an effective way to solve the problem of "abandoning wind and light" and other renewable energy consumption problems, the main problem faced by the development of natural gas hydrogen-mixed pipeline transportation technology is the hydrogen embrittlement problem of pipeline steel, and the higher the strength of pipeline steel, the more susceptible it is to hydrogen. The mechanical properties are degraded, causing accidents such as brittle fracture and leakage of the pipeline.
目前为提高临氢钢材的抗氢脆能力可以通过钢材改性和表面改性两种方法。其中钢材改性无法用于已建成的天然气管道，即便对于新建天然气管道，采用强度高的耐氢不锈钢会使得建设成本过高，而采用低强度管道钢则限制了管道的设计压力，降低输送效率；对于表面改性，多种阻氢涂层类产品应用在了高压储氢设备中，但长距离大管径的高压天然气管道相比储氢容器涂敷面积大得多，存在涂料使用成本高、脱落后难修复以及涂敷困难的问题。At present, in order to improve the resistance to hydrogen embrittlement of hydrogen steel, there are two methods: steel modification and surface modification. Among them, steel modification cannot be used for existing natural gas pipelines. Even for new natural gas pipelines, the use of high-strength hydrogen-resistant stainless steel will make the construction cost too high, while the use of low-strength pipeline steel will limit the design pressure of the pipeline and reduce the transmission efficiency. ; For surface modification, a variety of hydrogen barrier coating products are used in high-pressure hydrogen storage equipment, but the coating area of long-distance and large-diameter high-pressure natural gas pipelines is much larger than that of hydrogen storage containers, and the cost of using coatings is high. , difficult to repair after falling off and difficult to apply.
鉴于此，为克服以上现有技术中的不足，提出一种大规模、长距离的高压、高掺氢比天然气输送管道的耐氢改造方法成为本领域亟待解决的技术问题。In view of this, in order to overcome the above deficiencies in the prior art, it has become an urgent technical problem to be solved in the art to propose a large-scale, long-distance, high-pressure, high-hydrogen ratio natural gas pipeline transformation method for hydrogen resistance.
发明内容SUMMARY OF THE INVENTION
为了解决现有技术的不足，本发明的目的是一种利用基于竞争吸附的天然气添加剂的临氢管道耐氢改造方法。本发明针对材质为金属的氢气输送管道或者天然气掺氢输送管道，采用喷注添加剂的方式，将基于竞争吸附的天然气添加剂注入到临氢管道内，降低临氢管道表面氢气分子浓度，降低管壁金属基体中氢渗透、氢致开裂引发管体失效的可能性，实现对临氢管道的保护。In order to solve the deficiencies of the prior art, the purpose of the present invention is a hydrogen-resistant transformation method for a hydrogen pipeline using a natural gas additive based on competitive adsorption. Aiming at the hydrogen transmission pipeline or the natural gas hydrogen-mixed transmission pipeline made of metal, the invention injects the natural gas additive based on competitive adsorption into the hydrogen adjacent pipeline by injecting the additive, so as to reduce the hydrogen molecular concentration on the surface of the hydrogen adjacent pipeline and reduce the pipe wall. The possibility of pipe failure caused by hydrogen permeation and hydrogen-induced cracking in the metal matrix realizes the protection of hydrogen pipelines.
为了实现上述目的，本发明的技术方案为：In order to achieve the above object, the technical scheme of the present invention is:
一方面，基于竞争吸附的天然气添加剂在临氢管道保护中的应用，所述添加剂为烷烃、烯烃或含有C、H、O三种元素的化合物中的任一种，优选为醇类、醚类有机物中的一种，进一步优选为甲醇、乙醇、丙醇、乙醚中的一种。On the one hand, the application of a natural gas additive based on competitive adsorption in the protection of hydrogen pipelines, the additive is any one of alkanes, olefins or compounds containing three elements of C, H and O, preferably alcohols, ethers One of the organic substances, more preferably one of methanol, ethanol, propanol, and diethyl ether.
另一方面，利用基于竞争吸附的天然气添加剂的临氢管道保护方法，向临氢管道内注入基于竞争吸附的天然气添加剂，降低管道表面氢气分子浓度，降低管壁基体中氢渗透、氢致开裂引发管体失效的可能性，实现对临氢管道的保护；所述基于竞争吸附的天然气添加剂为烷烃、烯烃或含有C、H、O三种元素的化合物中的任一种；优选为醇类、醚类有机物中的一种。On the other hand, the hydrogen pipeline protection method based on competitive adsorption of natural gas additives is used to inject natural gas additives based on competitive adsorption into the hydrogen pipeline to reduce the concentration of hydrogen molecules on the surface of the pipeline, and reduce the hydrogen permeation and hydrogen-induced cracking in the pipe wall matrix. The possibility of failure of the pipe body to achieve the protection of the hydrogen pipeline; the natural gas additive based on competitive adsorption is any one of alkanes, olefins or compounds containing three elements of C, H and O; preferably alcohols, A kind of ether organic.
本发明的有益效果为：The beneficial effects of the present invention are:
1、本发明的临氢管道保护方法中，基于竞争吸附的天然气添加剂可分期加注，克服了更换钢材和涂敷内涂层一次性成本投资高的缺点。1. In the hydrogen pipeline protection method of the present invention, the natural gas additive based on competitive adsorption can be added in stages, which overcomes the shortcomings of high one-time investment in replacing steel and applying inner coating.
2、本发明的临氢管道保护方法中，基于竞争吸附的天然气添加剂注入临氢管道内的工艺简单，可以借鉴天然气管道中减阻剂、缓蚀剂的喷注方式注入，进而解决临氢管道内涂层涂敷设备昂贵，涂敷工艺复杂，涂层质量难以保证等问题。2. In the hydrogen pipeline protection method of the present invention, the process of injecting natural gas additives into the hydrogen pipeline based on competitive adsorption is simple, and the injection method of drag reducer and corrosion inhibitor in the natural gas pipeline can be used for reference, so as to solve the problem of the hydrogen pipeline. The inner coating coating equipment is expensive, the coating process is complicated, and the coating quality is difficult to guarantee.
3、本发明的临氢管道保护方法中，基于竞争吸附的天然气添加剂适用范围广，掺氢或纯氢输送管道均可使用。对于在役未涂敷内涂层的管道、小口径低压短距离输气管道及涂层脱落的管道等，均可以通过注入添加剂的方法实现耐氢改造。3. In the hydrogen pipeline protection method of the present invention, the natural gas additive based on competitive adsorption has a wide application range, and can be used in hydrogen-doped or pure hydrogen pipelines. For pipelines without inner coating in service, small-diameter low-pressure short-distance gas pipelines and pipelines with peeling coatings, etc., hydrogen-resistant transformation can be achieved by injecting additives.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1是本发明实验例1中充氢拉伸试样尺寸示意图；1 is a schematic diagram of the size of a hydrogen-charged tensile sample in Experimental Example 1 of the present invention;
图2是本发明实验例1中7MPa CH4+3MPa H2条件下有、无乙醇条件下充氢后样本与空气条件下样本的力学拉伸应力-应变曲线对比图。2 is a comparison diagram of the mechanical tensile stress-strain curves of the samples after hydrogen charging with and without ethanol under the conditions of 7MPa CH4 +3MPa H2 in Experimental Example 1 of the present invention and the samples under air conditions.
具体实施方式Detailed ways
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, 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.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.
如前所述，现有技术难以对天然气管道进行耐氢改造，无论是更换钢材还是内涂层涂敷都存在一次性成本投资高、施工困难，且适用性差的问题。鉴于此，本发明提供了一种利用基于竞争吸附吸附的临氢管道耐氢改造方法，解决了天然气管道耐氢改造中氢气管道建设成本高、施工困难且适用性差的难题，增加了氢能输送的灵活性。As mentioned above, it is difficult to carry out hydrogen-resistant transformation of natural gas pipelines in the existing technology. Whether it is steel replacement or inner coating application, there are problems of high one-time cost investment, difficult construction, and poor applicability. In view of this, the present invention provides a hydrogen-resistant transformation method for hydrogen pipelines based on competitive adsorption, which solves the problems of high construction cost, difficult construction and poor applicability of hydrogen pipelines in hydrogen-resistant transformation of natural gas pipelines, and increases hydrogen energy transportation. flexibility.
本发明的一种典型实施方式，提供基于竞争吸附的天然气添加剂在临氢管道保护中的应用，所述添加剂为烷烃、烯烃或含有C、H、O三种元素的化合物中的任一种；优选为醇类、醚类有机物中的一种；进一步优选为甲醇、乙醇、丙醇、乙醚中的一种。A typical embodiment of the present invention provides the application of a natural gas additive based on competitive adsorption in the protection of hydrogen pipelines, wherein the additive is any one of alkanes, olefins or compounds containing three elements of C, H, and O; Preferably, it is one of alcohols and ethers; more preferably, it is one of methanol, ethanol, propanol, and diethyl ether.
其中，基于竞争吸附的天然气添加剂的作用原理为：降低金属表面氢气分子浓度。具体为：在临氢管道金属表面加剧甲烷与氢气的竞争吸附，达到降低金属表面氢气分子浓度的有益效果；或，基于竞争吸附的天然气添加剂成分与氢气存在竞争吸附，达到降低金属表面氢气分子浓度的有益效果，最终实现降低管道钢氢脆系数，为管道钢提供抗氢脆能力。Among them, the action principle of the natural gas additive based on competitive adsorption is to reduce the concentration of hydrogen molecules on the metal surface. Specifically: intensifying the competitive adsorption of methane and hydrogen on the metal surface of the hydrogen pipeline to achieve the beneficial effect of reducing the concentration of hydrogen molecules on the metal surface; or, based on the competitive adsorption of natural gas additive components and hydrogen competitive adsorption, to reduce the concentration of hydrogen molecules on the metal surface The beneficial effect is finally realized to reduce the hydrogen embrittlement coefficient of the pipeline steel, and provide the anti-hydrogen embrittlement ability for the pipeline steel.
本发明的另一种典型实施方式，提供一种利用基于竞争吸附的天然气添加剂的临氢管道保护方法，向临氢管道内注入基于竞争吸附的天然气添加剂，降低管道内表面氢气分子浓度，降低管壁基体中氢渗透、氢致开裂引发管体失效的可能性，实现对临氢管道的保护；所述基于竞争吸附的天然气添加剂为烷烃、烯烃或含有C、H、O三种元素的化合物中的任一种；优选为醇类、醚类有机物中的一种；进一步优选为甲醇、乙醇、丙醇、乙醚中的一种。Another typical embodiment of the present invention provides a method for protecting a hydrogen pipeline using a natural gas additive based on competitive adsorption, injecting a natural gas additive based on competitive adsorption into the hydrogen pipeline, reducing the concentration of hydrogen molecules on the inner surface of the pipeline, reducing the The possibility of failure of the pipe body caused by hydrogen permeation and hydrogen-induced cracking in the wall matrix realizes the protection of the hydrogen pipeline; the natural gas additive based on competitive adsorption is alkane, alkene or a compound containing three elements of C, H and O. Any one; preferably one of alcohols and ethers; more preferably one of methanol, ethanol, propanol, and ether.
该实施方式的一些实施例中，所述临氢管道为材质为金属的氢气输送管道或天然气掺氢输送管道。In some examples of this embodiment, the hydrogen pipeline is a metal hydrogen transmission pipeline or a natural gas hydrogen-mixed transmission pipeline.
本发明中注入的方式并不作特殊的限定，在一些实施例中，所述注入为：采用喷注的方式，将基于竞争吸附的天然气添加剂注入到临氢管道内；在一些实施例中，采用雾化注入的方式喷注，可根据工况进行自主选择。The injection method in the present invention is not particularly limited. In some embodiments, the injection is: injecting the natural gas additive based on competitive adsorption into the hydrogen pipeline by means of injection; in some embodiments, using The method of atomization injection can be independently selected according to the working conditions.
该实施方式的一些实施例中，所述注入为采用雾化注入的方式喷注，通过高压泵和安装在管道入口的雾化喷嘴将添加剂雾化成微小的液滴，由高速气流携带雾化的添加剂液滴进入临氢管道。充分雾化的添加剂液滴均匀漂浮在管输天然气中，随着氢气的流动而流动，并依靠管道内高压气体流动时的紊动扩散作用均匀地打击管壁或近壁层，最终附着在管壁表面，发挥其降低管壁表面氢浓度的作用。In some examples of this embodiment, the injection is in the form of atomized injection, and 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 liquid is carried by a high-speed airflow. Additive droplets enter the hydrogen pipeline. The fully atomized additive droplets evenly float in the pipeline natural gas, flow with the flow of hydrogen, and rely on the turbulent diffusion of the high-pressure gas in the pipeline to evenly hit the pipe wall or near-wall layer, and finally adhere to the pipe wall. The wall surface plays a role in reducing the hydrogen concentration on the pipe wall surface.
该实施方式的一些实施例中，注入添加剂的方式可选分期注入，以克服更换钢材和涂敷内涂层一次性成本投资高的缺点。In some examples of this embodiment, the injection of the additive can be done in stages, so as to overcome the disadvantages of high one-time investment in steel replacement and inner coating application.
该实施方式的一些实施例中，基于竞争吸附的天然气添加剂的基本特点为：在临氢管道沿线运行温度条件下，基于竞争吸附的天然气添加剂的饱和蒸气压不高于管道沿线运行压力，以保证抗添加剂在管道表面的成膜过程以及成膜状态；对于不在临氢管道运输终点与输送气体分离的添加剂，可与空气发生燃烧化学反应，以通过燃烧去除添加的基于竞争吸附的天然气添加剂；对于在临氢管道终点分离的添加剂无成分要求，分离出的基于竞争吸附的天然气添加剂回收再次注入临氢管道内发挥作用。In some examples of this embodiment, the basic feature of the natural gas additive based on competitive adsorption is: under the operating temperature conditions 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 to ensure that The film formation process and film formation state of the anti-additives on the pipeline surface; for the additives that are not separated from the conveying gas at the transportation end of the hydrogen pipeline, they can undergo a combustion chemical reaction with air to remove the added natural gas additives based on competitive adsorption through combustion; The additive separated at the end of the hydrogen pipeline has no component requirements, and the separated natural gas additive based on competitive adsorption is recycled and injected into the hydrogen pipeline to play a role.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
实施例1：Example 1:
基于竞争吸附的天然气添加剂在临氢管道保护中的应用，基于竞争吸附的天然气添加剂为乙醇。Application of a natural gas additive based on competitive adsorption in the protection of hydrogen pipelines. The natural gas additive based on competitive adsorption is ethanol.
本发明添加剂可加入到临氢管道中，降低临氢管道表面氢气分子浓度，降低管壁金属基体中氢渗透、氢致开裂引发管体失效的可能性，实现对临氢管道的保护。The additive of the invention can be added to the hydrogen pipeline to reduce the concentration of hydrogen molecules on the surface of the hydrogen pipeline, reduce the possibility of failure of the pipe body caused by hydrogen permeation and hydrogen-induced cracking in the metal matrix of the pipe wall, and realize the protection of the hydrogen pipeline.
实验例1：Experimental example 1:
为验证本发明实施例1中添加剂是否有降低管壁金属基体中氢渗透、氢致开裂引发管体失效的可能性的作用，特作出以下试验验证：In order to verify whether the additive in Example 1 of the present invention has the effect of reducing the possibility of hydrogen permeation and hydrogen-induced cracking in the metal matrix of the pipe wall causing the failure of the pipe body, the following experimental verification is made:
原理：通过实验测试有无添加剂条件下充氢后金属试样拉伸的氢脆敏感性变化判定实施例1的添加剂是否有降低管壁金属基体中氢渗透、氢致开裂引发管体失效的可能性的作用。Principle: Determine whether the additive in Example 1 reduces the possibility of hydrogen permeation and hydrogen-induced cracking in the metal matrix of the pipe wall causing the failure of the pipe body by experimentally testing the change in the hydrogen embrittlement sensitivity of the metal sample after hydrogen charging with or without additives. the role of sex.
(1)将X80钢加工成如图1所示形状尺寸的棒材样本后，采用砂纸打磨试验区去除加工痕迹，冲洗脱脂后放入反应釜内密封；(1) After processing the X80 steel into a bar sample of the shape and size as shown in Figure 1, use sandpaper to polish the test area to remove the processing marks, rinse and degreasing, and put it into the reactor to seal;
(2)试样封装完成后，采用1MPa氮气反复吹扫反应釜三次，置换掉釜内空气；(2) After the sample is packaged, use 1MPa nitrogen to repeatedly purge the reaction kettle three times to replace the air in the kettle;
(3)充入3MPa氢气，再充入7MPa甲烷后将试样于10MPa混合气、室温条件下内充氢24h；(3) Charge 3MPa hydrogen, and then charge 7MPa methane, then charge the sample with hydrogen at 10MPa mixed gas and room temperature for 24h;
(4)至规定充氢时间后，从反应釜中拿出试样立刻进行力学拉伸实验，拉伸速率为2mm/min，并实时记录试样承受的载荷和变形量，据此计算得到应力-应变曲线。(4) After the specified hydrogen charging time, take out the sample from the reactor and immediately carry out the mechanical tensile test. The tensile rate is 2 mm/min, and the load and deformation of the sample are recorded in real time, and the stress is calculated accordingly. - Strain curve.
以乙醇作为添加剂，在上述实验过程中密封前将乙醇充分雾化喷洒在棒材表面，并在反应釜内加入不没过棒材标距段的乙醇，完成上述试验后得到应力应变曲线如图2。Using ethanol as an additive, in the process of the above experiment, the ethanol was fully atomized and sprayed on the surface of the bar before sealing, and ethanol that did not exceed the gauge length of the bar was added to the reaction kettle. After completing the above test, the stress-strain curve was obtained as shown in the figure. 2.
通过图2可以发现，由于乙醇的存在使得本该在3MPa H2+7MPa CH4环境下出现氢脆现象的样本的应力-应变曲线更接近在空气中直接拉伸的钢的应力-应变曲线。混合气条件下、混合气加乙醇条件下、空气条件下棒材的断后伸长率分别为20.03％、25.20％、24.48％，由此可以说明乙醇作为添加剂注入到临氢管道内，起到了降低管道钢在掺氢天然气下的氢脆敏感性的作用，提高了管道钢的力学性能，提高了临氢管道的耐氢性能，实现了临氢管道的保护。It can be found from Fig. 2 that, due to the presence of ethanol, the stress-strain curve of the sample that should have hydrogen embrittlement in the environment of 3MPa H2 +7MPa CH4 is closer to the stress-strain curve of the steel directly stretched in air. Under the condition of mixed gas, under the condition of mixed gas with ethanol, and under the condition of air, the elongation after fracture of the bar is 20.03%, 25.20%, and 24.48%, respectively, which shows that ethanol is injected into the hydrogen pipeline as an additive, which reduces the The role of the hydrogen embrittlement sensitivity of pipeline steel under hydrogen-doped natural gas improves the mechanical properties of pipeline steel, improves the hydrogen resistance of hydrogen-adjacent pipelines, and realizes the protection of hydrogen-adjacent pipelines.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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