CN113637891B - Alkali-brittleness-resistant low alloy steel, plate, welded pipe and seamless pipe and manufacturing method thereof - Google Patents

Alkali-brittleness-resistant low alloy steel, plate, welded pipe and seamless pipe and manufacturing method thereof Download PDF

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CN113637891B
CN113637891B CN202010343873.8A CN202010343873A CN113637891B CN 113637891 B CN113637891 B CN 113637891B CN 202010343873 A CN202010343873 A CN 202010343873A CN 113637891 B CN113637891 B CN 113637891B
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alloy steel
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CN113637891A (en
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张清廉
翟国丽
王孝兵
刘麒麟
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Baoshan Iron and Steel Co Ltd
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
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    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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    • C21D8/0226Hot rolling
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    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/008Ferrous alloys, e.g. steel alloys containing tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/60Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/009Pearlite

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Abstract

The invention discloses alkali-brittle-resistant low alloy steel which is characterized by comprising the following chemical elements in percentage by mass: 0 to less than or equal to 0.4 percent of C, 0.02 to 1.20 percent of Mn, 0.05 to 0.45 percent of Si, 0.001 to 0.75 percent of Cu, 0.001 to 0.4 percent of Sn and 0.001 to 0.35 percent of Sb. In addition, the invention also discloses a manufacturing method of the alkali-embrittlement-resistant low-alloy steel plate, the welded pipe and the seamless pipe. The alkali-brittleness resistant low alloy steel has excellent alkali-brittleness resistance and uniform corrosion resistance. Accordingly, the plate, the welded pipe and the seamless pipe made of the alkali-embrittlement resistant low alloy steel in the present invention also have excellent alkali-embrittlement resistance and excellent uniform corrosion resistance.

Description

Alkali-brittleness-resistant low alloy steel, plate, welded pipe, seamless pipe and manufacturing method thereof
Technical Field
The invention relates to a metal material and a manufacturing method thereof, in particular to low alloy steel and a manufacturing method thereof.
Background
In the prior art, the alkali represented by NaOH and NaHCO are used3The basic raw materials are the strong alkali and weak acid salts which are easy to hydrolyze and are alkaline, the pH value of the solutions is more than 7, namely the solutions are alkaline. In the Bayer process of producing alumina, NaOH is used as solvent to extract Al from bauxite2O3. However, it should be noted that the alkaline environment, particularly the alkaline environment at high temperature, is likely to cause brittle fracture of a metal material such as carbon steel, that is, ordinary alkaline brittleness.
In order to avoid the alkali brittleness of steel materials such as carbon steel, the long-period operation of the production line can be generally maintained only by the process measures of limiting the operation temperature and the alkali concentration, for example, in HG/T20581, the use concentration of un-stress-relieved carbon steel in caustic soda and the corresponding temperature are clarified in HG/T20581. However, as shown in the prior reference SH/T3096-2012 "high sulfur crude oil processing plant equipment and pipeline design selection guide", although stress relief annealing can suitably increase the applicable concentration and temperature of the carbon steel, when the maximum temperature increase is 20 wt% NaOH, the temperature can only be increased from 70 ℃ to 110 ℃, i.e. about 40 ℃. Therefore, the stress relief annealing has relatively limited application temperature for increasing the carbon steel, and is far inferior to the production requirement of high-temperature concentrated alkali required by industries such as Bayer process alumina and the like. When the temperature is more than or equal to 110 ℃, the requirement of adopting nickel-based alloy is stipulated in SH/T3096-2012, and the nickel-based alloy can be used in high-temperature alkali environment without alkali brittleness. However, the cost of the nickel-based alloy is very high, and the high cost cannot be borne by industries such as alumina and the like, so that the production is not facilitated. In industries such as alumina and the like, only processes with lower concentration and temperature can be adopted for production, and the performance of production line efficiency is restricted, so that the economic metal material is expected to break through the bottleneck restriction of alkali brittleness caused by temperature-concentration in industries such as alumina and the like.
Chinese patent publication No. CN201210578892.4, published as 2013, 4, 3 and entitled "reaction vessel for preventing alkali embrittlement", discloses a reaction vessel for preventing alkali embrittlement, which is obtained by using a nickel-chromium alloy composite coating and further requiring a non-stick coating to seal the outermost surface thereof to prevent alkali embrittlement of a stainless steel reactor.
The Chinese patent document with publication number CN201220733591.X, publication number of 6.12.2013, and name "a polyacrylamide reaction kettle with an anti-corrosion non-stick coating on the inner wall" discloses a polyacrylamide reaction kettle with an anti-corrosion non-stick coating on the inner wall, which is used for corrosion prevention by a composite metal coating of nickel-chromium alloy and other trace rare earth alloy, wherein the Ni content is 80%, and the Cr content is about 20%. The outer surface of the composite alloy coating also needs to be sealed by a non-stick coating to prevent the reactors of stainless steel, carbon steel and the like from generating alkali brittleness.
In the prior art, except for relying on the composite alloy coating which is actually nickel-chromium alloy to prevent alkali brittleness, other prior arts mostly adopt measures such as process, structure and the like to prevent alkali brittleness. The prior art does not have a technology for preventing alkali brittleness by using a base material, particularly an alloy steel material.
Disclosure of Invention
An object of the present invention is to provide an alkali embrittlement resistant low alloy steel which realizes alkali embrittlement resistance by alloying of carbon steel and at the same time has excellent uniform corrosion resistance in an alkaline environment. The alkali-embrittlement-resistant low alloy steel is effectively applied to a corrosion environment in which alkali embrittlement needs to be prevented, has a very wide application field, and has good popularization and application values and market prospects.
In order to achieve the purpose, the invention provides alkali-brittle-resistant low alloy steel which contains the following chemical elements in percentage by mass: 0 to less than or equal to 0.4 percent of C, 0.02 to 1.20 percent of Mn, 0.05 to 0.45 percent of Si, 0.001 to 0.75 percent of Cu, 0.001 to 0.4 percent of Sn and 0.001 to 0.35 percent of Sb.
Further, in the alkali-brittle and low-alloy steel of the invention, the chemical elements comprise the following components in percentage by mass:
c is more than 0 and less than or equal to 0.4 percent, Mn is 0.02 to 1.20 percent, Si is 0.05 to 0.45 percent, Cu is 0.001 to 0.75 percent, Sn is 0.001 to 0.4 percent, Sb is 0.001 to 0.35 percent, and the balance is Fe and other inevitable impurities.
In the alkali-brittle-resistant low alloy steel, the design principle of each chemical element is as follows:
c: in the alkali-brittle low alloy steel of the present invention, carbon is the most economical element for improving strength and is objectively present, but carbon is liable to form carbide, which is disadvantageous to the corrosion resistance of the low alloy steel. Therefore, the mass percent of C in the alkali-brittle resistant low alloy steel is controlled to be more than 0 and less than or equal to 0.4 percent.
In some preferred embodiments, the mass percent of C can be controlled to be 0 < C.ltoreq.0.3%.
Si: in the alkali-brittle-resistant low alloy steel, Si is also an inherent and objectively existing element in the steel, the unrealistic situation that the content of the Si element is too low is avoided, and the solid solution strengthening of the Si element is beneficial to improving the strength of the steel. However, too high Si content is not favorable for the workability of the steel sheet as well as improving the strength. The quality percentage of Si in the alkali-embrittlement resistant low alloy steel is controlled to be between 0.05 and 0.45 percent by comprehensively considering the performance improvement effect and adverse factors of Si on the alkali-embrittlement resistant low alloy steel.
In some preferred embodiments, the mass percentage of Si may be controlled between 0.17% and 0.37%.
Mn: in the alkali-brittle low alloy steel of the present invention, Mn can also effectively improve the strength of steel, but is likely to form inclusions. If the Mn content in the steel is too high, the tendency of structure segregation is increased. Therefore, the mass percent of Mn in the alkali-brittle-resistant low alloy steel is controlled to be between 0.02 and 1.20 percent.
In some preferred embodiments, the mass percentage of Mn may be controlled between 0.1% and 1.0%.
Cu: in the alkali-brittleness resistant low alloy steel, the addition of the Cu element is beneficial to improving the alkali-brittleness resistance of the steel. However, when the Cu content is too high, cracking tends to occur during rolling. In order to prevent the tendency of rolling cracking, the maximum content of Cu needs to be strictly controlled. Therefore, the mass percent of Cu in the alkali-brittle-resistant low alloy steel is controlled to be between 0.001 and 0.75 percent.
In some preferred embodiments, the mass percentage of Cu may be controlled between 0.05% and 0.55%.
Sn: in the alkali-brittleness resistant low alloy steel, the addition of Sn element is also beneficial to improving the alkali-brittleness resistance of the steel. However, if the Sn content in the steel is too high, the steel tends to crack during rolling. Therefore, in order to prevent the rolling cracking tendency, the mass percent of Sn in the alkali-brittle low-alloy steel is controlled to be between 0.001 and 0.4 percent.
In some preferred embodiments, the mass percentage content of Sn can be controlled between 0.05% and 0.55%
Sb: in the alkali-brittleness resistant low alloy steel, the addition of Sb is also beneficial to improving the alkali-brittleness resistance of the steel. However, if the Sb content in the steel is too high, the steel tends to crack during rolling. Therefore, in order to prevent the rolling cracking tendency, the mass percent of Sb in the alkali-brittle-resistant low-alloy steel is controlled to be between 0.001 and 0.35 percent.
In some preferred embodiments, the mass percentage of Sb may be controlled between 0.003% and 0.3%.
Further, the alkali-brittle resistant low alloy steel of the present invention further comprises at least one of the following elements:
0<Al≤0.4%;
0<V≤0.1%。
further, in the alkali-brittle-resistant low alloy steel, the contents of Al and V elements meet the following requirements: al is more than 0 and less than or equal to 0.25 percent; and/or V is more than 0 and less than or equal to 0.08 percent.
In the technical scheme, Al in the alkali-embrittlement-resistant low alloy steel can be used as a deoxidizer, and the deoxidizer can deoxidize in the steelmaking process and improve the quality of steel. Therefore, the mass percent of Al in the alkali-brittle resistant low alloy steel is controlled to be more than 0 and less than or equal to 0.4 percent.
In some preferred embodiments, the Al content may be controlled to 0 < Al < 0.25% by mass.
Likewise, V can be used as a grain refining element in the steel, and plays a role in refining grains, thereby improving the performance of the steel. Therefore, the mass percent of V in the alkali-brittle resistant low alloy steel is controlled to be more than 0 and less than or equal to 0.1 percent.
In some preferred embodiments, V may be present in an amount greater than 0 and less than or equal to 0.08% by weight.
Further, in the alkali-brittle-resistant low alloy steel of the present invention, the inevitable impurity elements at least include S and P, wherein P is less than or equal to 0.03% and/or S is less than or equal to 0.035%.
In the alkali-brittle low alloy steel of the present invention, S and P are objective, inevitable impurity elements. When the content of the impurity element P in the steel is too high, cold cracking is easily generated. If the content of the S element in the steel is too high, cracking is likely to occur during the hot rolling. Therefore, in order to ensure the performance of the low alloy steel, the mass percentage of P in the alkali-brittle and low alloy steel is strictly controlled to be less than or equal to 0.03 percent, and the mass percentage of S in the alkali-brittle and low alloy steel is controlled to be less than or equal to 0.035 percent.
Further, in the alkali-brittle and low-alloy steel of the present invention, the mass percentage of each chemical element satisfies at least one of the following:
0<C≤0.3%;
Mn:0.1%~1.0%;
Si:0.17%~0.37%;
Cu:0.05%~0.55%;
Sn:0.002%~0.33%;
Sb:0.003%~0.3%。
further, in the alkali-brittle-resistant low alloy steel of the present invention, the microstructure is ferrite + pearlite.
Furthermore, in the alkali-resistant brittle low alloy steel, the alkali-resistant uniform corrosion rate is less than or equal to 1 mm/a.
Furthermore, in the alkali-resistant brittle low alloy steel, the alkali-resistant uniform corrosion rate is less than or equal to 0.1 mm/a.
Accordingly, another object of the present invention is to provide a plate material having alkali embrittlement resistance, which has not only excellent alkali embrittlement resistance but also excellent uniform corrosion resistance in an alkaline environment.
In order to achieve the above object, the present invention proposes a plate made of the above alkali embrittlement resistant low alloy steel.
Further, the manufacturing method of the plate material comprises the following steps:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) and (3) heat treatment: and (4) keeping the heat treatment temperature of 880-960 ℃ for more than 15min, and then cooling in air.
It is still another object of the present invention to provide a welded pipe having alkali embrittlement resistance, which has not only excellent alkali embrittlement resistance but also excellent uniform corrosion resistance in an alkaline environment.
In order to achieve the above object, the present invention proposes a welded pipe made of the above alkali embrittlement resistant low alloy steel.
Further, the manufacturing method of the welded pipe of the present invention comprises the steps of:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃ to obtain a hot rolled plate or plate coil;
(3) welding the hot-rolled plate or plate coil to form a welded pipe;
(4) heat treatment of the welded pipe: and (3) carrying out heat treatment at 880-960 ℃, keeping the temperature for more than 15min, and then carrying out air cooling.
Further, the manufacturing method of the welded pipe of the present invention comprises the steps of:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) heat treatment of the plate: the heat treatment temperature is 880-960 ℃, the heat preservation time is more than 15min, and then air cooling is carried out to obtain a heat-treated plate or plate coil;
(4) welding the heat-treated plate or plate coil to form a welded pipe;
(5) heat treatment of welded pipes: and (4) keeping the heat treatment temperature of 880-960 ℃ for more than 15min, and then cooling in air.
It is still another object of the present invention to provide an alkali embrittlement resistant seamless pipe having not only excellent alkali embrittlement resistance but also excellent uniform corrosion resistance in an alkaline environment.
In order to achieve the above object, the present invention proposes a seamless pipe made of the above alkali embrittlement resistant low alloy steel.
Further, a method for manufacturing a seamless pipe according to the present invention includes the steps of:
(1) preparing a tube blank;
(2) heating the tube blank: controlling the heating temperature to be 1220-1280 ℃, and keeping the temperature for more than or equal to 40 min;
(3) perforating: controlling the perforation temperature to be 1120-1200 ℃;
(4) rolling: controlling the finishing temperature to be 830-950 ℃;
(5) the heat treatment process comprises the following steps: controlling the heat treatment temperature to 880-960 ℃, keeping the temperature for more than or equal to 15min, and then air-cooling.
Further, in the method for manufacturing a seamless pipe according to the present invention, there is further provided, between the steps (3) and (4), a step (3a) of reheating: the reheating temperature is 940-980 ℃, and the heat preservation time is more than or equal to 15 min.
Compared with the prior art, the alkali-embrittlement-resistant low alloy steel and the manufacturing method thereof have the advantages and beneficial effects as follows:
the alkali-brittleness resistant low alloy steel is creatively designed by controlling the chemical element components of the steel, and the alkali-brittleness resistance is realized by alloying the carbon steel, so that the low alloy steel not only has excellent alkali-brittleness resistance, but also has excellent uniform corrosion resistance, can be effectively applied to the corrosion environment needing to prevent the alkali-brittleness, has very wide application field, and has good popularization and application values and market prospects.
Accordingly, the plate, the welded pipe and the seamless pipe which are made of the alkali-embrittlement-resistant low alloy have the advantages and beneficial effects.
Drawings
FIG. 1 shows the metallographic structure of a plate or welded pipe or seamless pipe having the composition of example 1 of the alkali-brittle low alloy steel of the present invention.
FIG. 2 is a schematic representation of the average corrosion rate of the sheets or welded or seamless tubes of the alkali brittle low alloy steel of the present invention having the compositions of examples 1-7 as tested for their resistance to uniform corrosion.
Detailed Description
The alkali-embrittlement resistant low-alloy steel and the method for manufacturing the same according to the present invention will be further explained and illustrated with reference to specific examples and drawings of the specification, but the explanation and illustration should not be construed as unduly limiting the technical aspects of the present invention.
Examples 1 to 7
Table 1 shows the mass percentages of the chemical elements of the alkali-brittle resistant low alloy steels of examples 1 to 7.
TABLE 1 (wt%, balance Fe and unavoidable impurities other than P, S)
Figure BDA0002469373730000071
The alkali-embrittlement resistant low-alloy steels of examples 1 to 7 can be manufactured into plate materials, welded pipes and seamless pipes, and specific process parameters for manufacturing the plate materials, the welded pipes and the seamless pipes are shown in tables 2 to 1, tables 2 to 2 and tables 2 to 3.
The alkali embrittlement resistant low alloy steels of examples 1-1 to 7-1 were produced by the following steps:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) and (3) heat treatment: and (4) keeping the heat treatment temperature of 880-960 ℃ for more than 15min, and then cooling in air.
Table 2-1 lists specific process parameters in the method of making the sheet of examples 1-1 to 7-1.
Table 2-1.
Figure BDA0002469373730000072
The welded pipes correspondingly made of the alkali-embrittlement-resistant low-alloy steels of examples 1-2 to 3-2 were all made by the following steps:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃ to obtain a hot rolled plate or plate coil;
(3) welding the hot-rolled plate or plate coil to form a welded pipe;
(4) heat treatment of the welded pipe: and (3) carrying out heat treatment at 880-960 ℃, keeping the temperature for more than 15min, and then carrying out air cooling.
The welded pipes corresponding to the alkali-brittle-resistant low alloy steels of examples 4-2 to 7-2 were produced by the following steps:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) heat treatment of the plate: the heat treatment temperature is 880-960 ℃, the heat preservation time is more than 15min, and then air cooling is carried out to obtain a heat-treated plate or plate coil;
(4) welding the heat-treated plate or plate coil to form a welded pipe;
(5) heat treatment of the welded pipe: and (4) keeping the heat treatment temperature of 880-960 ℃ for more than 15min, and then cooling in air.
In the present invention, the welded pipes obtained in examples 1 to 3 were not subjected to the heat treatment of the plate material, as compared with the welded pipes obtained in examples 4 to 7.
Table 2-2 lists specific process parameters in the manufacturing method of the welded tubes of examples 1-2 to 7-2.
Table 2-2.
Figure BDA0002469373730000081
The alkali embrittlement resistant low alloy steels of examples 1-3 to 7-3 were produced by the following procedure corresponding to the seamless pipes:
(1) preparing a tube blank;
(2) heating the tube blank: controlling the heating temperature to be 1220-1280 ℃, and keeping the temperature for more than or equal to 40 min;
(3) perforating: controlling the perforation temperature to be 1120-1200 ℃;
(3a) reheating: the reheating temperature is 940-980 ℃, and the heat preservation time is more than or equal to 15 min.
(4) Rolling: controlling the finishing temperature to be 830-950 ℃;
(5) the heat treatment process comprises the following steps: controlling the heat treatment temperature to 880-960 ℃, keeping the temperature for more than or equal to 15min, and then air-cooling.
It should be noted that, in the present invention, the seamless tube manufacturing process of examples 4-3 to 7-3 proceeds directly to the rolling step of step 4 without the reheating treatment step of step 3a after the completion of the piercing in step 3, as compared to the seamless tube manufacturing process of examples 1-3 to 3-3.
Tables 2 to 3 list specific process parameters in the manufacturing methods of the seamless pipes of examples 1 to 3 to 7 to 3.
Tables 2 to 3.
Figure BDA0002469373730000091
The low alloy steel, the plate, the welded pipe and the seamless pipe in the embodiments 1 to 7 obtained by the above chemical element design and manufacturing process are tested for the alkali brittleness resistance, the uniform corrosion resistance and other related performances, so as to respectively obtain test data for evaluating each performance, and the specific test items and the test method are as follows:
1) alkali brittleness resistance:
the plates, welded tubes and seamless tubes made of the low alloy steels of examples 1 to 7 were processed into rectangular thin plate samples, and through holes were symmetrically punched at both ends of the samples; and bending the test sample into a U shape, loading the test sample until two straight sides of the U shape are parallel, and insulating the test sample and the loading fixing clamp by adopting ceramic rings to prepare the alkali-embrittlement-resistant corrosion test sample. The sample with the U-shaped loading state not only can keep the sample in plastic deformation, but also can have a larger stress state which is more rigorous than the loading state of practical engineering application; moreover, the insulation can prevent electrochemical corrosion between the samples and the clamp, so that the alkali resistance brittleness of the samples can be objectively evaluated.
The above samples were immersed in a 20 wt% NaOH solution at 125 deg.C for 7 days, i.e., 168 hours. When the samples were observed by microscope after the experiment, no cracking occurred in any of the samples having the compositions of examples 1 to 7 of the present invention, which indicates that they had excellent alkali embrittlement resistance.
2) Uniform corrosion resistance:
samples of the low alloy steels, plates, welded pipes, seamless pipes and the like in examples 1 to 7 were cut into rectangular sheet samples, which were washed, weighed, and measured for dimensions, and then immersed in a NaOH solution having an alkali concentration of 20 wt% at a temperature of 125 ℃ for 7 days, i.e., 168 hours. After the experiment, the local corrosion such as pitting corrosion was not observed by observation with a microscope, and the corrosion was uniform throughout. And weighing again, dividing the mass difference (namely mass loss) before and after the experiment by the surface area of the sample and the test time to obtain the corrosion rate of the weight-loss method, and judging the alkali-resistant uniform corrosion property according to the corrosion rate of the weight-loss method.
Table 3 lists the relevant performance parameters for the low alloy steels, sheet, welded and seamless tubes of examples 1-7.
Table 3.
Figure BDA0002469373730000101
As can be seen from Table 3, the low alloy steels of examples 1-7 have excellent properties, the uniform corrosion rates of alkali resistance are all less than or equal to 1mm/a, and all the U-shaped loading samples have no cracks (i.e. no cracks), which indicates that the low alloy steels have excellent alkali brittleness resistance and excellent uniform corrosion resistance.
Compared with common carbon steel, the alkali brittleness resistance temperature of the low alloy steel is at least increased by more than or equal to 50 ℃, and in certain alkali concentration areas, the alkali brittleness resistance temperature of the low alloy steel is increased by more than or equal to 100 ℃. Correspondingly, the plates, the welded pipes and the seamless pipes made of the alkali-brittle-resistant low alloy steel in the corresponding embodiments in the embodiments 1 to 7 have excellent alkali-brittle resistance and uniform corrosion resistance, are very wide in application field, and have good popularization and application values and market prospects.
FIG. 1 shows the metallographic structure morphology of the alkali-brittle-resistant low alloy steel of the invention in example 1. As can be seen from fig. 1, the microstructure of the alkali embrittlement resistant low alloy steel in the present example is ferrite + pearlite.
FIG. 2 is a schematic representation of the average corrosion rate of the low alloy steel of examples 1 to 7, which is subjected to the test for uniform corrosion resistance, of the alkali-brittle low alloy steel of the present invention.
As shown in fig. 2, γHIs the measured hourly corrosion rate, gammaYConverted annual corrosion rates. As can be seen from FIG. 2, the low alloy steels of examples 2 to 7 exhibited annual corrosion rates γYAll less than 1.0mm/a, all reach the general corrosion resistance level (0.1-1.0 mm/a), while the annual corrosion rate gamma of the low alloy steel of the embodiment 1YLess than 0.1mm/a, and example 1 achieved a corrosion resistance rating (0.01 to 0.1 mm/a).
It should be noted that the above-mentioned embodiments are only specific embodiments of the present invention. It is apparent that the present invention is not limited to the above embodiments and similar changes or modifications can be easily made by those skilled in the art from the disclosure of the present invention and shall fall within the scope of the present invention.

Claims (12)

1. The alkali-brittle-resistant low alloy steel is characterized by comprising the following chemical elements in percentage by mass:
0 < C < 0.4%, 0.02% -1.20% Mn, 0.05% -0.45% Si, 0.001% -0.75% Cu, 0.12% -0.4% Sn, 0.1% -0.35% Sb; at least one of Al and V, wherein Al is more than 0 and less than or equal to 0.4 percent, and V is more than 0 and less than or equal to 0.1 percent; p is less than or equal to 0.03 percent; s is less than or equal to 0.035%; the balance being Fe and other unavoidable impurities;
the alkali-resistant uniform corrosion rate of the low alloy steel is less than or equal to 1 mm/a.
2. The alkali-brittle resistant low alloy steel of claim 1, characterized in that the Al and V element contents are such that: al is more than 0 and less than or equal to 0.25 percent; and/or V is more than 0 and less than or equal to 0.08 percent.
3. The alkali-embrittlement resistant, low-alloy steel according to claim 1 or 2, characterized in that its chemical elements, in mass percent, satisfy at least one of:
0<C≤0.3%;
Mn:0.1%~1.0%;
Si:0.17%~0.37%;
Cu:0.05%~0.55%;
Sn:0.12%~0.33%;
Sb:0.1%~0.3%。
4. the alkali brittle-resistant low alloy steel according to claim 1 or 2, characterized in that the microstructure is ferrite + pearlite.
5. A sheet made of the alkali-embrittlement resistant low-alloy steel defined in any one of claims 1 to 4.
6. A method of manufacturing a panel as claimed in claim 5, comprising the steps of:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) and (3) heat treatment: and (3) carrying out heat treatment at 880-960 ℃, keeping the temperature for more than 15min, and then carrying out air cooling.
7. A welded pipe made of the alkali embrittlement resistant low alloy steel according to any one of claims 1 to 4.
8. A method of manufacturing a welded pipe according to claim 7, characterized by comprising the steps of:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃ to obtain a hot rolled plate or plate coil;
(3) welding the hot-rolled plate or plate coil to form a welded pipe;
(4) heat treatment of the welded pipe: and (3) carrying out heat treatment at 880-960 ℃, keeping the temperature for more than 15min, and then carrying out air cooling.
9. A method of manufacturing a welded pipe according to claim 7, characterized by comprising the steps of:
(1) smelting and casting;
(2) rolling: controlling the heating temperature of the plate blank to be 1160-1270 ℃, and controlling the finishing temperature to be 830-950 ℃;
(3) plate heat treatment: the heat treatment temperature is 880-960 ℃, the heat preservation time is more than 15min, and then air cooling is carried out to obtain a heat-treated plate or plate coil;
(4) welding the heat-treated plate or plate coil to form a welded pipe;
(5) heat treatment of the welded pipe: and (3) carrying out heat treatment at 880-960 ℃, keeping the temperature for more than 15min, and then carrying out air cooling.
10. Seamless tube made of the alkali embrittlement resistant low alloy steel according to any one of claims 1 to 4.
11. A method of manufacturing a seamless tube according to claim 10, comprising the steps of:
(1) manufacturing a tube blank;
(2) heating the tube blank: controlling the heating temperature to be 1220-1280 ℃, and keeping the temperature for more than or equal to 40 min;
(3) perforating: controlling the perforation temperature to be 1120-1200 ℃;
(4) rolling: controlling the finishing temperature to be 830-950 ℃;
(5) the heat treatment process comprises the following steps: controlling the heat treatment temperature to 880-960 ℃, keeping the temperature for more than or equal to 15min, and then air-cooling.
12. Process for manufacturing a seamless tube according to claim 11, characterized by the fact that between steps (3) and (4) there is also a step (3a) of reheating: the reheating temperature is 940-980 ℃, and the heat preservation time is more than or equal to 15 min.
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JP2013185197A (en) * 2012-03-07 2013-09-19 Kobe Steel Ltd Steel product for hydrogen sulfide environment excellent in hydrogen absorption resistance, and steel structure
CN104846280A (en) * 2014-02-13 2015-08-19 株式会社神户制钢所 Coating steel excellent in corrosion resistance
CN105088103A (en) * 2015-08-25 2015-11-25 广西南宁智翠科技咨询有限公司 Cold-brittleness-resistance alloy steel and preparation method thereof
CN108660385A (en) * 2017-03-30 2018-10-16 宝山钢铁股份有限公司 A kind of low-alloy steel of acid corrosion-resistant, steel pipe, steel plate and its manufacturing method
CN109487171A (en) * 2018-12-21 2019-03-19 中南大学 A kind of corrosion-resisting steel of hydrochloric acid corrosion resistant and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102686760A (en) * 2010-07-09 2012-09-19 住友金属工业株式会社 Corrosion-resistant steel material for cargo oil tank
JP2013185197A (en) * 2012-03-07 2013-09-19 Kobe Steel Ltd Steel product for hydrogen sulfide environment excellent in hydrogen absorption resistance, and steel structure
CN104846280A (en) * 2014-02-13 2015-08-19 株式会社神户制钢所 Coating steel excellent in corrosion resistance
CN105088103A (en) * 2015-08-25 2015-11-25 广西南宁智翠科技咨询有限公司 Cold-brittleness-resistance alloy steel and preparation method thereof
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