CN102732792A - Steel with thickness no lower than 100mm used in vessel in hydrogen environment, and production method thereof - Google Patents
Steel with thickness no lower than 100mm used in vessel in hydrogen environment, and production method thereof Download PDFInfo
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Abstract
The invention relates to steel with a thickness no lower than 100mm used in a vessel in a hydrogen environment, and a production method thereof. The steel comprises the components of, by weight: 0.08-0.12% of C, 0.05-0.12% of Si, 0.30-0.45% of Mn, no more than 0.012% of P, no more than 0.010% of S, 2.10-2.25% of Cr, no more than 0.18% of Ni, 0.95-1.10% of Mo, no more than 0.12% of Cu, no more than 0.005% of Sn, no more than 0.004% of As, no more than 0.003% of Sb, no more than 0.008% of N, and no more than 0.003% of O. A temper embrittlement sensitivity coefficient is that J=(Si+Mn)(P+Sn)*0000<=80. The production method comprises the steps of: electric furnace smelting; molten steel preheating; LF furnace processing; slag skimming; VD vacuum furnace processing; Si-Ca wire feeding; secondary argon blowing; continuous casting; heap-cooling to room temperature; electroslag re-melting and smelting; ingot drawing; mold cooling; pit cooling; slab heating; staged rolling; air cooling; and normalizing and tempering heat treatments. The obtained steel plate is ready for utilization. The steel plate provided by the invention has a thickness of 100-150mm. The purity of the steel is high. The surface of the ingot is smooth. Requirements of mechanical property are satisfied.
Description
Technical field
The present invention relates to pressure vessel steel and working method thereof, what specifically belong to a kind of thickness >=100 millimeter faces hydrogen tank with steel and working method thereof.
Background technology
The pressure vessel steel purposes is extremely wide, is widely used in industries such as oil, chemical industry, power station, boiler, generally is used to make reactor drum, heat exchanger, separator, gas tube, boiler-steam dome etc.12Cr2Mo1R faces the hydrogen tank steel and is mainly used in hydrogenator, and it is the great key equipment of modern petroleum refining industry, its normally at HTHP, face hydrogen, have under the abominable working conditions of corrosive mediums such as hydrogen sulfide and move.Therefore need anti-temper embrittlement ability, the strong starting material of anti-hydrogen etch ability to make hydrogenator.
Because pressurized vessel is worked under high temperature, high pressure and hydroconversion condition, a series of the key technical indexes such as material purity, anti-embrittlement ability, internal soundness are required very harsh.Make the hydrogenation reaction apparatus and use the demand of big substance ultra thick (greater than 100mm) steel plate also increasing, for reducing the manufacturing cost of various devices, these devices all trend towards maximizing; For improving the safe reliability of large-scale plant, the plate quality that uses is required more and more stricter.From the mode of present special heavy plate production, except adopting original forging method, also has popular continuous metal cast process.But continuous casting production receives the restriction of technical qualification can't produce the excessive special heavy plate of thickness; Maximum in the world at present revolving furnace continuous casting slab thickness is 390mm; Because the restriction of inner segregation of continuous-casting converter billet and compression ratio can only be produced the special heavy plate of thickness less than 100mm.
Chinese patent number is 201010598263.9 patent documentation; Disclose a kind of high-quality molten iron, KR hot metal pretreatment, 100 tons of top and bottom combined blown converters, Argon processing, the refining of LF stove, die casting cast, walking beam furnace, 3800mm milling train, the cooling of ACC laminar flow, 11 roller thermal straightening machines, cooling in heap, modified, finishing, outside inspection, flaw detection, warehouse-in process sequence down the big thickness C r-Mo of production be 12Cr2Mo1R container steel and working method thereof, its chemical ingredients and mass percent (%) C:0.10～0.14, Si:0.20～0.50, Mn:0.30～0.60, P :≤0.018, S :≤0.010, Cr:2.0～2.50, Ni :≤0.20, Mo:0.90～1.10, Als :≤0.040.But utilized the mode of converter smelting+die casting cast to make steel in this patent, enough draught have been arranged and become a useful person raw material though guaranteed big substance steel plate, can't guarantee high purity, and die casting cast lumber recovery has been lower, operating environment is relatively poor.The chemical ingredients of the steel that provides in this patent instance simultaneously can't satisfy faces hydrogen steel temper embrittlement sensitivity coefficient (J coefficient) index, therefore can't use as facing the hydrogen steel.
Summary of the invention
The problem that the present invention will solve is to face hydrogen steel temper embrittlement sensitivity coefficient (J coefficient) height; The cleaning of steel is poor; The lower problem of die casting cast lumber recovery provides a kind of temper embrittlement sensitivity coefficient J=(Si+ Mn) (P+ Sn) * 10000≤100J, and the cleanliness factor of molten steel is higher; Metal structure and chemical ingredients are even, steel plate thickness greater than 100 millimeters face hydrogen tank with steel and working method thereof.
Realize the measure of above-mentioned purpose:
The hydrogen tank that faces of a kind of thickness>=100 millimeter is used steel; Its component and weight percent content are: C:0.08～0.12%, Si:0.05～0.12%, Mn:0.30～0.45%, P: S≤0.012% :≤0.010%, Cr:2.10～2.25%, Ni :≤0.18%, Mo:0.95～1.10%, Cu: Sn≤0.12%: As≤0.005%: Sb≤0.004%: N≤0.003% :≤0.008%; O≤0.003%, all the other are Fe and unavoidable impurities; And should satisfy temper embrittlement sensitivity coefficient J=(Si+ Mn) (P+ Sn) * 10000≤80.
That produces a kind of thickness >=100 millimeter faces the method for hydrogen tank with steel, its step:
1) carry out electrosmelting, the control tapping temperature is at 1620～1640 ℃;
2) with molten steel preheating 3～5 minutes;
3) carrying out the LF stove handles: add quickened lime according to 45～70Kg/ ton steel, add silico-calcium or ferrosilicon powder according to 0.03～0.05Kg/ ton steel, add the AD15 reductor according to 0.015～0.025Kg/ ton steel;
4) skim, the weight percent content of Si exists in the control molten steel: 0.05～0.15%;
5) in the VD vacuum oven, carry out vacuum-treat and Argon, according to being blown into argon gas in 80～100ml/ minute; Control vacuum tightness is no more than 67Pa, and proceeds to few 25 minutes pressurize, and vacuum processing time is no less than 25 minutes and stops blowing argon gas simultaneously;
6) according to 2.7～3.0 meters/ton disposable feeding Si of steel-Ca lines;
7) carry out Argon once more, be blown into according to 80～100ml/ minute, argon blowing time was not less than 8 minutes;
8) carry out continuous casting, the control casting speed is at 1.6～1.7 meters/minute, and the control slab thickness is no less than 150 millimeters;
9) cooling in heap is to room temperature;
10) adopt low frequency bipolar series slab electroslag furnace to carry out electric slag refusion and smelting and stripping:
A) will splice the electroslag furnace of packing into by the strand of electrosmelting, and form consumable utmost point loop; And pre-melted slag packed in the mold of electroslag furnace according to 20～30Kg/ ton steel;
B) carrying out stripping also adopts protective guard to carry out slow cooling simultaneously: when the liquid steel level height in the electroslag furnace reached 60～＜70 millimeters, the stripping speed control was in 3.5～＜4.5 mm/min; When the liquid steel level height in the electroslag furnace reached 70～＜80 millimeters, the stripping speed control was in 4.5～＜6.5 mm/min; When the liquid steel level height in the electroslag furnace reach 80 millimeters and above after, the stripping speed control is in 6.5～8.5 mm/min;
C) when stripping speed control during, carry out remelting, and added aluminum shot according to 32～36g/ minute and finish until remelting in 7.5～8.5 mm/min;
D) carry out feeding, carry out feeding when consumable electrode is melted to when length remains 300～350 millimeters, and control stripping this moment speed and finish to become strand until remelting, and continue slow cooling in 6.5～7.5 mm/min;
In remelting, A, B, C and the D of control in the molten steel is mingled with total amount≤1.5 grade, O≤0.003%, N≤0.007%;
11) it is cold to carry out mould, and the mould cool time is 2～2.5 hours;
12) strand is inserted burial pit and cool off, the time is no less than 48 hours;
13) to the strand heating, the control soaking temperature is at 1200～1260 ℃, and the control heating rate was at 11～13 minutes/centimetre, and final heating and temperature control is at 1180～1230 ℃;
14) it is rolling to carry out segmentation: the start rolling temperature of control roughing section is at 1070～1130 ℃; The start rolling temperature of finish rolling section is at 890～910 ℃; Finishing temperature is at 860～880 ℃, and finish rolling open rolling thickness is at 220～240 millimeters, and the total draft of finish rolling end three passages is not less than 30%;
15) carry out air cooling, air cooling to 680～720 ℃;
16) adopt normalizing+tempering heat treatment, the control normalizing temperature is at 910～930 ℃, and the normalizing time was at 150～200 minutes; Tempering temperature is at 690～710 ℃, and tempering time was at 160～240 minutes;
17) for use.
The reason of the effect of each component and main technique and control among the present invention:
C:C is one of element of the indispensable raising steel strength of steel grade, and every increase by 0.10% tensile strength of carbon content approximately improves 60MPa, and yield strength approximately improves 20～30MPa.Along with the increase of carbon content, steel grade Fe3C increases, and hardenability also increases, and the tensile strength of steel and yield strength can improve, and plasticity and toughness index can descend, the welding property variation.And this steel grade is applicable to equipment such as hydrogenator, not only requires certain intensity, and mainly needs excellent toughness index and welding property.So regulation C content is on the low side, be limited to 0.05% down, on be limited to 0.12%.In this scope, not only guaranteed the intensity of steel and be fit to production operation, with the use properties that has guaranteed this steel grade.
Si:Si mainly improves steel strength with the solution strengthening form, also is the deoxidant element of steel grade.If but Si content is higher in the steel, can cause that then reduction of area descends, particularly impelling strength descends obviously; Also unfavorable to the weldableness of steel simultaneously; And this steel grade mainly is used for making equipment such as hydrogenator, and the Si height also is unfavorable for anti-hydrogen-type corrosion, therefore Si content is chosen in 0.05%～0.15%.
Mn: aspect the intensity of guaranteeing steel and toughness, Mn is indispensable element.And low manganese is favourable for the toughness of steel grade weld metal, and therefore the content with Mn is chosen in 0.30～0.60%.
P, S: control P≤0.012%, S≤.010%, this is owing to have only the smelting Clean Steel, could guarantee the over-all properties of steel of the present invention.
Cr: the content of Cr is chosen in 2.10～2.50%, is because Cr can improve steel plate hardening capacity, makes the ferritic phase apparition move to right, and the cooling rate of widening bainitic transformation is interval, promotes the formation of middle temperature transformation tissue, improves the steel plate ys.
Ni:Ni has strengthening effect, and the Ni of adding 1% can improve steel strength 20MPa.Ni can also improve the toughness, particularly low-temperature flexibility of steel significantly.Steel grade adds Ni, is that base material or simulation welded heat affecting zone have all improved low-temperature flexibility significantly. but during too high levels, except that increasing production cost, also cause the steel plate iron scale to be difficult to come off, so the upper limit be controlled at≤0.20%.
The content of Mo:Mo is chosen in 0.95～1.10%, is because Mo can improve steel plate hardening capacity, makes the ferritic phase apparition move to right, and the cooling rate of widening bainitic transformation is interval, promotes the formation of middle temperature transformation tissue, improves the steel plate ys.
Cu:Cu content is controlled at≤and 0.18%, be because Cu is an austenite former, when enlarging the austenite phase region, also in drawing process, promoted austenitic formation and stabilization.The low-temperature flexibility that Ni improves steel simultaneously also improves the intensity of steel, but when the Ni too high levels, can make the hardening capacity of steel plate and hardenability increase, and makes steel plate HAZ toughness reduce, and worsens the welding property of steel plate.The existence of a spot of Cu can obviously improve the corrosion potential of steel, thereby improves the corrosion resistance nature of steel.Simultaneously when the content of Cu acquires a certain degree, but the precipitate of ε-Cu can improve the intensity of steel plate. and the content of Cu is higher than at 0.18% o'clock, can cause the hot-short phenomenon of steel, worsens plate surface quality.
Sn:Sn, As and Sb element are harmful element for this invention, and these three kinds of elements are very big for the temper brittleness influence of steel grade of the present invention, therefore carried out ceiling restriction for these three kinds of elements.
N :≤0.008%, steel grade N element is bigger for the toughness influence of steel plate, has therefore done the restriction of the upper limit.
The present invention and existing converter compared with techniques; The steel of producing has the purity height, sulphur content is low, non-metallic inclusion is few, surface of steel ingot is smooth, crystallization even compact, metal structure and chemical ingredients evenly, the steel plate thickness produced can also satisfy market to facing the mechanical property requirements of hydrogen tank with steel fully at 100～150 millimeters.
Description of drawings
Accompanying drawing is metallographic structure figure of the present invention.
Embodiment
Describe in detail in the face of the present invention down:
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 various embodiments of the present invention and the tabulation of Comparative Examples Performance Detection situation;
Table 4 is various embodiments of the present invention and Comparative Examples drawing by high temperature mechanical properties test result.
Various embodiments of the present invention are according to following steps production:
Its step:
1) carry out electrosmelting, the control tapping temperature is at 1620～1640 ℃;
2) with molten steel preheating 3～5 minutes;
3) carrying out the LF stove handles: add quickened lime according to 45～70Kg/ ton steel, add silico-calcium or ferrosilicon powder according to 0.03～0.05Kg/ ton steel, add the AD15 reductor according to 0.015～0.025Kg/ ton steel;
4) skim, the weight percent content of Si exists in the control molten steel: 0.05～0.15%;
5) in the VD vacuum oven, carry out vacuum-treat and Argon, according to being blown into argon gas in 80～100ml/ minute; Control vacuum tightness is no more than 67Pa, and proceeds to few 25 minutes pressurize, and vacuum processing time is no less than 25 minutes and stops blowing argon gas simultaneously;
6) according to 2.7～3.0 meters/ton disposable feeding Si of steel-Ca lines;
7) carry out Argon once more, be blown into according to 80～100ml/ minute, argon blowing time was not less than 8 minutes;
8) carry out continuous casting, the control casting speed is at 1.6～1.7 meters/minute, and the control slab thickness is no less than 150 millimeters;
9) cooling in heap is to room temperature;
10) adopt low frequency bipolar series slab electroslag furnace to carry out electric slag refusion and smelting and stripping:
A) will splice the electroslag furnace of packing into by the strand of electrosmelting, and form consumable utmost point loop; And pre-melted slag packed in the mold of electroslag furnace according to 20～30Kg/ ton steel;
B) carrying out stripping also adopts protective guard to carry out slow cooling simultaneously: when the liquid steel level height in the electroslag furnace reached 60～＜70 millimeters, the stripping speed control was in 3.5～＜4.5 mm/min; When the liquid steel level height in the electroslag furnace reached 70～＜80 millimeters, the stripping speed control was in 4.5～＜6.5 mm/min; When the liquid steel level height in the electroslag furnace reach 80 millimeters and above after, the stripping speed control is in 6.5～8.5 mm/min;
C) when stripping speed control during, carry out remelting, and added aluminum shot according to 32～36g/ minute and finish until remelting in 7.5～8.5 mm/min;
D) carry out feeding, carry out feeding when consumable electrode is melted to when length remains 300～350 millimeters, and control stripping this moment speed and finish to become strand until remelting, and continue slow cooling in 6.5～7.5 mm/min;
In remelting, A, B, C and the D of control in the molten steel is mingled with total amount≤1.5 grade, O≤0.003%, N≤0.007%;
11) it is cold to carry out mould, and the mould cool time is 2～2.5 hours;
12) strand is inserted burial pit and cool off, the time is no less than 48 hours;
13) to the strand heating, the control soaking temperature is at 1200～1260 ℃, and the control heating rate was at 11～13 minutes/centimetre, and final heating and temperature control is at 1180～1230 ℃;
14) it is rolling to carry out segmentation: the start rolling temperature of control roughing section is at 1070～1130 ℃; The start rolling temperature of finish rolling section is at 890～910 ℃; Finishing temperature is at 860～880 ℃, and finish rolling open rolling thickness is at 220～240 millimeters, and the total draft of finish rolling end three passages is not less than 30%;
15) carry out air cooling, air cooling to 680～720 ℃;
16) adopt normalizing+tempering heat treatment, the control normalizing temperature is at 910～930 ℃, and the normalizing time was at 150～200 minutes; Tempering temperature is at 690～710 ℃, and tempering time was at 160～240 minutes;
17) for use.
The component value tabulation (one) of table 1 various embodiments of the present invention and Comparative Examples
The component value tabulation (two) of table 1 various embodiments of the present invention and Comparative Examples
The main technologic parameters tabulation (one) of table 2 various embodiments of the present invention and Comparative Examples
The main technologic parameters tabulation (two) of table 2 various embodiments of the present invention and Comparative Examples
The main technologic parameters tabulation (three) of table 2 various embodiments of the present invention and Comparative Examples
The main technologic parameters tabulation (four) of table 2 various embodiments of the present invention and Comparative Examples
The main technologic parameters tabulation (five) of table 2 various embodiments of the present invention and Comparative Examples
Table 3 is various embodiments of the present invention and Comparative Examples mechanical properties test the results list
Table 4Drawing by high temperature mechanical properties test the results list of various embodiments of the present invention and Comparative Examples
Annotate: Comparative Examples 1 and 2 is for adopting the situation of converter smelting.
As everyone knows, steel plate thickness is big more, and then mechanical property is difficult to guarantee more.But can find out that from table 3 and table 4 Comparative Examples 1 and 2 is compared with the present invention, though mechanical property is more or less the same, thickness differs widely, and the thicklyest reaches 150 millimeters.This is explanation just, and the present invention is guaranteeing that mechanical property satisfies under the prerequisite of the new market requirement, has satisfied user's needs steel plate thickness again greater than the new demand more than 100 millimeters.
Claims (2)
1. the hydrogen tank that faces of thickness>=100 millimeter is used steel; Its component and weight percent content are: C:0.08～0.12%, Si:0.05～0.12%, Mn:0.30～0.45%, P: S≤0.012% :≤0.010%, Cr:2.10～2.25%, Ni :≤0.18%, Mo:0.95～1.10%, Cu: Sn≤0.12%: As≤0.005%: Sb≤0.004%: N≤0.003% :≤0.008%; O≤0.003%, all the other are Fe and unavoidable impurities; And should satisfy temper embrittlement sensitivity coefficient J=(Si+ Mn) (P+ Sn) * 10000≤80.
2. that produces a kind of thickness as claimed in claim 1 >=100 millimeters faces the method for hydrogen tank with steel, its step:
1) carry out electrosmelting, the control tapping temperature is at 1620～1640 ℃;
2) with molten steel preheating 3～5 minutes;
3) carrying out the LF stove handles: add quickened lime according to 45～70Kg/ ton steel, add silico-calcium or ferrosilicon powder according to 0.03～0.05Kg/ ton steel, add the AD15 reductor according to 0.015～0.025Kg/ ton steel;
4) skim, the weight percent content of Si exists in the control molten steel: 0.05～0.15%;
5) in the VD vacuum oven, carry out vacuum-treat and Argon, according to being blown into argon gas in 80～100ml/ minute; Control vacuum tightness is no more than 67Pa, and proceeds to few 25 minutes pressurize, and vacuum processing time is no less than 25 minutes and stops blowing argon gas simultaneously;
6) according to 2.7～3.0 meters/ton disposable feeding Si of steel-Ca lines;
7) carry out Argon once more, be blown into according to 80～100ml/ minute, argon blowing time was not less than 8 minutes;
8) carry out continuous casting, the control casting speed is at 1.6～1.7 meters/minute, and the control slab thickness is no less than 150 millimeters;
9) cooling in heap is to room temperature;
10) adopt low frequency bipolar series slab electroslag furnace to carry out electric slag refusion and smelting and stripping:
A) will splice the electroslag furnace of packing into by the strand of electrosmelting, and form consumable utmost point loop; And pre-melted slag packed in the mold of electroslag furnace according to 20～30Kg/ ton steel;
B) carrying out stripping also adopts protective guard to carry out slow cooling simultaneously: when the liquid steel level height in the electroslag furnace reached 60～＜70 millimeters, the stripping speed control was in 3.5～＜4.5 mm/min; When the liquid steel level height in the electroslag furnace reached 70～＜80 millimeters, the stripping speed control was in 4.5～＜6.5 mm/min; When the liquid steel level height in the electroslag furnace reach 80 millimeters and above after, the stripping speed control is in 6.5～8.5 mm/min;
C) when stripping speed control during, carry out remelting, and added aluminum shot according to 32～36g/ minute and finish until remelting in 7.5～8.5 mm/min;
D) carry out feeding, carry out feeding when consumable electrode is melted to when length remains 300～350 millimeters, and control stripping this moment speed and finish to become strand until remelting, and continue slow cooling in 6.5～7.5 mm/min;
In remelting, A, B, C and the D of control in the molten steel is mingled with total amount≤1.5 grade, O≤0.003%, N≤0.007%;
11) it is cold to carry out mould, and the mould cool time is 2～2.5 hours;
12) strand is inserted burial pit and cool off, the time is no less than 48 hours;
13) to the strand heating, the control soaking temperature is at 1200～1260 ℃, and the control heating rate was at 11～13 minutes/centimetre, and final heating and temperature control is at 1180～1230 ℃;
14) it is rolling to carry out segmentation: the start rolling temperature of control roughing section is at 1070～1130 ℃; The start rolling temperature of finish rolling section is at 890～910 ℃; Finishing temperature is at 860～880 ℃, and finish rolling open rolling thickness is at 220～240 millimeters, and the total draft of finish rolling end three passages is not less than 30%;
15) carry out air cooling, air cooling to 680～720 ℃;
16) adopt normalizing+tempering heat treatment, the control normalizing temperature is at 910～930 ℃, and the normalizing time was at 150～200 minutes; Tempering temperature is at 690～710 ℃, and tempering time was at 160～240 minutes;
17) for use.
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| CN103215512A (en) * | 2013-03-16 | 2013-07-24 | 南阳汉冶特钢有限公司 | Pressure vessel steel 12Cr2Mo1R and production technology of 150mm thick pressure vessel steel 12Cr2Mo1R plate |
| CN103484636A (en) * | 2013-09-05 | 2014-01-01 | 通裕重工股份有限公司 | Production process of forged tee |
| CN103740912A (en) * | 2013-12-28 | 2014-04-23 | 首钢总公司 | Processing method for improving temper embrittlement resistance of steel plate for pressure vessels |
| CN104164573A (en) * | 2014-07-11 | 2014-11-26 | 武汉钢铁(集团)公司 | Premelting slag used for producing container steel of hydrogenation reactor and application thereof |
| CN106011626A (en) * | 2016-07-04 | 2016-10-12 | 湖南华菱湘潭钢铁有限公司 | Production method for hydrogenation medium-thickness steel plate |
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| CN108330248A (en) * | 2018-01-04 | 2018-07-27 | 舞阳钢铁有限责任公司 | The smelting process of hydrogenation reactor steel 12Cr2Mo1R (H) |
| CN109972062A (en) * | 2019-04-09 | 2019-07-05 | 舞阳钢铁有限责任公司 | A kind of high-purity large size ESR ingot and its production method |
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| CN103215512B (en) * | 2013-03-16 | 2016-01-27 | 南阳汉冶特钢有限公司 | The production technique of a kind of pressure vessel steel 12Cr2Mo1R and 150mm slab thereof |
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| CN109972062B (en) * | 2019-04-09 | 2021-06-18 | 舞阳钢铁有限责任公司 | High-purity large electroslag ingot and production method thereof |
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