CN102925814A - Steel for hydrogen sulfide stress corrosion resisting pressure container and production method of steel - Google Patents
Steel for hydrogen sulfide stress corrosion resisting pressure container and production method of steel Download PDFInfo
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Abstract
The invention provides steel for a hydrogen sulfide stress corrosion resisting pressure container and a production method of the steel. The steel comprises the chemical components in percentage by weight of 0.05-0.12 percent of C, 0.15-0.35 percent of Si, 0.50-1.20 percent of Mn, less than or equal to 0.008 percent of P, less than or equal to 0.003 percent of S, 0.010-0.050 percent of Alt, 0.01-0.06 percent of V, 0.010-0.030 percent of Ti, 0.10-0.30 percent of Cu, 0.20-0.60 percent of Cr, 0.002-0.006 percent of Ca and less than or equal to 0.004 percent of N. The production method comprises the steps of: adopting molten iron desulphurization; smelting; refining; continuously casting into blanks; heating blanks; roughly rolling; precisely rolling; normalizing; tempering; and preparing for use. Low carbon and low alloy are adopted, and contents of P, S and N are strictly controlled, so that the steel has excellent hydrogen sulfide stress corrosion resisting capacity. A stable ferrite-pearlitic structure is obtained by using normalizing and tempering. The steel can be used for manufacturing pressure container devices used in various kinds of acid medium environments.
Description
Technical field
The present invention relates to steels for pressure vessel use and production method, refer to particularly anti-H 2 S stress corrosion steels for pressure vessel use and production method thereof.
Background technology
Before the present invention proposed, it was more with the product of steel to relate to hydrogen sulfide corrosion resistant, but for steels for pressure vessel use, particularly the anti-H 2 S stress corrosion steels for pressure vessel use is less.Name is called the Chinese patent literature of " a kind of large thickness novel anti-hydrogen sulfide steel and production method thereof ", number of patent application 200710193032.8, its disclosed composition and mass percent are C:0.17 ~ 0.20, Si:0.30 ~ 0.40, Mn:1.10 ~ 1.20, P≤0.008, S≤0.003, Ni:0.020 ~ 0.030, Nb:0.025 ~ 0.35, all the other are Fe and inevitable impurity.Added Nb on this steel chemical composition, C content is higher in the steel simultaneously, and the intensity of steel is higher, can only use under the sour environment of general requirement.
Name is called " a kind of anti-H 2 S stress corrosion tubing and casing ", the Chinese patent literature of number of patent application 200510029218.0, its composition quality per-cent is C:0.20 ~ 0.32, Si:0.1 ~ 0.5, Mn:0.4 ~ 1.0, Cr:0.1 ~ 0.8, Mo:0.5 ~ 1.2, V:0.01 ~ 0.10, Nb:0.01 ~ 0.10, P≤0.015, S≤0.010, all the other are Fe and inevitable impurity.Added more alloying element in this patent documentation, such as Cr, Mo, V, Nb, with useful to the anti-H 2 S stress corrosion performance, but high expensive.And this steel C content is higher, is not suitable for being applied to pressure vessel industries.
Number of patent application is that JP112040521, name are called the Japanese documentation of " the high chromium oil well pipe of a kind of low-carbon (LC) alloy ", its disclosed composition quality per-cent is C:0.005 ~ 0.05, Si≤1.0, Mn:0.05 ~ 0.30, Cr:12 ~ 16, Mo:1.5 ~ 2.5, Ni:3.5 ~ 6.0, V:0.01 ~ 0.05, N≤0.02, all the other are Fe and inevitable impurity.This patent documentation has added more Cr, Mo in chemical ingredients, and Ni belongs to the stainless steel field, therefore can obtain good anti-H 2 S stress corrosion performance, but production cost is high, is not suitable for the steels for pressure vessel use industry.
In oil and petrochemical industry, pressure vessel and equipment produces the embrittlement phenomenon easily under sour environment, and the performances such as resistance against hydrogen cracking (HIC) and anti-H 2 S stress corrosion (SSC) are not high, so that greatly reduce equipment life.
Summary of the invention
Purpose of the present invention overcomes the resistance against hydrogen cracking (HIC) of prior art existence and the deficiency of anti-H 2 S stress corrosion (SSC) performance, anti-H 2 S stress corrosion steels for pressure vessel use and the production method thereof of the anti-H 2 S stress corrosion ability of raising steel plate and the ability of resistance against hydrogen cracking are provided under a kind of prerequisite obtaining good obdurability, welding property.
Realize the measure of above-mentioned purpose:
A kind of anti-H 2 S stress corrosion steels for pressure vessel use, its chemical ingredients and weight percent content are: C: 0.05 ~ 0.12%, Si:0.15 ~ 0.35%, Mn:0.50 ~ 1.20%, P≤0.008, S≤0.003%, Alt:0.010 ~ 0.050%, V:0.01 ~ 0.06%, Ti:0.010 ~ 0.030%, Cu:0.10 ~ 0.30%, Cr:0.20 ~ 0.60%, Ca:0.002 ~ 0.006%, N≤0.004%, surplus is Fe and inevitably is mingled with.
It is characterized in that: C: 0.06 ~ 0.12%, Mn:0.50 ~ 1.00%, Alt:0.015 ~ 0.040%, V:0.01 ~ 0.05%, Ti:0.020 ~ 0.030%, Cr:0.30 ~ 0.60%.
Produce a kind of method of anti-H 2 S stress corrosion steels for pressure vessel use, its step:
1) adopts desulfurizing iron;
2) converter smelting;
3) in the LF stove, carry out refining, and add the Si-Ca line by 3 ~ 4Kg/ ton steel;
4) process in the RH vacuum oven, the control treatment time is no less than 18min;
5) continuous casting becomes base;
6) to the strand heating, the control Heating temperature is at 1200 ~ 1300 ℃, and heating rate is controlled at 9 ~ 12min/cm;
7) be rolled: control roughing start rolling temperature is not less than 1050 ℃, and the slab thickness that roughing finishes is at 40 ~ 120mm;
8) carry out finish rolling, and control finish rolling start rolling temperature is not higher than 930 ℃, the finish rolling finishing temperature is 760 ~ 860 ℃;
9) carry out normalizing, the control normalizing temperature is at 860 ~ 920 ℃, and the control normalizing time is not less than 35min;
10) carry out tempering, the control tempering temperature is at 600 ~ 680 ℃, and the control tempering time is not less than 50min;
11) stand-by.
The composition of steel of the present invention and production technique are set reason.
The reason of a chemical ingredients and main technologic parameters limited amount among the present invention:
C improves the most effective element of steel strength, along with the increase of C content, and Fe in the steel
3C increases, and hardenability also increases, and the tensile strength of steel and yield strength improve.But, increase C content in the steel, can improve the susceptibility of the stress corrosion cracking of steel in sulfide.Therefore, with reference to the Composition Design scheme of existing low alloy steel, the C content of steel of the present invention should be controlled in 0.12%.
The avidity of Si and carbon is very weak, and carburet not in steel, but can dissolve in ferrite produces solution strengthening effect, so that ferritic intensity and hardness improves, but plasticity and toughness descend to some extent.When Si content greater than 0.50% the time, can promote the island martensite body to form, harmful to anti-H 2 S stress corrosion and welding heat influence area toughness, as seen, Si has certain help to intensity, but content can not be too high.The Si content of steel of the present invention is controlled in 0.15% ~ 0.35% scope and can meets the demands.
The avidity of Mn and carbon is stronger, is the effective element that enlarges austenite phase region, crystal grain thinning and assurance over-all properties and improve hardening capacity, and it does not worsen the deformability of steel, and 1.00% Mn can be tensile strength contribution 100MPa approximately.But the Mn element is a kind of element of easy segregation, as line of segragation Mn, when C content reaches certain proportion, can produce martensitic phase in steel production and welding process, and this is met and shows very high hardness, and equipment anti-H 2 S stress corrosion performance is had considerable influence.Therefore, when this steel of design, Mn content is limited in 1.20%.Consider the strength range of steel of the present invention, therefore Mn is controlled at 0.50% ~ 1.20%.
Al is the main deoxidant element in the steel, and the maxima solubility in austenite is about 0.6%, and it only faintly increases hardening capacity after dissolving in austenite.But when Al content is higher, easily causes being mingled with in the steel and increase, unfavorable to the toughness of steel, can reduce simultaneously hardenability and the toughness of steel, reduce the hydrogen sulfide corrosion resistance energy of steel.Therefore Alt content in the steel is controlled in 0.050%.
V is one of carbide forming element of Effective Raise armor plate strength, and the effect in steel is only second to Nb, Ti.To form VC after adding V in the steel, improve fusing point, hardness and the wear resistance of cementite.Therefore, the content of V can not be too high, in order to avoid reduce the hydrogen sulfide corrosion resistance energy of steel.Simultaneously, dispersion-strengthened occurs in V when middle temperature, and is helpful to Plate Steel heart section intensity.Therefore, V is controlled at 0.01% ~ 0.06% during design.
Ti is little on the impact of low alloy steel stress corrosion opening cracking maleate sensitivity in hydrogen sulfide medium, but Plate Welding heat affected zone structure refinement is had remarkable effect, considers the armor plate strength scope and on the impact of welding property, so Ti is controlled at 0.010% ~ 0.030%.
Cu mainly plays the precipitation strength effect in steel, useful to the atmospheric corrosion resistance of steel, can improve the fatigue crack extended capability that can also improve in addition steel.But when the Cu too high levels, steel is prone to map cracking when rolling.Consider Cu to the impact of steel plate comprehensive mechanical property and corrosion resistance, Cu content is controlled at 0.10 ~ 0.30%.
Cr is element commonly used in the hydrogen sulfide corrosion resistant steel, can obtain stable tissue after under thermal treatment, can improve steel anti-hydrogen embrittlement ability and anti-H 2 S stress corrosion performance.Simultaneously, consider cost of alloy and service requirements, Cr content is controlled at 0.20% ~ 0.60%.
Ca is that steel carries out the element that increases when Ca-Si processes, and element itself did not have no significant effect plate property when its content was high, but through after the Ca-Si processing, the steel inclusion appearance changes, size reduces, and the nodularization rate improves, and is conducive to the hydrogen sulfide corrosion resistance energy of steel.But consider that Ca-Si processes impurity element increase in the rear steel, therefore, add-on is unsuitable excessive, and Ca content was controlled at 0.002% ~ 0.006% after this steel will be processed.
The impact of impurity element and gas antagonism H 2 S stress corrosion rigidity energy
The anti-H 2 S stress corrosion steel need be guaranteed the use of steel in acidic medium, although the impurity element content in the steel is very few, can have a significant impact the hydrogen sulfide corrosion resistance of steel.
P can cause the meltable eutectic inclusion of steel red crisp (hot-short) and Plasticity Decreasing except forming in steel, also hydrogen atom is reconfigured process and play restraining effect, increase so that steel increases the hydrogen effect, thereby also can reduce the stability of steel in acidity, sulfide hydrogen medium.S is harmful to the stress corrosion crack stability of steel.Along with the increase of sulphur content, the stability of steel sharply worsens.Sulfide inclusion is gathering a little of hydrogen, makes metal form defective tissue.Simultaneously, sulphur also is the promotor of absorption hydrogen.Therefore, P should be controlled in 0.008% for this steel, S is controlled in 0.005%.
In addition, this steel should reduce gas content in the steel as far as possible, reduces the segregation of steel.Simultaneously, in order to reduce the influence of time effect of steel, the content of N is controlled in 0.004%.
The reason that main technologic parameters limits
Process for making
Carry out Ca-Si at the LF stove during this smelting steel and process, inclusion is carried out sex change, can effectively reduce inclusion size, change the shape of inclusion, be conducive to the hydrogen sulfide corrosion resistance energy of steel.Simultaneously, this steel vacuum processing time is grown (vacuum processing time is not less than 18min), can reduce preferably impurity in the steel, gas content.
Steel rolling process
Steel of the present invention is rolled by low alloy steel technique.Rolling front slab heating temperature is 1200 ~ 1300 ℃, and heating rate is 9 ~ 12min/cm, guarantees that the strand temperature is even.
During roughing, according to finished steel plate thickness, the thickness of intermediate blank when controlling the end of this stage rolling.During finish rolling, after temperature is avoided austenite part recrystallization zone temperature, the district's controlled rolling of beginning austenite non-recrystallization.At this moment, the rolling of non-recrystallization district has enough compression ratios, so that produce the distortion accumulation of high distortion in the deformed austenite, forms a large amount of deformed belts and high density dislocation.After the finish rolling finish to gauge, the deformation dislocation will occur to reply and polygonization, thereby thinning microstructure improves intensity and the toughness of steel plate, can be also useful to the hydrogen sulfide corrosion resistance of steel.When rolling, consider the critical point temperature of steel, avoid occurring mixed crystal phenomenon.Therefore consider, the roughing start rolling temperature of steel is not less than 1050 ℃, and the roughing finishing temperature is not less than 980 ℃, and the finish rolling start rolling temperature is not higher than 930 ℃, and 760 ℃ ~ 860 ℃ of finishing temperatures are rolled in finish rolling.
Processing, thermal treatment process
Because steel of the present invention will be at life-time service under the acidic medium, its anti-H 2 S stress corrosion performance requriements to steel is higher, so be normalizing+tempering for the characteristics design thermal treatment process of this steel.The tissue of this steel is a kind of more stable ferrite+pearlitic structure after normalizing+tempering, can not occur anti-H 2 S stress corrosion cracking and hydrogen induced cracking (HIC) are had the martensitic stucture of considerable influence in the steel.Normalizing temperature is designed to 860 ~ 920 ℃, is in order to allow the abundant austenitizing of steel, to obtain stable tissue.Tempering temperature is designed to 600 ~ 680 ℃, is in order to allow steel interalloy element V, Cu fully separate out, to improve Plate Steel heart section performance.
The present invention compared with prior art adopts low-carbon (LC) and low-alloy at Composition Design, adds a certain amount of Mn, Cr, Cu, V, Ti etc., strictly controls P, S, N content, and carries out Ca-Si and process, so that this steel has good anti-H 2 S stress corrosion performance.Utilize normalizing+tempering heat treatment to obtain stable ferrite+pearlitic structure, utilize the complex intensifying effect of the microalloies such as Cu in the steel, V, Ti to guarantee that steel obtain enough intensity and toughness, can be used for making the pressure vessel and equipment that all kinds of acidic medium environment use
Embodiment
The below is described in detail the present invention:
Table 1 is the value tabulation of various embodiments of the present invention and Comparative Examples;
Table 2 is the main technologic parameters tabulation of various embodiments of the present invention and Comparative Examples;
Table 3 is the mechanics assay of various embodiments of the present invention and Comparative Examples;
Table 4 is the hydrogen sulfide corrosion resistant assay of various embodiments of the present invention and Comparative Examples;
Table 5 is the inclusion assay of various embodiments of the present invention and Comparative Examples.
Various embodiments of the present invention are according to following steps production:
1) adopts desulfurizing iron;
2) converter smelting;
3) in the LF stove, carry out refining, and add the Si-Ca line by 3 ~ 4Kg/ ton steel;
4) process in the RH vacuum oven, the control treatment time is no less than 18min;
5) continuous casting becomes base;
6) to the strand heating, the control Heating temperature is at 1200 ~ 1300 ℃, and heating rate is controlled at 9 ~ 12min/cm;
7) carry out roughing: control roughing start rolling temperature is not less than 1050 ℃, and the slab thickness that roughing finishes is at 40 ~ 120mm;
8) carry out finish rolling, and control finish rolling start rolling temperature is not higher than 930 ℃, the finish rolling finishing temperature is 760 ~ 860 ℃;
9) carry out normalizing, the control normalizing temperature is at 860 ~ 920 ℃, and the control normalizing time is not less than 35min;
10) carry out tempering, the control tempering temperature is at 600 ~ 680 ℃, and the control tempering time is not less than 50min.
11) stand-by.
Table 1 various embodiments of the present invention and Comparative Examples chemical ingredients (wt%)
The main technologic parameters of table 2 various embodiments of the present invention and Comparative Examples (one)
Table 2 various embodiments of the present invention and Comparative Examples main technologic parameters (two)
The mechanics assay of table 3 various embodiments of the present invention and Comparative Examples
The hydrogen sulfide corrosion resistant assay of table 4 various embodiments of the present invention and Comparative Examples
The inclusion assay of table 5 various embodiments of the present invention and Comparative Examples
Can find out that from table 3 ~ 5 steel grade steel of the present invention is pure, good obdurability, resistance against hydrogen cracking and anti-H 2 S stress corrosion performance are arranged, can be used for making all kinds of pressure vessel and equipments that use under the sour environment.
Above-described embodiment only exemplifies for the best, and is not to be restriction to embodiments of the present invention.
Claims (3)
1. anti-H 2 S stress corrosion steels for pressure vessel use, its chemical ingredients and weight percent content are: C: 0.05 ~ 0.12%, Si:0.15 ~ 0.35%, Mn:0.50 ~ 1.20%, P≤0.008, S≤0.003%, Alt:0.010 ~ 0.050%, V:0.01 ~ 0.06%, Ti:0.010 ~ 0.030%, Cu:0.10 ~ 0.30%, Cr:0.20 ~ 0.60%, Ca:0.002 ~ 0.006%, N≤0.004%, surplus is Fe and inevitably is mingled with.
2. a kind of anti-H 2 S stress corrosion steels for pressure vessel use as claimed in claim 1 is characterized in that: C: 0.06 ~ 0.12%, Mn:0.50 ~ 1.00%, Alt:0.015 ~ 0.040%, V:0.01 ~ 0.05%, Ti:0.020 ~ 0.030%, Cr:0.30 ~ 0.60%.
3. produce the method for a kind of anti-H 2 S stress corrosion steels for pressure vessel use as claimed in claim 1, its step:
1) adopts desulfurizing iron;
2) converter smelting;
3) in the LF stove, carry out refining, and add the Si-Ca line by 3 ~ 4Kg/ ton steel;
4) process in the RH vacuum oven, the control treatment time is no less than 18min;
5) continuous casting becomes base;
6) to the strand heating, the control Heating temperature is at 1200 ~ 1300 ℃, and heating rate is controlled at 9 ~ 12min/cm;
7) carry out roughing: control roughing start rolling temperature is not less than 1050 ℃, and the slab thickness that roughing finishes is at 40 ~ 120mm;
8) carry out finish rolling, and control finish rolling start rolling temperature is not higher than 930 ℃, the finish rolling finishing temperature is 760 ~ 860 ℃;
9) carry out normalizing, the control normalizing temperature is at 860 ~ 920 ℃, and the control normalizing time is not less than 35min;
10) carry out tempering, the control tempering temperature is at 600 ~ 680 ℃, and the control tempering time is not less than 50min;
11) stand-by.
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| CN106756538A (en) * | 2016-11-30 | 2017-05-31 | 武汉钢铁股份有限公司 | The high intensity moving pressure container steel and its manufacture method of anticorrosive and cracking |
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| CN108588570A (en) * | 2018-08-10 | 2018-09-28 | 武汉钢铁集团鄂城钢铁有限责任公司 | 600 DEG C of medium temperature acid corrosion-resistant pressure vessel steels of one kind and preparation method thereof |
| CN109082591A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | The high-strength oil annular tube steel of 125ksi anti-H 2 S stress corrosion and its preparation process |
| CN109234500A (en) * | 2018-11-20 | 2019-01-18 | 山西太钢不锈钢股份有限公司 | A method of improving iron abros oil well pipe anti-stress corrosion performance |
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| CN106756538A (en) * | 2016-11-30 | 2017-05-31 | 武汉钢铁股份有限公司 | The high intensity moving pressure container steel and its manufacture method of anticorrosive and cracking |
| CN110088338A (en) * | 2016-12-20 | 2019-08-02 | 株式会社Posco | There is the steels for pressure vessel use and its manufacturing method of excellent drag to high tempering heat treatment and post weld heat treatment |
| CN110088338B (en) * | 2016-12-20 | 2021-10-29 | 株式会社Posco | Steel for pressure vessel having excellent resistance to high-temperature tempering heat treatment and post-weld heat treatment, and method for manufacturing same |
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| CN108342649A (en) * | 2018-03-27 | 2018-07-31 | 武汉钢铁有限公司 | A kind of quenched steel for high strength pressure vessel and production method of acid corrosion-resistant |
| CN108342649B (en) * | 2018-03-27 | 2020-08-04 | 武汉钢铁有限公司 | Acid corrosion resistant quenched and tempered high-strength steel for pressure vessel and production method thereof |
| CN108588570A (en) * | 2018-08-10 | 2018-09-28 | 武汉钢铁集团鄂城钢铁有限责任公司 | 600 DEG C of medium temperature acid corrosion-resistant pressure vessel steels of one kind and preparation method thereof |
| CN109082591A (en) * | 2018-08-22 | 2018-12-25 | 东北大学 | The high-strength oil annular tube steel of 125ksi anti-H 2 S stress corrosion and its preparation process |
| CN109234500A (en) * | 2018-11-20 | 2019-01-18 | 山西太钢不锈钢股份有限公司 | A method of improving iron abros oil well pipe anti-stress corrosion performance |
| CN111926253A (en) * | 2020-07-31 | 2020-11-13 | 五矿营口中板有限责任公司 | Hydrogen sulfide corrosion resistant high-strength toughness normalized steel and manufacturing method thereof |
| CN111926253B (en) * | 2020-07-31 | 2021-10-22 | 五矿营口中板有限责任公司 | Hydrogen sulfide corrosion resistant high-strength toughness normalized steel and manufacturing method thereof |
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