CN103205645A - Superlarge thickness hydrogen chromium molybdenum steel plate for hydrogenation equipment and manufacture method thereof - Google Patents
Superlarge thickness hydrogen chromium molybdenum steel plate for hydrogenation equipment and manufacture method thereof Download PDFInfo
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Abstract
The invention relates to a superlarge thickness hydrogen chromium molybdenum steel plate for hydrogenation equipment and a manufacture method thereof, and belongs to the technical field of ferrous metallurgy. A technical scheme is as below: the steel plate comprises the following components by weight: no more than 0.15% of C, no more than 0.10% of Si, 0.300.60% of Mn, no more than 0.007% of P, no more than 0.005% of S, 2.00-2.50% Cr, 0.90-1.10% of Mo, no more than 0.02% of Nb, no more than 0.20% of Cu, no more than 0.20% of Ni, no more than 0.003% of Sb, no more than 0.005% of Sn, no more than 0.016% of As, no more than 0.003% of O, N no more than 0.008%, no more than 0.0002% of H, no more than 0.03 of Ti and the balance of Fe and unavoidable impurities; a round steel ingot with piece weight of 80 tons is produced by electric arc furnace smelting and casting; and the steel ingot is subjected to forging cogging, rolling and a heat treatment process including normalizing, accelerated cooling and tempering to prepare the superlarge thickness chromium molybdenum steel plate with a maximum thickness of 256mm for hydrogenation equipment. A finished steel plate has maximum single weight reaching 60 tons, good cold bending property, no cracking during material manufacture and good resilience. The method provided by the invention reduces labor intensity, saves time and improves the utilization rate of materials.
Description
Technical field
The present invention relates to a kind of hydrogenation unit and face hydrogen chrome molybdenum steel plate and production method thereof with ultra-thick, belong to technical field of ferrous metallurgy.
Background technology
The development of petrochemical industry is in recent years mainly maximized around the deep processing of oil product secondary, device, with the flag that is applied as of hydrogen addition technology.Hydrogen addition technology is the advanced technologies that improves oil quality and change the secondary deep processing of oil product structure, is the sign of weighing a national petroleum refining state of the art and overall national strength.For shortening the gap between China's Petrochemical and external advanced level, [1983] No. 110 literary compositions of State Council's promulgated by the State Council in July nineteen eighty-three have been made " about promptly developing the decision of major technologies and equipment ".National major technologies and equipment ethene leading group determined in 1986, with five factories such as Zhenghai refinery, positive refinerys, 91 key equipments in seven cover 40～800,000 t/a hydrofinings and the cracker, classify " the Seventh Five-Year Plan " production domesticization project as, and by grind certainly and with the mode of external cooperation, progressively grasped conventional Cr-Mo steel pressurized vessel manufacturing technology.Owing to the working conditions harshness, material is in high temperature, high pressure and faces under the hydrogen operating mode hydrogenation for a long time with steel plate.Material also need satisfy the requirement of intensity under the high temperature, anti-temper embrittlement and hydrogen-type corrosion except satisfying basic ambient temperature mechanical properties.Therefore carried out a large amount of research and development at hydrogenator with steel both at home and abroad.Nineteen eighty-three American Petroleum Institute (API) (API) has formulated High Temperature High Pressure and has faced the material evolutionary operation (EVOP) of hydrogen pressure container, and U.S. material performance association (MPC) is responsible for concrete enforcement.AISI (AISI), American Society of Mechanical Engineers (ASME), U.S. material and test association (ASTM) and part enterprise customer have participated in exploitation.Development group has at first been developed enhancement type 2.25Cr-1Mo steel, and U.S. ASME boiler and the code cases 1960-1 in 1984 of the boilers and pressure vessel standard council are approved.Meanwhile, Japanese new energy development tissue (NEDO) has been formulated " sunlight program " and has been developed the hydrogen-contacting equipment steel.The external hydrogen-contacting equipment of producing mainly contains the Arcelor of France, the Di Lingen company of Germany and the company of Kobe Steel of Japan with the producer of steel at present.But can produce the 50t level at present and face the Arcelor that hydrogen Cr-Mo steel plate has only France.At present, background technology generally can only be produced the hydrogenation unit steel plate of thickness below 100mm, the problem that the performance of each side of steel plate thickness tending to run into to the development of big thickness direction the time reduces, if directly increase the thickness of steel plate on the basis that keeps existing composition proportion and production method, resulting big thickness steel plate does not just reach the various performance parameters that standard GB 713-2008 formulates.
Summary of the invention
The object of the invention provides a kind of hydrogenation unit and faces hydrogen chrome molybdenum steel plate and production method thereof with ultra-thick, and cold-bending property is good, and material does not ftracture when making, rebound resilience is good, reduce labour intensity, saved man-hour and the utilization ratio that has improved material, solved the problems referred to above that exist in the background technology.
Technical scheme of the present invention is: a kind of hydrogenation unit faces hydrogen chrome molybdenum steel plate with ultra-thick, formed by following components in weight percentage content: 0.12%≤C≤0.15%, 0.02%≤Si≤0.07%, Mn:0.50-0.60%, P≤0.007%, S≤0.005%, Cr:2.35-2.50%, Mo:0.95-1.10%, 0.012%≤Nb≤0.02%, Cu≤0.20%, Ni≤0.20%, Sb≤0.003%, Sn≤0.005%, As≤0.016%, O≤0.003%, N≤0.008%, H≤0.0002%, Ti≤0.03 surplus is Fe and unavoidable impurities.
The thickness of described steel plate is 256mm.
A kind of hydrogenation unit faces hydrogen chrome molybdenum steel plate and production method thereof with ultra-thick, comprises smelting procedure, hammer cogging operation, heating rolling operation, heat treatment step, and each process is as follows:
(1) smelting procedure: adopt the electric arc furnace mode to smelt, melting period is adopted oxygen blast, stream slag operation, and vacuum decarburization is sent into then and carried out refining in the LF refining furnace, enters the die casting operation after the refining, waters to cast out substance and reach 80 tons positive 16 rib steel ingots, is referred to as large steel ingot;
(2) hammer cogging operation: described large steel ingot is put into process furnace and is heated, and forges into the forging base of 470 * 2320 * 7450mm subsequently;
(3) heating rolling operation: it is rolling that described Steel Bloom is put into the continuous oven internal heating, be heated to 1200～1260 ℃, be incubated 12 hours, adopt the two-stage controlled rolling process, fs is the austenite recrystallization stage, the control draught, and subordinate phase is the non-recrystallize stage of austenite, it is too fast to roll the cooling of laggard windrow buttress cooling prevention steel plate, guarantees surface of steel plate and internal soundness;
(4) heat treatment step: adopt the thermal treatment process of normalizing+acceleration cooling+tempering, normalizing temperature is 920～950 ℃, puts into the acceleration heat-eliminating medium then and accelerates cooling, pass through tempering afterwards again, tempering temperature is 700-750 ℃, and soaking time is 2-3.5min/mm, makes the finished product steel plate; Stating the finished product steel plate is made up of following components in weight percentage content: C≤0.15%, Si≤0.10%, Mn:0.30-0.60%, P≤0.007%, S≤0.005%, Cr:2.00-2.50%, Mo:0.90-1.10%, Nb≤0.02%, Cu≤0.20%, Ni≤0.20%, Sb≤0.003%, Sn≤0.005%, As≤0.016%, O≤0.003%, N≤0.008%, H≤0.0002%, Ti≤0.03 surplus is Fe and unavoidable impurities.
The mode of described operation employing electrosmelting and directional solidification technique are smelted substance and are reached 80 tons, top maximum diameter 1950mm, bottom maximum diameter 2100mm, and the huge billet of high 2900mm has satisfied the requirement of producing Plate Steel compression ratio and substance.
Described heating rolling operation, the rate of heating of steel ingot when the soaking pit internal heating is: when temperature is lower than 700 ℃, rate of heating≤100 ℃/h, temperature is in the time of 700 ℃～950 ℃, rate of heating≤110 ℃/h, temperature in the time of 950 ℃～1200 ℃, rate of heating≤150 ℃/h.
Described heating rolling operation, the percentage pass reduction of fs 〉=20%, accumulative total draft 〉=70%.
Described heating rolling operation, accumulative total draft 〉=50% of subordinate phase.
Described science and engineering order, fast heat-eliminating medium are water.
Product of the present invention adopts Cr, Mo, Nb alloying element complex intensifying, through rational heat treatment technology, has obtained good obdurability coupling, does not reduce the welding property of steel plate simultaneously again.C among the present invention≤0.15%, Si≤0.07%, Si mainly improve the intensity of steel plate with the solution strengthening form, but can not too high levels, in order to avoid reduce the toughness of steel plate; Mn content is chosen in 0.50-0.60%, Mn mainly plays solution strengthening, reduces transformation temperature and improves armor plate strength, and Mn can significantly improve the hardening capacity of steel plate, with the increase of Mn content, plasticity and the low-temperature impact toughness of steel plate slightly descend, and intensity significantly improves; Cr content 2.35-2.50%, Mo content 0.95-110%, Cr, Mo all can increase austenite and cross cold energy power, improve the hardening capacity of steel plate, promote the formation of bainite; Ni, Mo content are low, both can satisfy steel plate obdurability demand, save alloy again, reduce cost; Nb≤0.02%, Nb is, and the grain refining effect is fairly obvious; P≤0.007%, S≤0.005% is pure in order to guarantee the steel plate steel, higher impelling strength and the resistance to embrittlement energy that influences steel plate of P content.The bullion content that adds in the steel plate of the present invention is less relatively, and cost is lower, has the market competitiveness.
Production method of the present invention is smelted with the electrosmelting mode, and impurity harmful element content such as P, S are low, and steel is pure; It is the controlled rolling of II type and principal-employment rolling technology that steel plate of the present invention adopts the two-stage controlled rolling process, has solved the mill milling insufficient pressure and the thick inequality of crystal grain, the impelling strength that cause lower problem; The rolling technology of steel plate of the present invention is simple, and easy handling is suitable for that quenching press is arranged, the ordinary steel ironworks of normalizing furnace, outer machine stove, car bottom furnace produces.Production method of the present invention has realized lower carbon equivalent and the chemical composition design of alloy content, obtained simultaneously having more tiny weave construction and Geng Jia resistance to embrittlement can steel plate, the every mechanical performance index of producing of steel plate all meets the technical qualification requirement, and production cost significantly reduces.The mechanical property of steel plate of the present invention after the simulation postweld heat treatment reaches following requirement: Rp0.2＞310MPa, Rm 520-680MPa, A 〉=22% ,-30 ℃ of A after testing
KV〉=80J, J coefficient≤90, P+Sn≤0.012% has good anti-hydrogen-type corrosion and resistance to embrittlement energy.
The present invention adopts the mode guaranteed performance requirement that increases the Nb element, increases alloying elements such as C, Cr, Mo, and has suitably added the Ti element in order to guarantee to produce the chrome molybdenum steel plate of qualified big thickness, big substance on the composition.In order to satisfy the requirement of steel plate gauge, adopt the mode of design super large ingot mould, water and outpour the large-scale steel ingot that substance reaches 80 tons.Adopt forging, controlled rolling, normalizing to accelerate the mechanical property that thermal treatment process such as cooling, tempering guarantee steel plate subsequently.
Advantage of the present invention and effect: hydrogenation unit of the present invention can reach 256mm with the maximum ga(u)ge of big thickness chrome molybdenum steel plate, the maximum substance of steel plate reaches 60 tons, plate has satisfied domestic and international pressurized vessel manufacturing to the demand of big thickness steel plate, can be widely used on the petrochemical equipments such as high pressure hot separator, hydrogenator; The cold-bending property of steel plate is good, and material does not ftracture when making, and rebound resilience is good, has reduced labour intensity, has saved man-hour and the utilization ratio that has improved material; The steel plate template is good, and roughness reaches≤4mm/m, can reduce about 50 yuan/ton of the making mangling expense of equipment making side.
Description of drawings
Fig. 1 is the metallographic structure (maximum analog postweld heat treatment state) on steel plate head surface;
Fig. 2 is the metallographic structure (maximum analog postweld heat treatment state) of steel plate tail surface;
Fig. 3 is the metallographic structure (maximum analog postweld heat treatment state) of steel plate head 1/2 thickness of slab;
Fig. 4 is the metallographic structure (maximum analog postweld heat treatment state) of steel plate afterbody 1/2 thickness of slab.
Embodiment
The present invention will be further described by the following examples.
The hydrogenation unit of example is made up of following components in weight percentage content with big thickness chrome molybdenum steel plate: 0.12%≤C≤0.15%, 0.02%≤Si≤0.07%, Mn:0.50-0.60%, P≤0.007%, S≤0.005%, Cr:2.35-2.50%, Mo:0.95-1.10%, 0.012%≤Nb≤0.02%, Cu≤0.20%, Ni≤0.20%, Sb≤0.003%, Sn≤0.005%, As≤0.016%, O≤0.003%, N≤0.008%, H≤0.0002%, Ti≤0.03, the hydrogenation unit of present embodiment is that 41.3, P+Sn content is 0.007% with the J coefficient of big thickness chrome molybdenum steel plate, and the thickness of steel plate is 256mm.
The hydrogenation unit of the present embodiment production method of ultra-thick chrome molybdenum steel plate, concrete steps are:
(1) smelt step: smelt with the 100T ultra-high power electric arc furnace earlier, melting period is adopted big quantity of slag stream slag operation, vacuum decarburization, and when molten steel temperature reaches 1600 ℃, tapping.Send into then and carry out refining 1 hour in the LF refining furnace, deoxidation fast, according to taking off the S situation, fine setting Mn, Mo, Nb, Ni, Cr content enter evacuation after the refining, enter the die casting operation after vacuumizing in 30 minutes, prepare the large-scale steel ingot that substance reaches 80t.
(2) hammer cogging step: described large steel ingot is put into the process furnace internal heating, is heated to 1210 ± 10 degree insulations 8 hours, and the beginning forging is through chamfered edge, the side of pulling out, pull out the forging base that technology such as flat forges 470 * 2320 * 7450mm.
(2) heating rolling step: it is rolling that described Steel Bloom is put into the continuous oven internal heating, be heated to 1200 ℃, be incubated 12 hours, rate of heating when the soaking pit internal heating is: when temperature is lower than 700 ℃, rate of heating is 100 ℃/h, temperature is in the time of 700 ℃～950 ℃, and rate of heating is 110 ℃/h, and temperature is in the time of 950 ℃～1200 ℃, rate of heating is 150 ℃/h, adopt the two-stage controlled rolling process, the fs is the austenite recrystallization stage, in this stage, austenite deformation and recrystallize carry out simultaneously, the percentage pass reduction of fs is 10%, and the accumulative total draft is 60%, and subordinate phase is (950 ℃～A of non-recrystallize stages of austenite
R3), the accumulative total draft of subordinate phase is 50%, in this stage, austenite crystal is elongated, form high-density mechanical twin and deformed belt in the austenite of non-recrystallization in elongation, microalloy carbon, nitride are separated out because of deformation induced simultaneously, roll the cooling of laggard windrow buttress;
(3) heat treatment step: the thermal treatment process that adopts normalizing+acceleration cooling+tempering, normalizing temperature is 920-950 ℃, put into water then and accelerate cooling, pass through tempering afterwards again, tempering temperature is 670 ℃-750 ℃, soaking time is 2.5-3.5min/mm, is rolled into the thick steel plate of 256mm afterwards.
The steel plate of embodiment is through the simulation postwelding, and again through postweld heat treatment, heat-treat condition is 690 ℃ * 32h, afterwards the mechanical property of steel plate is tested, and test result is shown in Table 1.Embodiment 1 steel plate is done cold bending test after normalizing+tempering, D=3a, and 180 °, cold bending test result is intact.
Table 1 embodiment steel plate Composition Control
The mechanical property (1/2) of table 2 embodiment steel plate after the simulation postweld heat treatment
Table 3 steel plate inclusion fabric analysis result
By table 1, table 2, table 3 and Fig. 1 as can be seen, hydrogenation unit of the present invention is higher than the standard-required value far away with the mechanical property of ultra-thick chrome molybdenum steel plate, and crystal grain is superfine, is organized as the tempering bainite of homogeneous.And the thickness of steel plate of the present invention reaches 256mm, is the thickness of 100mm far above this kind steel plate maximum ga(u)ge at present also, satisfied market to the demand of hydrogenation unit with ultra-thick chrome molybdenum steel plate.
Claims (7)
1. a hydrogenation unit faces hydrogen chrome molybdenum steel plate with ultra-thick, it is characterized in that: formed by following components in weight percentage content: 0.12%≤C≤0.15%, 0.02%≤Si≤0.07%, Mn:0.50-0.60%, P≤0.007%, S≤0.005%, Cr:2.35-2.50%, Mo:0.95-1.10%, 0.012%≤Nb≤0.02%, Cu≤0.20%, Ni≤0.20%, Sb≤0.003%, Sn≤0.005%, As≤0.016%, O≤0.003%, N≤0.008%, H≤0.0002%, Ti≤0.03 surplus is Fe and unavoidable impurities.
2. a kind of hydrogenation unit according to claim 1 faces hydrogen chrome molybdenum steel plate with ultra-thick, and the thickness that it is characterized in that described steel plate is 256mm.
3. a hydrogenation unit is characterized in that comprising smelting procedure, hammer cogging operation, heating rolling operation, heat treatment step with the production method that ultra-thick faces hydrogen chrome molybdenum steel plate, and each process is as follows:
(1) smelting procedure: adopt the electric arc furnace mode to smelt, melting period is adopted oxygen blast, stream slag operation, and vacuum decarburization is sent into then and carried out refining in the LF refining furnace, enters the die casting operation after the refining, waters to cast out substance and reach 80 tons positive 16 rib steel ingots, is referred to as large steel ingot;
(2) hammer cogging operation: described large steel ingot is put into process furnace and is heated, and forges into the forging base of 470 * 2320 * 7450mm subsequently;
(3) heating rolling operation: it is rolling that described Steel Bloom is put into the continuous oven internal heating, be heated to 1200～1260 ℃, be incubated 12 hours, adopt the two-stage controlled rolling process, fs is the austenite recrystallization stage, the control draught, and subordinate phase is the non-recrystallize stage of austenite, it is too fast to roll the cooling of laggard windrow buttress cooling prevention steel plate, guarantees surface of steel plate and internal soundness;
(4) heat treatment step: the thermal treatment process that adopts normalizing+acceleration cooling+tempering, normalizing temperature is 920～950 ℃, put into the acceleration heat-eliminating medium then and accelerate cooling, pass through tempering afterwards again, tempering temperature is 700-750 ℃, soaking time is 2-3.5min/mm, makes the finished product steel plate; Stating the finished product steel plate is made up of following components in weight percentage content: C≤0.15%, Si≤0.10%, Mn:0.30-0.60%, P≤0.007%, S≤0.005%, Cr:2.00-2.50%, Mo:0.90-1.10%, Nb≤0.02%, Cu≤0.20%, Ni≤0.20%, Sb≤0.003%, Sn≤0.005%, As≤0.016%, O≤0.003%, N≤0.008%, H≤0.0002%, Ti≤0.03 surplus is Fe and unavoidable impurities.
4. a kind of hydrogenation unit according to claim 3 faces the production method of hydrogen chrome molybdenum steel plate with ultra-thick, it is characterized in that: the mode of described operation employing electrosmelting and directional solidification technique are smelted substance and are reached 80 tons, top maximum diameter 1950mm, bottom maximum diameter 2100mm, the huge billet of high 2900mm has satisfied the requirement of producing Plate Steel compression ratio and substance.
5. a kind of hydrogenation unit according to claim 3 faces the production method of hydrogen chrome molybdenum steel plate with ultra-thick, it is characterized in that: described heating rolling operation, the rate of heating of steel ingot when the soaking pit internal heating is: when temperature is lower than 700 ℃, rate of heating≤100 ℃/h, temperature is in the time of 700 ℃～950 ℃, rate of heating≤110 ℃/h, temperature in the time of 950 ℃～1200 ℃, rate of heating≤150 ℃/h.
6. a kind of hydrogenation unit according to claim 3 is characterized in that: described heating rolling operation, the percentage pass reduction of fs 〉=20%, accumulative total draft 〉=70% with the production method that ultra-thick faces hydrogen chrome molybdenum steel plate; Accumulative total draft 〉=50% of subordinate phase.
7. a kind of hydrogenation unit according to claim 3 is with the production method that ultra-thick faces hydrogen chrome molybdenum steel plate, and it is characterized in that: described heat treatment step operation, fast heat-eliminating medium are water.
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| CN103710628A (en) * | 2013-12-30 | 2014-04-09 | 南阳汉冶特钢有限公司 | Large-thickness hydrogenating 14Cr1MoR steel plate and production method thereof |
| CN104971962A (en) * | 2014-04-10 | 2015-10-14 | 鞍钢股份有限公司 | Method of producing super-thick steel plate through two-dimensional deformation of continuous casting billet |
| CN104971960A (en) * | 2014-04-10 | 2015-10-14 | 鞍钢股份有限公司 | Method of producing super-thick steel plate through three-dimensional deformation of continuous casting billet |
| CN104971961B (en) * | 2014-04-10 | 2017-01-18 | 鞍钢股份有限公司 | Method of producing super-thick steel plate through one-dimensional deformation of continuous casting billet |
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Application publication date: 20130717 |