CN101397635B - 12Cr2Mo1R thick steel plate for equipment contacting hydrogen and method for producing the same - Google Patents
12Cr2Mo1R thick steel plate for equipment contacting hydrogen and method for producing the same Download PDFInfo
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Abstract
The invention discloses a 12Cr2Mo1R thick steel plate used in equipment contacting hydrogen and a production method thereof which includes the following steps: a) The mass percentage of constituents is as follows: C: 0.10 to 0.15, Si: less than or equal to 0.10, Mn: 0.40 to 0.60, P: less than or equal to 0.010, S: less than or equal to 0.003, Cr: 2.0 to 2.5, Mo: 0.90 to 1.10, Cu: 0.10 to 0.20, Ni: 0.10 to 0.20, Sn is less than or equal to 0.003, Sb is less than or equal to 0.003, As is less than or equal to 0.003, Ca: 0.001 to 0.005, and Fe as the rest; b) The invention adopts converter smelting, and are casted into ingots; c) The ingots are bloomed, cogged and rolled; d) After being rolled, the ingots are normalized, and the temperature is 900 to 950 DEG C; e) Being accelerating-cooled by a pressure quenching machine based on the core part (more than or equal to 0.5 DEG C/s), bainite structures are obtained in whole thickness range; and f) Tempering treatment is carried out at 700 to 760 DEG C. The invention uses the pressure quenching machine, ensures that the microstructure of the finished product plate is tempering bainite by normalizing, accelerating cooling and tempering treatment, and obtains excellent mechanical property and weldability.
Description
Technical field
The present invention relates to a kind of Plate Steel and manufacture method thereof, particularly obtain to satisfy the 12Cr2Mo1R Plate Steel that hydrogen-contacting equipment uses (50～100mm) and manufacture method in the 2.25Cr1Mo alloy system.
Background technology
The petroleum refining pressurized vessel except that requiring hot strength, also has other requirement with 12Cr2Mo1R (SA387Gr22Cl2) Plate Steel.With the heavy oil desulfurization tower is example, and 12Cr2Mo1R (SA387Gr22Cl2) Plate Steel must have the ability of works better under High Temperature High Pressure and hydrogen environmental activity.
At present, being hydrogen-contacting equipment to 2.25Cr1Mo has with the basic demand of 12Cr2Mo1R (SA387Gr22Cl2) Plate Steel: J coefficient and X coefficient satisfy: J=(Si+Mn) * (P+Sn) * 10
4≤ 150, X=(10P+5 Sb+4Sn+As)/100≤15; The tough-brittle transition condition satisfies:
vTr5 5+2.5 Δ
vTr55≤10 ℃; Intensity satisfies: yield strength 〉=310Mpa, tensile strength: 515～690MPa.In CrMo series low-alloy steel, J coefficient and X coefficient depend primarily in the steel or the welding material deposited metal in what of P, Sb, Sn, As content, other performance is except that outside the Pass having with chemical ingredients, also relevant with the process system of manufacturing processed, especially intensity, toughness, and intensity and toughness final decision are in the microstructure state of finished product Plate Steel.But the Cr-Mo steel often owing to do not have suitable equipment and processing method, can not get desirable microstructure when producing, can't satisfy the requirement of hydrogen-contacting equipment working conditions.
Existing hydrogen-contacting equipment steel, usually it is domestic when manufacturing 2.25Cr1Mo is the CrMo steel, adopt electric arc furnace smelting, thermal treatment process adopts normalizing+tempering to produce the 12Cr2Mo1R Plate Steel, also can satisfy the hydrogen-contacting equipment device with Plate Steel standard-required " pressurized vessel is with the development of 1 2Cr2Mo1R steel plate; Yang Hailin etc.; Wide and Thick Slab 1997,1: 17～21 ", because the electric arc furnace smelting raw material limits, J coefficient maximum reaches 145.8, and the X coefficient reaches 17.30.
When Japanese kobe steel manufacturing 2.25Cr1Mo is ASTM A387Gr.22, taking off S, P and converter by molten iron takes off P and reduces P, S content in the steel, thermal treatment is that air cooling behind the employing N, tempering process are made petroleum refining heavy oil desulfurization device Plate Steel " ultralow P, S21/4Cr1Mo materials A STMA387Gr.22. Kobe Steel skill newspaper; holt is second-class clearly, Vol.33 (4) 1983:17～20 ".
Pass through to add V and micro-B on NKK's chemical ingredients, with unidirectional solidification ingot and the big reduction method of Ultra-Low Speed, thermal treatment process is produced this abundant clear etc., that welding low temperature crack sensitivity is low normalizing type 21/4Cr1Mo special heavy plate exploitation of 2.25Cr1Mo Plate Steel “ Jian mound of special thick specification with N+T.NKK skill newspaper, No.111 (1986): 9～16 "; Di Lingen makes SA387 Gr.22 and adopts N+AC+T " Heavy plate for petrochemical reactors Sophistication inChromium-Molybdenum steel http://www.dillinger.de ".
Summary of the invention
The object of the present invention is to provide a kind of hydrogen-contacting equipment 12Cr2Mo1R Plate Steel and manufacture method thereof, based on 2.25Cr1Mo is the CrMo steel, add proper C u, Ni, harmful elements such as control Sn, As, Sb, P, S, utilize the press quenching machine equipment,, guarantee that the microstructure of finished product steel plate is a tempering bainite by normalizing+acceleration cooling+tempering process, obtain excellent mechanical property and good weldability, be used to make various hydrogen-contacting equipments.
For achieving the above object, technical scheme of the present invention is:
The present invention is CrMo steel (satisfying 12Cr2Mo1R (SA387Gr22Cl2) standard-required) based on 2.25Cr1Mo, add proper C u, Ni, harmful elements such as control Sn, As, Sb, P, S, utilize the press quenching machine equipment, by normalizing+acceleration cooling+tempering process, the microstructure that guarantees the finished product steel plate is a tempering bainite, obtain excellent mechanical property and good weldability, produced (50～100mm) 12Cr2Mo1R (SA3 87Gr22Cl2) Plate Steel can be used for making various hydrogen-contacting equipments.
Particularly, hydrogen-contacting equipment of the present invention 12Cr2Mo1R steel, its composition quality per-cent is: C:0.10～0.1 5, Si :≤0.10, Mn:0.40～0.60, P≤0.010, S≤0.003, Cr:2.0～2.5, Mo:0.90～1.10, Cu:0.10～0.20, Ni:0.10～0.20, Sn≤0.003, Sb≤0.003, As≤0.003, Ca:0.001～0.005, all the other are Fe and inevitable impurity.
In 12Cr2Mo1R steel of the present invention,
C, very big to intensity, low-temperature flexibility and the weldability influence of steel, from low-temperature flexibility and the weldability of improving steel, wish that C content is controlled lowlyer in the steel, still, do not wish that again C is low excessively from the intensity of steel; Therefore C content should not be higher than 0.15%.
The minimizing of Si content can improve high temperature tensile strength, and its effect temperature is high more remarkable more; Si also is that embrittlement promotes element, and low Siization is to reduce the effective measure of embrittlement; Therefore Si content is controlled at below 0.10%.
Mn is identical with Si also to be that embrittlement promotes element, but Mn is different with Si, and Mn has big influence to hardening capacity, prevents promptly that for guaranteeing hardening capacity ferrite from generating necessity and setting out, and low Mnization is along with the increase of steel plate thickness is restricted naturally; Consider the thickness of finished product, so Mn contains the upper limit of measuring standard range, require Mn greater than 0.4%.
EMBRITTLEMENT ELEMENTS Sn, Sb, P, with the increase of Sn, Sb, P,
All increase, its degree Sn, Sb are roughly the same, and P significantly increases embrittlement than Sn, Sb; Guarantee angle to require Sn, Sb, P low as far as possible from performance, but consider cost factor and satisfy user demand, so Sn, Sb content be controlled at below 0.003%, P content is controlled at below 0.01%.
S has very big detrimental effect as harmful low-temperature flexibility that is mingled with steel in the steel, but considers factors such as steel-making operability, steel-making cost, and S content need be controlled at≤and 0.003%.
Ni and Mn play retarding action to the proeutectoid ferrite reaction kinetics in single iron carbon system, can change the form of bainite under certain speed of cooling, promote the production of lower bainite.Add an amount of Ni and can also reduce FATT.Therefore Ni is controlled at 0.10～0.20%.
Cu and Ni coexistence produce precipitated phase Ni
3Cu is favourable to high temperature creep property.Therefore Cu is controlled at 0.10%～0.20%.
Ca carries out denaturing treatment to sulfide in the steel, make it to become non deformable, stablize tiny spherical sulfide, so the OK range of Ca content is 0.001～0.005%.
The hydrogen-contacting equipment of the present invention manufacture method of 12Cr2Mo1R Plate Steel, it comprises the steps:
A) hydrogen-contacting equipment steel, its composition quality per-cent is: C:0.10～0.15, Si :≤0.10, Mn:0.40～0.60, P≤0.010, S≤0.003, Cr:2.0～2.5, Mo:0.90～1.10, Cu:0.10～0.20, Ni:0.10～0.20, Sn≤0.003, Sb≤0.003, As≤0.003, Ca:0.001～0.005, all the other are Fe and inevitable impurity;
B) press mentioned component and adopt converter smelting, and be cast as ingot casting;
C) ingot casting is rolled after the breaking down cogging again;
D) carry out normalizing treatment, normalizing temperature after rolling: 900～950 ℃;
E) utilize the press quenching machine to quicken cooling (ACC) with core 〉=0.5 ℃/s speed of cooling after the normalizing, bainitic transformation fully takes place to cool off continuously in Plate Steel, suppresses the proeutectoid ferrite phase transformation, obtains bainite structure in the full thickness range;
F) temper, tempering temperature are 700～760 ℃.
Further, die casting is adopted in step b) casting of the present invention, from the inner segregation angle of strand.
In addition, the low-pressure stage discharge 20～35m of the press quenching machine of the present invention's employing
3/ min, water yield ratio in top and bottom is 1: 1.1～1.2; Water-cooled time 5～10min, press quenching machine outlet surface of steel plate temperature is greater than 100 ℃.
Existing thermal treatment process can be divided into three kinds of situations: 1. normalizing+tempering, 2. normalizing+acceleration cooling+tempering, 3. quenching+tempering.Domestic Wuyang steel mill and Japan factory adopt normalizing+tempering, and Dillingen, Germany adopts normalizing+acceleration cooling+tempering, and French A Sainuo adopts quenching+tempering.
According to research, in theory, 2. method is best, obtains bainite structure, the most desirable.Method is 1. to the steel plate greater than 50mm, and the core speed of cooling is too slow, can not get bainite structure, and is least desirable, is difficult to reach the requirement of hydrogen-contacting equipment with steel.Method 3. speed of cooling is too fast, and perhaps full thickness of slab obtains martensitic stucture, and perhaps the surface is a bainite for martensite, core; The former hardness is too high, and user's difficult forming, martensitic stucture are the low-temperature transformation tissues, may bring the instability of performance when at high temperature using; The tissue odds of latter's thickness of slab direction is even, and is unfavorable to use properties.
Pass through computer Simulation, can draw, under atmosphere hollow cool condition (natural condition), the speed of cooling of the core of 50mm thickness steel plate (1/2 thickness place) is about 0.5 ℃/s, therefore the steel plate that surpasses 50mm for thickness, when its core speed of cooling requires greater than 0.5 ℃/s, need reach by forced cooling method, means have gas blower air blast cooling, atomized water spray cooling and water-cooled according to the difference of water-cooled speed, can be divided into again and quicken cooling and quenching, for 12Cr2Mo1R, in general, the water yield is little, the acceleration that is called that obtains bainite structure is cooled off, and the water yield is big, obtain the quenching that is called of martensitic stucture.
It is inequality to realize that the acceleration cooling way respectively has, and the simple spray equipment of the employing that has cools off, and the employing cooling facility for laminar flow that has cools off.
The present invention adopts the press quenching machine to quicken cooling.Generally, because the quenching press water yield is too big, cold too soon, what obtain is martensitic stucture, and characteristics of the present invention are the characteristics of dividing two sections of high and low pressures according to quenching press, utilize low-pressure stage water-cooled 12Cr2Mo1R, obtain required tissue.
Press quenching machine parameter is selected as follows:
Normalizing temperature: 900～950 ℃, low-pressure stage discharge 20～35m
3/ min, water yield ratio in top and bottom is 1: 1.1～1.2; Water-cooled time 5～10min, press quenching machine outlet surface of steel plate temperature is greater than 100 ℃.
The selection of press quenching machine mode of operation
The press quenching machine divides two sections of high and low pressures, and high pressure section maximum flow of water amount is 90m
3/ min (8bar), long 3273mm, low-pressure stage maximum flow of water amount 150m
3/ min (4bar), long 19431mm; High pressure section is generally 70～85m during the quenching mode
3/ min, low-pressure stage are usually greater than 70m
3/ min, press quenching machine outlet steel billet temperature is 80 ℃ to the maximum; The quenching mode water yield is big, makes the powerful water yield of steel plate steel plate cool to room temperature, particularly high pressure section make surface of steel plate quench into martensitic stucture rapidly at short notice; Therefore need avoid high pressure section, enter the low-pressure stage cooling, low-pressure stage is selected less discharge (the acceleration type of cooling), make steel plate with certain rate of cooling (core greater than 0.5 ℃/s) be cooled to certain temperature (surface temperature is greater than 100 ℃); Consider the limited length of press quenching machine, steel plate is in low-pressure stage swing cooling; Top and bottom discharge is distributed rationally, obtains good plate shape.
The present invention adopts converter smelting can make Sb, Sn, As content lower, and then reduces J coefficient, X coefficient; It is better that acceleration cooling after the normalizing helps 1/2 thickness place microstructure, thereby guarantee the performance at 1/2 thickness place; On chemical ingredients, do not use V and B.
Beneficial effect of the present invention
It is that CrMo steel series low-alloy steel is as basis (satisfying the 12Cr2Mo1R standard-required) that the present invention adopts 2.25Cr1Mo, CrMo contains to measure in 12Cr2Mo1R (SA387Gr22Cl2) standard-required and limits, adding an amount of Ni can promote bainite to form, it is favourable to high temperature creep property to add proper C u and Ni coexistence, harmful elements such as control Sn, As, Sb, P, S can reduce Plate Steel temper brittleness, accelerated cooling process after the normalizing can make Plate Steel obtain bainite structure, obtains excellent mechanical property and good weldability.
Description of drawings
Fig. 1 is the micro-metallographic structure photo of one embodiment of the invention normalizing+acceleration cooling back core.
Embodiment
The embodiment of the invention is referring to table 1, and the target in kind of producing Plate Steel is referring to table 2,4, and table 3 is that its thermal treatment process compares.
The present invention utilizes the press quenching machine, by normalizing+acceleration cooling+tempering process, guarantees that the microstructure of 12Cr2Mo1R finished product steel plate is a tempering bainite, referring to Fig. 1.
As seen from Table 1, the Si content of embodiment is lower than comparative example 1 and 3; Sn, Sb, As content are lower than comparative example 3.
As seen from Table 2, the J coefficient of embodiment is higher than comparative example 1,2, but far below comparative example 3.Embodiment's
vThe Tr55+2.5 Δ
vTr55 and comparative example are suitable substantially.
As seen from Table 4, the intensity of embodiment is higher than comparative example; Akv is lower than comparative example slightly, but far above standard-required.
Table 1
Unit: mass percent
| C | Si | Mn | P | ?S | ?Cu | ?Ni | ?Cr | ?Mo | ?Ca?ppm | ?Sn | Sb | As | | ||
| Embodiment | |||||||||||||||
| 1 | 0.132 | 0.099 | 0.49 | 0.007 | ?0.0022 | ?0.16 | ?0.17 | ?2.34 | ?0.99 | ?30 | ?0.0008 | 0.0006 | 0.003 | Surplus | |
| 2 | 0.148 | 0.081 | 0.46 | 0.008 | ?0.0027 | ?0.17 | ?0.17 | ?2.39 | ?0.98 | ?20 | ?0.0010 | 0.0007 | 0.002 | Surplus | |
| 3 | 0.127 | 0.040 | 0.53 | 0.008 | ?0.0020 | ?0.18 | ?0.15 | ?2.25 | ?1.05 | ?22 | ?0.0012 | 0.0010 | 0.001 | Surplus | |
| 4 | 0.120 | 0.051 | 0.59 | 0.006 | ?0.0017 | ?0.15 | ?0.20 | ?2.23 | ?1.07 | ?17 | ?0.0009 | 0.0008 | 0.002 | Surplus | |
| 5 | 0.125 | 0.063 | 0.48 | 0.009 | ?0.0020 | ?0.12 | ?0.18 | ?2.21 | ?1.03 | ?35 | ?0.0006 | 0.0007 | 0.001 | Surplus | |
| 6 | 0.129 | 0.089 | 0.49 | 0.009 | ?0.0025 | ?0.19 | ?0.10 | ?2.45 | ?0.95 | ?50 | ?0.0005 | 0.0009 | 0.002 | Surplus | |
| 7 | 0.119 | 0.092 | 0.58 | 0.005 | ?0.0017 | ?0.16 | ?0.18 | ?2.28 | ?1.00 | ?23 | ?0.003 | 0.0030 | 0.001 | Surplus | |
| 8 | 0.135 | 0.088 | 0.57 | 0.006 | ?0.0025 | ?0.18 | ?0.15 | ?2.10 | ?1.03 | ?12 | ?0.0011 | 0.0015 | 0.003 | Surplus | |
| Comparative example | 1 | 0.132 | 0.163 | 0.47 | 0.007 | ?0.0005 | ?0.155 | ?0.16 | ?2.292 | ?0.971 | ?0.000 | 0.0005 | 0.001 | Surplus | |
| 2 | 0.14 | 0.07 | 0.53 | 0.005 | ?0.003 | ?0.15 | ?0.152 | ?2.37 | ?1.03 | ?0.002 | 0.001 | 0.002 | Surplus | ||
| 3 | 0.13 | 0.17 | 0.55 | 0.004 | ?0.002 | ?0.06 | ?0.09 | ?2.24 | ?1.05 | ?0.006 | 0.0011 | 0.006 | Surplus | ||
Annotate: comparative example 1 is a Di Lingen company, and comparative example 2 is a company of Kobe Steel, and comparative example 3 is a A Sainuo company
Table 2 temper brittleness
| The steel sample | The J coefficient | The X coefficient | vTr55+2.5Δ |
| Embodiment | 45.63 | 7.92 | -86.7℃ |
| Comparative example 1 | 31.6 | 5.71 | -94.6℃ |
| Comparative example 2 | 35 | 6.0 | |
| Comparative example 3 | 72 | 8.0 |
Table 3 thermal treatment process
| The steel sample | Thermal treatment process | ACC equipment |
| Embodiment | Normalizing+ACC+ tempering | Utilize the press quenching machine to quicken cooling (ACC) |
| Comparative example 1 | Normalizing+AC+ tempering | |
| Comparative example 2 | Normalizing+tempering | |
| Comparative example 3 | Quenching+tempering |
Table 4 plate property
| The steel sample | YP MPa | TS MPa | δ ％ | Akν(-30℃)J |
| Embodiment | 434 | 572 | 26 | 292 |
| Comparative example 1 | 381 | 537 | 31.3 | 373 |
| Comparative example 2 | 375 | 535 | 33 | 392 |
| Comparative example 3 | 429 | 567 | 35 | 321 |
In sum, the present invention is the CrMo steel based on 2.25Cr1Mo exactly, add proper C u, Ni, harmful elements such as control Sn, As, Sb, P, S, utilize the press quenching machine equipment,, guarantee that the microstructure of 12Cr2Mo1R (SA387Gr22Cl2) finished product steel plate is a tempering bainite by normalizing+acceleration cooling+tempering process, obtain excellent mechanical property and good weldability, can be used for making various hydrogen-contacting equipments.
Claims (2)
1. hydrogen-contacting equipment is with the manufacture method of 12Cr2Mo1R Plate Steel, and it comprises the steps:
A) hydrogen-contacting equipment 12Cr2Mo1R steel, its composition quality per-cent is: C:0.10～0.15, Si :≤0.10, Mn:0.40～0.60, P≤0.010, S≤0.003, Cr:2.0～2.5, Mo:0.90～1.10, Cu:0.10～0.20, Ni:0.10～0.20, Sn≤0.003, Sb≤0.003, As≤0.003, Ca:0.001～0.005, all the other are Fe and inevitable impurity;
B) press mentioned component and adopt converter smelting, and be cast as ingot casting;
C) ingot casting is rolled after the breaking down cogging again;
D) carry out normalizing treatment, normalizing temperature after rolling: 900～950 ℃;
E) utilize the press quenching machine to quicken cooling after the normalizing, obtain bainite structure in the full thickness range with core 〉=0.5 ℃/s speed of cooling; The low-pressure stage discharge 20～35m of press quenching machine
3/ min; Water-cooled time 5～10min, press quenching machine outlet surface of steel plate temperature is greater than 100 ℃; Press quenching machine top and bottom water yield ratio is 1: 1.1～1.2;
F) temper, tempering temperature is 700～760 ℃, obtains thickness 50～100mm finished product Plate Steel.
2. hydrogen-contacting equipment as claimed in claim 1 is characterized in that with the manufacture method of 12Cr2Mo1R Plate Steel die casting is adopted in the step b) casting.
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