CN115094314A - Special pipeline alloy for hydrogen energy, pipeline and preparation method of pipeline - Google Patents

Special pipeline alloy for hydrogen energy, pipeline and preparation method of pipeline Download PDF

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CN115094314A
CN115094314A CN202210692465.2A CN202210692465A CN115094314A CN 115094314 A CN115094314 A CN 115094314A CN 202210692465 A CN202210692465 A CN 202210692465A CN 115094314 A CN115094314 A CN 115094314A
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hydrogen
pipeline
less
alloy
special
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曾泽瑶
罗许
刘序江
胡浩然
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0639—Steels
    • F17C2203/0643—Stainless steels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00—Vessel construction, in particular methods of manufacturing
    • F17C2209/21—Shaping processes
    • F17C2209/2181—Metal working processes, e.g. deep drawing, stamping or cutting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

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Abstract

The invention provides a pipeline alloy special for hydrogen energy, a pipeline and a preparation method of the pipeline, wherein the alloy comprises the following elements in percentage by mass: c: 0.02 to 0.04%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 16-21%, Al: 1.2-2%, Ti 1-2%, V: 0.08 to 0.3, Nb: 0.06-0.3, B: 0.0015-0.0028, N: less than 0.0005%, Ni: 25-33%, Mo: 1-3%, Cu: 2-4.5%, and satisfies the condition that Ti + Al is less than 4%, Ti/Al is approximately equal to 0.6-1.0, V + Nb is less than or equal to 0.6%, and the balance is Fe and inevitable impurities; the pipeline comprises a gamma' -strengthening phase which is composed of Ni, Al and Ti and has an average grain diameter of less than 100 nm; the preparation method of the pipeline comprises a heat treatment process of tempering treatment at 670-850 ℃. The technical scheme of the invention solves the problem that the conventional natural gas pipeline adopted for conveying pure hydrogen in the prior art does not have hydrogen loss resistance.

Description

Special pipeline alloy for hydrogen energy, pipeline and preparation method of pipeline
Technical Field
The invention relates to the technical field of design of materials for hydrogen energy industrial pipelines, in particular to a special pipeline alloy for hydrogen energy, a pipeline and a preparation method of the pipeline.
Background
Hydrogen energy is a clean energy which is currently concerned, various hydrogen production and purification technologies are available at present, the hydrogen is widely applied in the civil and industrial fields, the hydrogen is an important secondary energy in the new century, and the development and utilization of the hydrogen energy are one of the important directions of energy transformation in China. Because hydrogen is easy to permeate into the hydrogen material, hydrogen induced plasticity loss, namely hydrogen brittleness, is caused, and along with the increase of the hydrogen pressure and the concentration, higher requirements on the hydrogen brittleness resistance of the material are made. The mature hydrogen storage and transportation technology utilizes a pressure vessel and a high-pressure pipeline to store and transport hydrogen in a high-pressure gaseous hydrogen form, but the hydrogen brittleness problem of metal vessels and pipelines is one of the difficulties for large-scale popularization as natural gas and even long-distance transportation as western gas is transported from east to east.
With the popularization and utilization of hydrogen, hydrogen conveying pipelines are widely applied to scenes such as hydrogenation stations, fuel cell automobiles, industrial plants and the like. The diameter of the hydrogen conveying pipe is large or small, the conveying pressure range is also large, the diameter is as low as 0.1MPa, and the diameter is as large as 100 MPa; the difference of the use amount is very large. The hydrogen transportation pipeline also has the characteristics that the newly-built hydrogen pipeline can meet the hydrogen resistance grade in a matched environment.
The pipeline is in contact with hydrogen for a long time, and the hydrogen can invade into the pipeline material, so that the metal material is damaged and has high crack expansion speed and low fracture toughness. The conventional natural gas pipeline used for conveying pure hydrogen in the prior art has no hydrogen loss resistance.
Disclosure of Invention
According to the technical problem that a conventional natural gas pipeline adopted for conveying pure hydrogen in the prior art does not have the capability of resisting hydrogen loss, the special pipeline alloy for hydrogen energy, the pipeline and the preparation method of the pipeline are provided, and the nanoscale gamma' -enhanced phase is used as a capture site of hydrogen in steel to adsorb non-diffusible hydrogen so as to inhibit hydrogen brittleness.
The technical means adopted by the invention are as follows:
a pipeline alloy special for hydrogen energy comprises the following elements in percentage by mass:
c: 0.02-0.04%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 16-21%, Al: 1.2-2%, Ti 1-2%, V: 0.08 to 0.3, Nb: 0.06-0.3, B: 0.0015-0.0028, N: less than 0.0005%, Ni: 25-33%, Mo: 1-3%, Cu: 2-4.5%, and satisfies the condition that Ti + Al is less than 4%, Ti/Al is approximately equal to 0.6-1.0, V + Nb is less than or equal to 0.6%, and the balance is Fe and inevitable impurities.
Furthermore, the alloy has yield strength of 620-680 MPa, tensile strength of 1080-1280 MPa and elongation after fracture of 38-45%; after hydrogen is charged under the conditions of 200 ℃, 0.1Mpa, 72 hours or 300 ℃, 0.1Mpa and 48 hours, the elongation after fracture is 36-42%, the hydrogen induced plasticity loss is less than 8%, and the hydrogen content is 5-20 ppm.
Further, the method is used for a high-pressure hydrogen storage container or a seamless pipe for high-pressure hydrogen transportation.
The invention also provides a special pipeline for hydrogen energy, which adopts the alloy as claimed in claim 1, and comprises a gamma prime strengthening phase consisting of Ni, Al and Ti and having an average grain diameter of less than 100 nm.
Further, the average particle size of the gamma' -reinforcing phase is 20-80 nm.
Further, the pipeline is used for a high-pressure bearing structural material of a hydrogen storage container or a non-pipeline material of a heat exchanger and a regulating valve in a high-pressure pure hydrogen environment of 30-90 MPa.
The invention also provides a preparation method of the special hydrogen energy pipeline, which comprises the following steps:
s1: preparing materials according to elements contained in the alloy components and corresponding mass percentages, smelting to obtain steel ingots, and homogenizing the steel ingots;
s2: the homogenized steel ingot is subjected to cogging forging to form a bar, and is subjected to water cooling after being homogenized again or is directly transferred to an extruder to be punched to be used as an original blank;
s3: sequentially carrying out perforation, extrusion, acid washing, cold rolling, straight operation, heat treatment, acid washing and finishing on an original blank to obtain a finished product of the hydrogen energy special pipeline with a strengthening phase less than 100 nm; wherein the heat treatment is the tempering treatment at 670-850 ℃.
Further, the tempering temperature is 840 ℃.
Compared with the prior art, the invention has the following advantages:
the pipeline prepared by the special pipeline alloy for hydrogen energy, the pipeline and the preparation method of the pipeline provided by the invention have high hydrogen resistance level, good comprehensive performance in a high-pressure hydrogen environment, high safety level and capability of ensuring the strength use requirement in the high-pressure hydrogen environment and avoiding safety accidents such as explosion, leakage and the like.
Based on the reasons, the invention can be widely popularized in the field of hydrogen energy industrial pipelines.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a drawing of a nanoscale gamma prime strengthening phase in a tube according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
The invention provides a pipeline alloy special for hydrogen energy, which comprises the following elements in percentage by mass:
c: 0.02 to 0.04%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 16-21%, Al: 1.2-2%, Ti 1-2%, V: 0.08 to 0.3, Nb: 0.06-0.3, B: 0.0015-0.0028, N: less than 0.0005%, Ni: 25-33%, Mo: 1-3%, Cu: 2-4.5%, and satisfies the condition that Ti + Al is less than 4%, Ti/Al is approximately equal to 0.6-1.0, V + Nb is less than or equal to 0.6%, and the balance is Fe and inevitable impurities.
Further, the yield strength of the alloy is 620-680 MPa, the tensile strength is 1080-1280 MPa, and the elongation after fracture is 38-45%; before and after hydrogen charging, the strength of the material is basically unchanged, the hydrogen induced plasticity loss is less than 8%, and the fracture surface does not have brittle fracture characteristics after hydrogen charging.
Processing the alloy provided by the invention into a smooth disc-shaped tensile sample, wherein the surface roughness of the sample is less than 0.7, hydrogen enters the tensile sample through adsorption, dissolution and diffusion by utilizing a high-pressure gas-phase thermal hydrogen charging technology, the hydrogen content in the sample is controlled by changing the hydrogen pressure, the hydrogen charging temperature and the hydrogen charging time, and the hydrogen charging environment is a high-purity hydrogen (99.99%) atmosphere;
the method comprises the steps of (1) charging a sample with hydrogen charging parameters of 200 ℃, 0.1Mpa, 72 hours or 300 ℃, 0.1Mpa and 48 hours, measuring the hydrogen content in the sample after hydrogen charging by using an oxygen nitrogen hydrogen analyzer, measuring the hydrogen content to 5-20 ppm, and then carrying out mechanical property test, wherein the deformation is controlled by adopting a constant strain rate in the mechanical property test, and the deformation rate is controlled to be 0.001 mm/min; through tests, the alloy provided by the invention has a better hydrogen resistance grade, the content of hydrogen elements in hydrogen charging equipment does not linearly increase along with the increase of the hydrogen charging time, temperature and pressure, and the hydrogen is not continuously dissolved in a matrix after the hydrogen content is saturated; after hydrogen charging, the elongation after fracture is 36-42%, and the hydrogen induced plasticity loss is less than 8%;
in conclusion, compared with the common solid solution strengthening hydrogen-resistant austenitic stainless steel, the alloy provided by the invention has higher strength, relatively less hydrogen induced plasticity loss capacity and good comprehensive performance.
Further, the method is used for a high-pressure hydrogen storage container or a seamless pipe for high-pressure hydrogen transportation.
Further, the alloy can be used for a hydrogen station or a hydrogen storage container of a hydrogen fuel cell transportation tool which takes pure hydrogen as power and has the grades of 30MPa, 45MPa, 60MPa and 70MPa to bear high-pressure structure.
The process principle of the design of the special pipeline alloy for hydrogen energy provided by the invention is as follows:
(1) c is an austenite forming element, and in the invention, C can obviously improve the strength of the alloy and precipitate M under a specific heat treatment process system 23 C 6 MX and the like can improve the overall strength of the alloy, but in the Cr alloyed (16-28%) iron-nickel base alloy, the temperature is 650-850 DEG CIn the enclosure, M 23 C 6 The precipitation of MX and the like can cause intergranular poor Cr, at the moment, the intergranular corrosion sensitivity is increased, the hydrogen-induced expansion rate along the crystal cracks is greatly improved, and the hydrogen-induced plasticity loss is large, so that the content of C is controlled to be not more than 0.04 percent;
(2) al and Ti are ferrite forming elements and are main strengthening phase gamma 'forming elements in the high-temperature alloy, generally, the higher the Al and Ti ratio is, the service temperature of parts can be greatly improved, the Al and Ti content in the alloy reaches 10%, the gamma' content can reach 30 vol%, and the high-temperature strengthening alloy is widely applied to large turbine disc forgings.
(3) Cr is the most important corrosion resistant element in stainless steel, Cr is ferrite forming element, the addition amount in austenitic steel is generally 16-21%, the Cr has good acid corrosion resistance, and the nano-scale Cr is formed in the pickling process 2 O 3 The invention is the guarantee of the corrosion resistance, therefore, the invention controls the Cr content to be 18 wt.%;
(4) the main function of Ni is to stabilize austenite phase and improve the low-temperature toughness of the stainless steel, meanwhile, Ni element can also improve the strength of a passivation film and improve the intergranular corrosion resistance, and Ni is used as a forming matrix of gamma' phase and generally has a content of 25-35% in the iron-nickel-based alloy;
(6) cu is an austenitizing element, so that the cold processing performance and the cutting performance of the alloy can be improved, the stability of a surface passivation film is improved, the corrosion resistance of the alloy is improved, and the Cu content is controlled to be 2-4.5% due to the antibacterial performance of the alloy in the medical industry;
(7) v, Nb is ferrite forming element, which is easy to contact with N and C in the solution to form second phase particles Nb (C, N) in the melting process, the melting process controls the dispersibility of the particles, and the grain boundary can be effectively pinned in the solidification process to obtain fine crystal structure; in the heat treatment process, the second phase of VxCy and NbC which is precipitated along the grain boundary can further improve the overall strength of the alloy, and the content of V and Nb is controlled below 0.6 percent.
(8) Mo is a ferrite forming element, and in Cr-Ni austenitic stainless steel, 304 and 316 are different in that 1-2 wt.% of Mo is added to 316, and Mo is a grain boundary strengthening element, so that the performance related to grain boundary strengthening can be obviously improved, particularly the corrosion resistance is improved, the intergranular corrosion resistance is more excellent in the corrosion resistance, particularly the hydrogen embrittlement resistance, and the content of Mo is controlled to be 1-3%;
(9) b is a ferrite forming element, and the addition of B can strongly inhibit the precipitation of a second phase at a crystal boundary, so that the inter-crystal Cr-rich tendency is avoided, and the inter-crystal corrosion resistance, especially the hydrogen embrittlement resistance, can be obviously improved.
The invention also provides a special pipeline for hydrogen energy, which adopts the alloy as claimed in claim 1, and comprises a gamma prime strengthening phase consisting of Ni, Al and Ti and having an average grain diameter of less than 100 nm.
Further, the average particle size of the gamma' -reinforcing phase is 20-80 nm.
Preferably, the gamma prime reinforcing phase has an average particle size of 50 to 80 nm.
Furthermore, the pipeline is used for a high-pressure bearing structural material of a hydrogen storage container or a non-pipeline material of a heat exchanger and a regulating valve in a high-pressure pure hydrogen environment of 30-90 MPa.
The invention also provides a preparation method of the special hydrogen energy pipeline, which comprises the following steps:
s1: preparing materials according to elements contained in the alloy components and corresponding mass percentages, smelting to obtain 3-6 tons of steel ingots, and carrying out homogenization treatment on the steel ingots;
s2: the homogenized steel ingot is cogging forged into a bar with the diameter of 30mm, and is homogenized again at 1100-1150 ℃, and then is cooled by water or directly transferred to an extruder for punching to serve as an original blank;
s3: sequentially carrying out perforation, extrusion, acid washing, cold rolling, straight operation, heat treatment, acid washing and finishing on an original blank to obtain a finished product of the hydrogen energy special pipeline with a strengthening phase less than 100 nm; wherein the heat treatment is tempering treatment at 670-850 ℃, and through the tempering treatment, a nanoscale gamma ' -strengthening phase is uniformly precipitated in a crystal, a gamma ' -strengthening phase is uniformly precipitated in a crystal, and a tempering process is necessary, and if the tempering temperature is not set to be a gamma ' -strengthening phase precipitation sensitive temperature range, a desired fine precipitate cannot be prepared; when the average particle size of the nanoscale gamma '-strengthening phase is less than 50-80 nm, the interface area of the precipitate and the parent phase is small, the degree of lattice mismatching is low, and the hydrogen capturing effect is good, and when the average particle size of the nanoscale gamma' -strengthening phase exceeds 100nm, the interface gap with the parent phase is large, the surface compactness is reduced, and the hydrogen capturing effect is also reduced under the condition.
Further, the parameter of the homogenization treatment in step S1 was 1200 ℃ × 12 h.
Further, the temperature of the tempering treatment was 840 ℃.
Further, the heat treatment is a heat treatment under vacuum conditions or under an inert gas protective atmosphere.
Further, the smelting in step S1 adopts vacuum induction, vacuum consumable electrode or electroslag remelting.
The high-pressure hydrogen energy special pipeline prepared from the alloy provided by the invention has the advantages that in a low-strain-rate tensile test, the tensile strength after high-pressure hydrogen charging is not greatly reduced compared with that in the atmosphere, and the pipeline can be used as a high-pressure hydrogen pipeline for a hydrogen station of an urban hydrogen fuel carrier.
Further, according to different wall thickness designs, the hydrogen conveying pressure of the pipeline provided by the invention can reach 80 MPa.
Example 1
The alloy of the embodiment comprises the following elements in percentage by mass: c: 0.02%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 16%, Al: 2%, Ti: 2%, V: 0.08%, Nb: 0.06%, B: 0.0015%, N: less than 0.0005%, Ni: 25% of Mo; 1%, Cu: 2% and the balance of Fe and inevitable impurities.
Further, the alloy of this example had a yield strength of 680MPa, a tensile strength of 1280MPa, and an elongation after fracture of 38%.
Further, after the alloy of the embodiment is subjected to a hydrogen filling test at 200 ℃, 0.1MPa, 72 hours or 300 ℃, 0.1MPa and 48 hours, the elongation after fracture is 36%, the hydrogen induced plasticity loss is less than 8%, and the hydrogen content is 6 ppm.
Example 2
The alloy of the embodiment comprises the following elements in percentage by mass: c: 0.04%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 21%, Al: 1.2%, Ti: 1%, V: 0.3%, Nb: 0.3%, B: 0.0028%, N: less than 0.0005%, Ni: 33%, Mo: 3%, Cu: 4.5%, and the balance of Fe and inevitable impurities.
Further, the alloy of this example had a yield strength of 620MPa, a tensile strength of 1192MPa, and an elongation after fracture of 45%.
Further, after the alloy of the embodiment is subjected to a hydrogen filling test at 200 ℃, 0.1MPa, 72 hours or 300 ℃, 0.1MPa and 48 hours, the elongation after fracture is 42%, the hydrogen induced plasticity loss is less than 8%, and the hydrogen content is 5 ppm.
Example 3
The alloy of the embodiment comprises the following elements in percentage by mass: c: 0.03%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 19%, Al: 1.4%, Ti 1.5%, V: 0.21%, Nb: 0.15%, B: 0.0022%, N: less than 0.0005%, Ni: 31%, Mo: 2%, Cu: 3.3 percent, and the balance of Fe and inevitable impurities.
Further, the alloy of this example had a yield strength of 680MPa, a tensile strength of 1080MPa, and an elongation after fracture of 44%.
Further, after the alloy of the embodiment is subjected to a hydrogen filling test at 200 ℃, 0.1MPa, 72 hours or 300 ℃, 0.1MPa and 48 hours, the elongation after fracture is 42%, the hydrogen induced plasticity loss is less than 8%, and the hydrogen content is 9 ppm.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. The pipeline alloy special for hydrogen energy is characterized by comprising the following elements in percentage by mass:
c: 0.02 to 0.04%, Si: less than 0.3%, Mn: less than 0.5%, P: less than 0.003%, S: less than 0.005%, Cr: 16-21%, Al: 1.2-2%, Ti 1-2%, V: 0.08 to 0.3, Nb: 0.06-0.3, B: 0.0015-0.0028, N: less than 0.0005%, Ni: 25-33%, Mo: 1-3%, Cu: 2-4.5%, and satisfies the condition that Ti + Al is less than 4%, Ti/Al is approximately equal to 0.6-1.0, V + Nb is less than or equal to 0.6%, and the balance is Fe and inevitable impurities.
2. The special pipeline alloy for hydrogen energy as claimed in claim 1, wherein the alloy has yield strength of 620-680 MPa, tensile strength of 1080-1280 MPa, and elongation after fracture of 38-45%; after hydrogen is charged under the conditions of 200 ℃, 0.1Mpa, 72 hours or 300 ℃, 0.1Mpa and 48 hours, the elongation after fracture is 36-42%, the hydrogen induced plasticity loss is less than 8%, and the hydrogen content is 5-20 ppm.
3. The pipe alloy for hydrogen energy use according to claim 1, which is used for a high-pressure hydrogen storage container or a seamless pipe for high-pressure hydrogen gas transfer.
4. A pipeline dedicated to hydrogen energy, characterized in that the alloy of claim 1 is used, and the pipeline comprises a gamma prime strengthening phase composed of Ni, Al, Ti and having an average particle size of less than 100 nm.
5. The pipeline special for hydrogen energy of claim 4, wherein the average particle size of the gamma prime strengthening phase is 20-80 nm.
6. The pipeline special for hydrogen energy as claimed in claim 4, wherein the pipeline is used as a high pressure bearing structural material of a hydrogen storage container or a non-pipeline material of a heat exchanger and a regulating valve in a high-pressure pure hydrogen environment with the pressure of 30-90 MPa.
7. The method for preparing the pipeline special for hydrogen energy according to claim 4, comprising the following steps:
s1: preparing materials according to elements contained in the alloy components and corresponding mass percentages, smelting to obtain a steel ingot, and carrying out homogenization treatment on the steel ingot;
s2: the homogenized steel ingot is subjected to cogging and forging to form a bar, and is subjected to water cooling after being homogenized again or is directly transferred to an extruder to form a through hole as an original blank;
s3: sequentially perforating, extruding, pickling, cold rolling, straightening, heat treating, pickling and finishing the original blank to obtain a finished product of the special hydrogen energy pipeline with a gamma' strengthening phase smaller than 100 nm; wherein the heat treatment is tempering treatment at 670-850 ℃.
8. The method for manufacturing a pipeline dedicated to hydrogen energy according to claim 7, wherein the tempering temperature is 840 ℃.
CN202210692465.2A 2022-06-17 2022-06-17 Special pipeline alloy for hydrogen energy, pipeline and preparation method of pipeline Pending CN115094314A (en)

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CN115255022A (en) * 2022-09-27 2022-11-01 江苏恒阳冶金科技有限公司 Hydrogen-resistant high-temperature alloy pipe and preparation method thereof

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CN105063507A (en) * 2015-08-20 2015-11-18 中国科学院金属研究所 High-strength hydrogen-brittleness-resistant austenite alloy with mark of J75 and preparation method of high-strength hydrogen-brittleness-resistant austenite alloy
JP2016074976A (en) * 2014-10-07 2016-05-12 新日鐵住金株式会社 Austenitic stainless steel and device for high-pressure hydrogen gas or device for liquid hydrogen

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Publication number Priority date Publication date Assignee Title
JP2016074976A (en) * 2014-10-07 2016-05-12 新日鐵住金株式会社 Austenitic stainless steel and device for high-pressure hydrogen gas or device for liquid hydrogen
CN105063507A (en) * 2015-08-20 2015-11-18 中国科学院金属研究所 High-strength hydrogen-brittleness-resistant austenite alloy with mark of J75 and preparation method of high-strength hydrogen-brittleness-resistant austenite alloy

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Publication number Priority date Publication date Assignee Title
CN115255022A (en) * 2022-09-27 2022-11-01 江苏恒阳冶金科技有限公司 Hydrogen-resistant high-temperature alloy pipe and preparation method thereof
CN115255022B (en) * 2022-09-27 2022-12-20 江苏恒阳冶金科技有限公司 Hydrogen-resistant high-temperature alloy pipe and preparation method thereof

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