CN107312937A - A kind of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method and its equipment - Google Patents

A kind of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method and its equipment Download PDF

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CN107312937A
CN107312937A CN201710494008.1A CN201710494008A CN107312937A CN 107312937 A CN107312937 A CN 107312937A CN 201710494008 A CN201710494008 A CN 201710494008A CN 107312937 A CN107312937 A CN 107312937A
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electrode
slag
steel
stainless steel
calcium powder
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CN107312937B (en
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王新鹏
张春林
罗利阳
张娟娟
梁晓辉
朱晓锋
陈帅超
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CSSC Shuangrui Luoyang Special Equipment Co Ltd
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Luoyang Sunrui Special Equipment Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16Remelting metals
    • C22B9/18Electroslag remelting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Abstract

The present invention relates to a kind of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method and its equipment, first, the chemical composition composition of design steel ingot smelts circular electrode by refining at the beginning of intermediate frequency furnace+argon oxygen decarburizing furnace refinery practice;Pass through electroslag remelting(ESR)Technique smelts steel ingot.For the equipment of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, including electrode and liquid slag bath;Protective cover is provided with above liquid slag bath, the protective cover, which is provided with inner chamber, inner chamber, is provided with electrode;Protective cover bottom is provided with the inwall venthole of inert gas, and side lower section is provided with the primary inlet port of inert gas, and side top is provided with the primary inlet port of inert gas.High silicon stainless steel prepared by this method and equipment of the present invention, in high temperature environments, Resistance to Concentrated Sulfuric Acid Corrosion are strong, in the H of 150 DEG C of 98% concentration2SO4In solution, corrosion rate of the invention is less than 0.08mm/.

Description

A kind of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method and its equipment
Technical field
The present invention relates to technical field of material, specifically a kind of high temperature resistant concentrated sulfuric acid is manufactured with high silicon stainless steel Method and its equipment.
Background technology
Sulfuric acid is the basic chemical raw materials that a kind of corrosivity is strong, corrosion process is complicated, and high-temperature concentrated sulfuric acid produces hydrogen depolarization Corrosion and oxygen depolaxization corrosion.In high-temperature concentrated sulfuric acid, high silicon stainless steel has extremely excellent decay resistance, is sulfuric acid work Preferred material in industry.Due to the application circumstances of high silicon stainless steel, material is not required nothing more than in high-temperature concentrated sulfuric acid with excellent The good crevice corrosion of resistance to spot corrosion and stress corrosion cracking performance, and require that it has excellent plastically deformed performance, it can use In the machining deformation technique such as hammer cogging, hot rolling, cold rolling, low cost production and commercial Application are met.
By being retrieved to high silicon steel Patents, it is analyzed as follows:
" CN 101228287A " disclose the manufacture method of a kind of high silicon stainless steel and its material and high silicon stainless steel to patent, should High silicon steel described by patent is characterised by that the percentage by weight of each element is:C:0.02;Si:4;Cr:12;Ni:7;Surplus For Fe.The advantage of the patent is:By the method for crystal grain thinning, make material that there is higher fracture elongation, can be with this material Make in long-life, the spring of high abrasion, the load circumstance applied to high loading.
" CN 1544680A " disclose a kind of high silicon steel and its manufacture method to patent, the high silicon steel described by the patent It is characterised by, the percentage by weight of each element is:C:0.007-1;Si:5-10;Cr≤0.01; Ni≤0.01; Mn≤0.01; P≤0.01; S≤0.01;Surplus is Fe.The advantage of the patent is:The stretching plastic and processing characteristics of silicon steel are improved, favorably In the high silicon chip large-scale production of different-thickness, using thermo-mechanical processi technology, its microstructure carbon content and soft magnetism are controlled Energy.
" CN 101985679A " disclose a kind of productive technology of short flow of high silicon steel plate to patent, described by the patent High silicon steel is characterised by that the percentage by weight of each element is: Si:3.5-7;Surplus is Fe.The advantage of the patent is:Using The three layers composite metal pipe of casting method for centrifugal production, three-layer metal is the different high silicon steel of silicone content, is become using thermoplasticity Shape produces the steel plate that thickness is 0.1-1mm with the cold rolling method being combined.
" CN 102139279A " disclose a kind of utilization directional solidification and bar plate and prepare orientation high silicon steel flat cold-rolled sheet patent Method, the high silicon steel described by the patent is characterised by that the percentage by weight of each element is: Si:4.5-1.0;B:50- 2000ppm;Surplus is Fe.The advantage of the patent is:The orientation of the > directions of < 110 growth is prepared using remelting directional solidification technique Slab, then, then is rolled, and is obtained oriented high-silicon-steel thin plates, the soft magnet performance of high silicon steel is further improved.
" CN 102321785A " disclose a kind of smelting process of high silicon low-oxygen clean steel to patent, described by the patent The high silicon steel trade mark is 60Si2MnA, and the advantage of the patent is:Using the top of the slag diffusive deoxidation of Al+carbide slag, ferrosilicon is prohibitted the use of Powder or carborundum, by the Control for Oxygen Content in steel in 6-10ppm, improve the fatigue behaviour of the high silicon steel of stove.
" CN 103266215A " disclose a kind of high silicon steel thin belt based on alloying and its manufacture method to patent, and this is special High silicon steel described by profit is characterised by that the percentage by weight of each element is: Si:5.5-7.0;Cu:0.05-2.5;Surplus For Fe and inevitable impurity.The advantage of the patent is:The low of the high silicon steel thin belt of stove is not only improved using the method for alloying Warm ductility, it is ensured that it has preferable soft magnet performance with stove, allows high silicon steel thin belt to pass through traditional rolling mode system It is standby.
" CN 104372238A " disclose a kind of preparation method for being orientated high silicon steel, the high silicon described by the patent to patent Steel is characterised by that the percentage by weight of each element is:C:0.001-0.003; Si:5.0-6.6;Mn:0.2-0.3;Al: 0.05-0.12;V:0.01-0.03;Nb:0.03-0.06;S:0.02-0.03;N:0.009-0.02;O:≤0.002;Surplus is Fe and inevitable impurity.The advantage of the patent is:Inhibitor is designed, Behavior- Based control box is solidified-grow up by Cast Strip crystal grain Inhibitor element solid solution pick-up behavior is designed, and is realized tissue-texture-precipitation Flexible Control, is obtained high magentic induction oriented high silicon steel.
" CN 104630619A " disclose a kind of high silicon steel produced for CSP and preparation side to patent Method, the high silicon steel described by the patent is characterised by that the percentage by weight of each element is:C≤0.003; Si:4.5-7.0; Mn:0.25-1.0;Al≤0.008; S≤0.005;N≤0.003;O:≤0.002;Surplus is Fe and inevitable impurity. The advantage of the patent is:Using continuous casting and rolling short route, obtain column crystal volume ratio and be not less than 90%, fine fibrous tissue, magnetic The good high silicon steel of energy.
The high silicon steel low for alloy content involved by these patents, be mainly used to make various transformers, motor and The iron core of generator, the heavy soft magnetic material applied to electric power, electronics and war industry.But, it may not apply to high temperature sulphur In acid environment.
By literature search, 1980s foreign countries begin one's study it is stainless applied to the high silicon in high-temperature sulfuric acid environment Steel, develops the high silicon stainless steel of multiple trades mark in succession, still, and its manufacturing process is not reported disclosure, and the country is in height The research of silicon stainless steel is also in the starting stage.At present, production high silicon stainless steel is mainly using two kinds of manufacturing process, the first work Skill is:Electric arc furnaces+AOD(Aod)Or V O D (vacuum-oxygen decarbonizing) furnace outer refining process smelts steel ingot, by steel ingot Hot rolling, cold rolling is carried out after hammer cogging.The advantage of the technique is:Production efficiency is high, and cost is low.The shortcoming of the technique is:Steel ingot Hammer cogging lumber recovery it is low, highest 75%, the degree of purity of material is low, and inclusion content is high, influences the decay resistance of material. Second of technique is:Electric arc furnaces or intermediate frequency furnace+AOD(Aod)+ electroslag furnace under protective Ar gas furnace technology smelts steel ingot, Hot rolling, cold rolling will be carried out after steel ingot hammer cogging.The advantage of the technique is:The utilization of steel ingot is improved using electroslag remelting process Rate, can improve steel ingot hammer cogging lumber recovery to 95%.Homogeneity of ingredients, the high purity of material, inclusion content are low, Material has more excellent decay resistance.The shortcoming of the technique is:In order to avoid the scaling loss of Si elements in esr process, Smelted using full guard atmosphere electroslag refining furnace, it is to avoid oxygen in air enters scaling loss Si elements in steel, and full guard atmosphere Electroslag refining furnace equipment investment is high, is 5-6 times of conventional electroslag refining furnace, causes production cost high, ton steel production cost is normal Advise electroslag refining furnace 2 times, it is difficult to popularization and application.
The content of the invention
The present invention seeks to the deficiency for solution above-mentioned technical problem, there is provided a kind of high temperature resistant concentrated sulfuric acid high silicon stainless steel High silicon stainless steel prepared by manufacture method and its equipment, this method and equipment, in high temperature environments, Resistance to Concentrated Sulfuric Acid Corrosion By force.
The present invention is for the technical scheme that is used of solution above-mentioned technical problem:
A kind of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, comprises the following steps:
(1)By simulating phasor, the content of each element is matched, the chemical composition composition of steel ingot is designed, it is ensured that high silicon stainless steel In stable austenitic area, the delta ferrite level in steel ingot is reduced, uniform austenite structure is obtained;Each element constitute and Mass percentage content is:C≤0.03;Si:5.2-5.8;Mn≤1.0;P≤0.025;S≤0.01;Cr:17.5-18.5;Ni: 21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:≤0.05;Ce:≤0.05;Nb:0.02-0.05;O:≤0.006;N:≤ 0.01;Remaining is inevitable impurity and Fe;
(2), pass through refining+aod at the beginning of intermediate frequency furnace(AOD)Stove refinery practice smelts circular electrode;
The element of the electrode is constituted and percentage by weight is:C≤0.03;Si:5.8-6.0;Mn≤1.0;P≤0.025;S≤ 0.01;Cr:17.5-18.5;Ni:21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:0.04-0.06;Ce≤0.05;Nb: 0.02-0.05;O:≤0.006;N:≤0.01;Remaining is inevitable impurity and Fe;The diameter d and the diameter of steel ingot of electrode D ratio is 0.7-0.8;
(3), pass through electroslag remelting(ESR)Technique smelts steel ingot.
The electroslag remelting(ESR)Technique, comprises the following steps:
(1), the oxide skin of electrode surface cleaned out, and be welded on dummy electrode, in feeding well formula resistance-heated furnace, Electrode is preheated to 500-600 DEG C, is incubated 5-6 hours, removes the moisture of electrode surface;
(2), select slag charge constituent element and percentage by weight be:CaF260%~70%, Al2O315%~20%, CaO 10%~ 20%, SiO22%~5%, slag charge is 50-200kg, and slag charge baking temperature is 800 DEG C, and baking time is 8-10 hours;
(3), using graphite electrode striking slag making, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order be added to In crystallizer, slag charge is fused into liquid, liquid slag temperature control is at 1650-1700 DEG C;
(4), consutrode moved in liquid slag bath, under atmospheric environment, start electroslag remelting, the diameter D tables of ESR ingot Show, corresponding electrode melting speed V is selected according to steel ingot diameter D size, wherein, V=(0.7-0.8) × D, ESR ingot diameter D Unit be mm, electrode melting speed V unit is kg/h;
(5), into slag bath, the uniform silicon calcium powder that adds carries out deoxidation, oxygen of the silicon calcium powder in the top of the slag and air in smelting process Reaction generation CaO and SiO2, reduce air in oxygen enter liquid slag bath in, oxidation molten steel in Si elements;The weight of electrode Amount is expressed as W, and W unit is kg, and the addition of silicon calcium powder is expressed as W1, and W1 unit is g, and the addition of silicon calcium powder is:W1= (3-4)×W;Electric slag refusion and smelting process average is divided into two stages, electroslag remelting starts, the addition frequency representation of silicon calcium powder For m1, m1 unit is g/min, and the addition frequency of silicon calcium powder is:m1=(3-4)×V/60;When electrode weight is smelted to half When, the addition frequency representation of silicon calcium powder is m2, and m2 unit is g/min, and the addition frequency of silicon calcium powder is:m2=(1-3)×V/ 60;The electroslag remelting feeding phase, the addition frequency representation of silicon calcium powder is m3, and m3 unit is g/min, the addition frequency of silicon calcium powder For:m3=(0.5-2)×V/60;The silicon calcium powder Si:Ca=1:1;
(6), in smelting process, fire door is placed and argon gas is passed through in protective cover, protection device, and the flow of argon gas is controlled in 20-40m3/ h;Argon gas in protective cover is flowed out by the aperture on its inwall, is collected to form protective layer in fire door, is reduced the oxygen in air Gas enters in liquid slag bath;
(7), after electrode melting finishes, steel ingot is Slow cooling 40-90 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
For the equipment of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, including electrode and liquid slag bath; Protective cover is provided with above liquid slag bath, the protective cover, which is provided with inner chamber, inner chamber, is provided with electrode;Protective cover bottom is provided with indifferent gas The inwall venthole of body, side lower section is provided with the primary inlet port of inert gas, and side top is provided with the primary inlet port of inert gas.
Beneficial effect is:
(1)Under atmospheric environment, steel ingot is smelted using conventional electroslag refining furnace, being manufactured into for equipment investment and steel ingot is reduced This, with obvious economic benefit;(Prior art:Using totally-enclosed electroslag furnace under protective Ar gas remelting furnace smelting process.Why not The reason for steel ingot is smelted using conventional electroslag refining furnace:This material contains substantial amounts of oxidizable elements Si, this process high-temperature steel Liquid is contacted all the time with the oxygen in air, and oxidation reaction easily occurs in smelting process, produces SiO2, cause the Si members in material Element is reduced, or even unqualified, and technology stability is poor, it is difficult to control);
(2)By design protection cover, inert gas cover is formed in electroslag refining furnace mouthful in smelting process, and in smelting not In the same stage, the silicon calcium powder deoxidier of various dose is uniformly added into slag, the scaling loss of element silicon is effectively controlled, smelts low The uniform high-silicon austenite stainless steel steel ingot of nitrogen, hypoxemia, composition, is closed by better than composition design, adding micro Ce, Nb, Al etc. Gold element, improves the hot-working character and decay resistance of steel.
(3)Manufacturing process of the present invention is simple, and low production cost, steel ingot has good homogeneity of ingredients, and excellent is resistance to High-temperature sulfuric acid corrosive nature, the evil that can be applied in sulfuric acid industry is omited in corrosive environment, substantially prolongs the service life of product, The security of equipment is improved, with good social benefit;High temperature resistant sulfuric acid corrosion resistance is tested according to standard, with material list Face does not have corrosion phenomenon to be standard, the corrosion data of prior art:In the H of 150 DEG C of 98% concentration2SO4In solution, average corruption Erosion speed is 0.09-0.125mm/, and corrosion rate of the invention is less than 0.08mm/.
Brief description of the drawings
Fig. 1 is the device structure schematic diagram of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method of the present invention;
Fig. 2 is the protective cover structural representation of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacturing approach apparatus of the present invention;
Mark is in figure:1st, electrode lifting mechanism, 2, electrode, 3, protective cover, 4, liquid slag bath, 5, metal bath, 6, crystallization Device, 7, steel ingot, 8, bottom water tank, 9, control system;31st, primary inlet port, 32, inwall venthole, 33, main venthole.
Embodiment
A kind of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, comprises the following steps:
(One)By simulating phasor, the content of each element is matched, the chemical composition composition of steel ingot is designed, it is ensured that high silicon stainless steel In stable austenitic area, the delta ferrite level in steel ingot is reduced, uniform austenite structure is obtained;Each element constitute and Mass percentage content is:C≤0.03;Si:5.2-5.8;Mn≤1.0;P≤0.025;S≤0.01;Cr:17.5-18.5;Ni: 21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:≤0.05;Ce:≤0.05;Nb:0.02-0.05;O:≤0.006;N:≤ 0.01;Remaining is inevitable impurity and Fe;
(Two), pass through refining+aod at the beginning of intermediate frequency furnace(AOD)Stove refinery practice smelts circular electrode;
The element of the electrode is constituted and percentage by weight is:C≤0.03;Si:5.8-6.0;Mn≤1.0;P≤0.025;S≤ 0.01;Cr:17.5-18.5;Ni:21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:0.04-0.06;Ce≤0.05;Nb: 0.02-0.05;O:≤0.006;N:≤0.01;Remaining is inevitable impurity and Fe;The diameter d and the diameter of steel ingot of electrode D ratio is 0.7-0.8;Invention increases the content of Al, Ce element, the effect reached:Reduce impurity O elements in steel ingot Content, improves the hot-working character of steel ingot.The content of Nb elements is added, the effect reached:Improve the decay resistance of material.
Steel ingot Design of Chemical Composition principle is as follows:
(1)C≤0.03%
Carbon is strong formation and stable austenite element, and can improve the mechanical performance of material, and still, it is obvious that carbon content crosses high energy Promote carbide Cr23C6 to be separated out along intergranular, cause crystal boundary chromium depleted, decline the intergranular corrosion resistance performance of material.High silicon stainless steel Reduce carbon content as far as possible in smelting process, still, carbon content is too low, can significantly increase smelting cost.Therefore, it is of the invention Carbon element content percentage by weight is:C≤0.03%, the preferred scope of carbon element content percentage by weight is:C≤0.02%.
(2)Si:5.2-5.8
Si is one of important corrosion resistant alloy element, with excellent antioxygenic property, can stainless steel Surface Creation SiO2Oxide-film.During Si≤5.2, it is impossible to the siliceous complex chemical compound of some cathodics is formed with the chromium in stainless steel, nickel element, Promote the passivation of stainless steel, causing the corrosion resistance of stainless steel reduces.During Si >=5.8, too high silicon content makees the passivation of chromium, nickel With decrease, weaken the corrosion resistance of stainless steel on the contrary.Moreover, excessive ferrite former silicon can make to produce largely in steel ingot A delta ferrite, reduce steel ingot hot-workability.Therefore, silicon content percentage by weight of the invention is:Si: 5.2-5.8, the preferred scope of silicon content percentage by weight is:5.5-5.8.
(3)Mn≤1%
Mn influences little to the corrosion resistance of stainless steel in concentrated sulfuric acid, is brought into primarily as deoxidier in steel, it is contemplated that steel Deoxidation effect in smelting process and economy is smelted, Mn constituent content percentage by weights of the invention are:Mn≤1%
(4)S≤0.01%
S is the impurity element in steel, can reduce the hot-working character and decay resistance of material, therefore, contents of the S in steel Smelting process that is more low better, being taken according to the present invention, on the basis of production cost is not increased, S constituent contents weight hundred Point ratio is:The preferred scope of S≤0.01%, S constituent content percentage by weights is:S≤0.006%.
(5)P≤0.025%
P is the impurity element in steel, be easily collected on crystal boundary deteriorate material performance, therefore, contents of the P in steel it is more low more Smelting process that is good, being taken according to the present invention, on the basis of production cost is not increased, phosphorus element content percentage by weight For:P≤0.025%, the preferred scope of sulfur content percentage by weight is:P≤0.02%.
(6)17.5%≤Cr≤18.5%
Cr elements significantly improve the decay resistance of material, act on improving decay resistance of the stainless steel in high-temperature concentrated sulfuric acid It is only second to Si.Therefore, Cr elements are the indispensable elements of high silicon stainless steel of the present invention.As Cr≤17.5%, it is impossible to silicon, Nickel element forms sufficiently thick siliceous complex chemical compound film, causes the corrosion resistance of stainless steel and reduces.Meanwhile, Cr elements are strong Formed and stablize ferritic element, reduced single phase austenite area, with the increase of Cr contents, the analysis of intermetallic phase can be promoted Go out, so as to reduce the plasticity and toughness of material.When Cr constituent contents percentage by weight is more than 18.5%, the austenite structure of material is steady It is qualitative to be deteriorated, a number of high temperature ferritic structure can be retained in steel, the hot-workability of material is reduced.Therefore, it is of the invention Cr constituent content percentage by weights be:17.5%≤Cr≤18.5%.
(7)21%≤Ni≤22%
Nickel has certain effect to improving decay resistance of the stainless steel in high-temperature concentrated sulfuric acid, but not fairly obvious.In the present invention In, nickel is the strong element for forming simultaneously stable austenite and expanding single phase austenite area, and its main function is to maintain nickel, chromium equivalent Balance, the austenite structure stablized, ensure deformation performance.Therefore, Ni constituent content percentage by weights of the invention are: 21%≤Ni≤22%。
(8)0.5%≤ Mo≤1.3%
Mo elements can promote passivation for stainless steel.As Mo≤0.5%, stainless steel is improved in dense sulphur by the compound action of chromium, molybdenum Corrosion proof effect in acid is not obvious;As Mo >=1.3%, molybdenum easily produces transpassivation in the Oxidant concentrated sulfuric acid, right The corrosion resistance of stainless steel is unfavorable.Therefore, Mo constituent content percentage by weights of the invention are:Mo:0.5%≤Mo≤1.3%, Mo The preferred scope of constituent content percentage by weight is:0.6%≤ Mo≤1.0%.
(9)2.0%≤Cu≤2.5%
Cu elements can improve the corrosion resistance of stainless steel in concentrated sulfuric acid.Main cause is:The electrode potential of copper is higher than hydrogen, can Suppress gas-evolving electrodes.But, Cu constituent contents are too high to reduce the hot-workability of steel.Therefore, Cu constituent contents of the invention Percentage by weight is:Mo:2%≤ Mo≤2.5%.
(10)0.02%≤Nb≤0.05%
Niobium is stabilizing element, and the adhesion of niobium and carbon, which is better than in chromium, steel, to be added after niobium, preferentially combines to form chemical combination with carbon Thing is separated out in transgranular or crystal boundary, can not only suppress Cr23C6Separate out, improve the corrosion resistance of material, and the precipitation of niobium Thing can improve the intensity of material, and when the addition percentage by weight of niobium is more than 0.05%, invigoration effect reaches saturation.Work as niobium Addition percentage by weight be less than 0.02% when, it is impossible to effectively suppress Cr23C6Separate out, influence decay resistance.Therefore, this hair Bright Nb constituent content percentage by weights are:0.02%≤Nb≤0.05%.
(11)Ce:≤0.05
Rare-Earth Ce can change the sulfur content in the composition and form of the sulphide inculsion that spot corrosion is easily formed in steel, reduction steel, Improve the corrosion-resistant ability of steel.In addition, Rare-Earth Ce can be enriched with crystal boundary and carbide-basal body interface, the heat of steel ingot is improved Processing characteristics, when Ce addition percentage by weight is more than 0.05%, production cost is improved.Therefore, Ce elements of the invention contain Measuring percentage by weight is: Ce≤0.05%.
(12)Al≤0.05%
Al elements are brought into steel primarily as deoxidier, in addition, aluminium appropriate in steel can suppress in esr process The scaling loss of element silicon.As Al >=0.05%, thick crystal grain can be formed, making the hot-working character of steel ingot reduces.Exist in view of steel The scaling loss rule of element silicon during deoxidation effect, electric slag refusion and smelting in smelting process, Al constituent content weights of the invention Measuring percentage is: Al≤0.05%.
(13)N≤0.01%
N element is the impurity element in steel, and nitride can be formed in steel, influences the decay resistance of steel, it is necessary to carry out strict Control.It is lower that N element content is controlled, and the performance of steel is better, still, can greatly increase difficulty and the production of smelting process Cost, is not suitable for mass production applications.Therefore, with reference to manufacturing process adaptability production cost, N element content of the invention Percentage by weight is: N≤0.01%.
(14)O≤0.006%
Too high oxygen level can deteriorate the degree of purity of steel, reduce the hot-working character of steel ingot, the decay resistance and toughness of material, Oxygen content is too low to increase smelting cost.Therefore, smelting cost and the performance of material, O elements of the invention are considered Content percentage by weight is: O≤0.006%.
(Three), pass through electroslag remelting(ESR)Technique smelts steel ingot.
The electroslag remelting(ESR)Technique, comprises the following steps:
(1), the oxide skin of electrode surface cleaned out, and be welded on dummy electrode, in feeding well formula resistance-heated furnace, Electrode is preheated to 500-600 DEG C, is incubated 5-6 hours, removes the moisture of electrode surface;
(2), select slag charge constituent element and percentage by weight be:CaF2 60%~70%, Al2O315%~20%, CaO 10%~ 20%, SiO22%~5%, slag charge is 50-200kg, and slag charge baking temperature is 800 DEG C, and baking time is 8-10 hours;
(3), using graphite electrode striking slag making, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order be added to In crystallizer, slag charge is fused into liquid, liquid slag temperature control is at 1650-1700 DEG C;
(4), consutrode moved in liquid slag bath, under atmospheric environment, start electroslag remelting, the diameter D tables of ESR ingot Show, corresponding electrode melting speed V is selected according to steel ingot diameter D size, wherein, V=(0.7-0.8) × D, ESR ingot diameter D Unit be mm, electrode melting speed V unit is kg/h;
(5), into slag bath, the uniform silicon calcium powder that adds carries out deoxidation, oxygen of the silicon calcium powder in the top of the slag and air in smelting process Reaction generation CaO and SiO2, reduce air in oxygen enter liquid slag bath in, oxidation molten steel in Si elements;The weight of electrode Amount is expressed as W, and W unit is kg, and the addition of silicon calcium powder is expressed as W1, and W1 unit is g, and the addition of silicon calcium powder is:W1= (3-4)×W;Electric slag refusion and smelting process average is divided into two stages, electroslag remelting starts, the addition frequency representation of silicon calcium powder For m1, m1 unit is g/min, and the addition frequency of silicon calcium powder is:m1=(3-4)×V/60;When electrode weight is smelted to half When, the addition frequency representation of silicon calcium powder is m2, and m2 unit is g/min, and the addition frequency of silicon calcium powder is:m2=(1-3)×V/ 60;The electroslag remelting feeding phase, the addition frequency representation of silicon calcium powder is m3, and m3 unit is g/min, the addition frequency of silicon calcium powder For:m3=(0.5-2)×V/60;The silicon calcium powder Si:Ca=1:1;
(6), in smelting process, fire door is placed and argon gas is passed through in protective cover, protection device, and the flow of argon gas is controlled in 20-40m3/ h;Argon gas in protective cover is flowed out by the aperture on its inwall, is collected to form protective layer in fire door, is reduced the oxygen in air Gas enters in liquid slag bath;
(7), after electrode melting finishes, steel ingot 7 is Slow cooling 40-90 minutes in crystallizer, it is ensured that liquid metal and slag are solidifying Gu fully, it is air-cooled to room temperature after the steel ingot demoulding.
For the equipment of the high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, equipment include electrode lifting mechanism 1, The parts such as electrode 2, crystallizer 6, bottom water tank 8, protective cover 3, liquid slag bath 4, metal bath 5 and control system 9, as shown in Figure 1;
The elevating mechanism is act as:It will insert in crystallizer, be driven from top to bottom after electrode firm grip.
The electrode is act as:It is frozen into ESR ingot after electrode melting again in crystallizer.
The crystallizer is act as:After electrode is gradually melted by high-temperature liquid state slag bath, molten drop is dripped in crystallizer Metal bath is formed, metal bath is frozen into ESR ingot under the cooling condition of crystallizer cooling water.
The protection is located above liquid slag pond, and the protective cover 3, which is provided with inner chamber, inner chamber, is provided with electrode 2;Protective cover 3 bottoms are provided with the inwall venthole 32 of inert gas, and side lower section is provided with the primary inlet port 31 of inert gas, and side top is provided with The primary inlet port 33 of inert gas.The inert gas of certain pressure is entered from 31 holes, is gone out from 32,33 holes, wherein being gone out from 32 Gas equipment fire door formation one layer of inert gas, rise and the oxygen buffer action in air)
The protective cover 3 is act as:In esr process, aperture of the argon gas in protective cover from its inwall surrounding is passed through Interior outflow, in crystallizer formation argon shield suitable for reading, prevents the oxygen in air from entering in liquid slag bath, in the drop of oxidized metal Element silicon, as shown in Figure 2.
The bottom water tank is act as:In electroslag remelting firm incipient stage, the space with crystallizer formation closing, metal melts It is dropped in formation metal bath in the space.
The control system is act as:Control elevating mechanism decrease speed.
The present invention is described in detail with reference to embodiments:
Embodiment 1:Φ 360mm high silicon stainless steel electric slag refusion ingot.
The first step, using " Medium frequency induction+AOD refinings " technique smelt consutrode, electrode specification be Φ 260mm × 2500mm, the chemical composition of electrode is as shown in table 1.
The electrode chemical composition of table 1(Weight %)
Second step, consutrode surface polished clean.
3rd step, according to thermodynamic principles, calculates when the reaction of Si scaling loss reaches balance and goes out the SiO needed for slag system2It is theoretical Content, then by SiO2Theoretical content selects the slag system of matching, and specific method is:
(1)Gradually melt, during molten drop passes through slag bath, occur in electroslag remelting stage, electrode insertion molten slag Reaction:
[Si]+2[O]= SiO2Formula 1
According to thermodynamic principles, when reaction reaches chemical balance:
Formula 2
- 480626+213.389T formula 3
=Formula 4
=Formula 5
lg=Formula 6
lg=Formula 7
During for 1873K, each element and Si interaction coefficient in molten steel,During for 1873K, each element in molten steel With O interaction coefficient.TFor the equilibrium temperature of chemical equation, 1873K;R is gas constant, 8.314.
Using 1~formula of formula 7, calculateActivity value be:=0.031, then design the SiO in slag system2's Theoretical molar concentration is 0.031, and mass percent is 2%.
3rd step, prepare slag charge.Slag system uses CaF2、Al2O3、CaO、SiO2Quaternary slag system, the percentage by weight of each constituent element Respectively 70%, 15%, 13%, 2%, quantity of slag 50kg.Slag charge is separated and inserted in electric furnace, temperature control is toasted 8 hours at 850 DEG C.
4th step, protective cover is placed on crystallizer, connects the inlet and outlet of argon gas;
5th step, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order add crystallizer in, using graphite electricity Slag charge is fused into liquid by pole, and liquid slag temperature control system is at 1650-1700 DEG C, it is ensured that slag system is melted, changed clearly;
6th step, preheated consutrode is moved in liquid slag bath, starts electroslag remelting, voltage is 38-52V, and electric current is 0.4-0.8KA, electrode melting speed is 290kg/h, and the flow of argon gas is 20m3Argon gas in/h, protective cover passes through its inwall On aperture outflow, collect to form protective layer in fire door, reduce oxygen in air and enter in liquid slag bath.Electroslag remelting is opened Begin, the addition frequency of silicon calcium powder is m1=15g/min.When electrode weight is smelted to half, the addition frequency meter of silicon calcium powder is m2 =10 g/min.Electroslag remelting feeding phase, the addition frequency m of silicon calcium powder3=5 g/min;
7th step, after electrode melting is finished, steel ingot Slow cooling 40 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
A diameter of Φ 360mm high silicon stainless steel Ingot Surface Quality is good, without defects such as pipe, slag inclusion, ripples.Root According to GB/T 1979-2001《Structural steel macrostructure defect judge picture》Standard, is detected to embodiment steel ingot internal soundness, Loose, segregation, white band, rimhole, Residual hole, skull patch, white point, cracks in crystal boundary, air entrapment, non-gold are not found Belong to the defect such as field trash and slag inclusion, Non-metallic inclusion thing, steel ingot internal soundness is good.After steel ingot is forged, with good heat Processing characteristics.
According to GB/T 4334.6-2015《The sulfuric acid corrosion test method of stainless steel 5%》、JB/T 7901-1999 《Metal Material laboratory homogeneous corrosion total immersion test method》It is required that, sample is placed on to the H of 150 DEG C of 98% concentration2SO4Soaked in solution Bubble 7 days, specimen surface does not have significant change, does not occur local corrosion phenomenon, and average corrosion rate is 0.075mm/, can See, high silicon stainless steel of the present invention has good decay resistance.
Embodiment 2:Φ 440mm high silicon stainless steel electric slag refusion ingot.
The first step, using " Medium frequency induction+AOD refinings " technique smelt consutrode, electrode specification be Φ 310mm × 3500mm, the chemical composition of electrode is as shown in table 1.
The electrode chemical composition of table 2(Weight %)
Second step, consutrode surface polished clean.
3rd step, is calculated according to the method for implementing 1Activity value be:=0.04, then design in slag system SiO2 theoretical molar concentration is 0.04, and mass percent is 3%.
3rd step, prepare slag charge.Slag system uses CaF2、Al2O3、CaO、SiO2Quaternary slag system, the percentage by weight of each constituent element Respectively 69%, 15%, 13%, 3%, quantity of slag 80kg.Slag charge is separated and inserted in electric furnace, temperature control is toasted 8 hours at 850 DEG C.
4th step, protective cover is placed on crystallizer, connects the inlet and outlet of argon gas;
5th step, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order add crystallizer in, using graphite electricity Slag charge is fused into liquid by pole, and liquid slag temperature control system is at 1650-1700 DEG C, it is ensured that slag system is melted, changed clearly;
6th step, preheated consutrode is moved in liquid slag bath, starts electroslag remelting, voltage is 60-40V, and electric current is 0.5-11.5KA, electrode melting speed is 360kg/h, and the flow of argon gas is 25m3Argon gas in/h, protective cover passes through its inwall On aperture outflow, collect to form protective layer in fire door, reduce oxygen in air and enter in liquid slag bath.Electroslag remelting is opened Begin, the addition frequency of silicon calcium powder is m1=20g/min.When electrode weight is smelted to half, the addition frequency meter of silicon calcium powder is m2 =12g/min.Electroslag remelting feeding phase, the addition frequency m of silicon calcium powder3=6g/min;
7th step, after electrode melting is finished, steel ingot Slow cooling 50 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
A diameter of Φ 440mm high silicon stainless steel Ingot Surface Quality is good, without defects such as pipe, slag inclusion, ripples.Root According to GB/T 1979-2001《Structural steel macrostructure defect judge picture》Standard, is detected to embodiment steel ingot internal soundness, Loose, segregation, white band, rimhole, Residual hole, skull patch, white point, cracks in crystal boundary, air entrapment, non-gold are not found Belong to the defect such as field trash and slag inclusion, Non-metallic inclusion thing, steel ingot internal soundness is good.After steel ingot is forged, with good heat Processing characteristics.
According to GB/T 4334.6-2015《The sulfuric acid corrosion test method of stainless steel 5%》、JB/T 7901-1999 《Metal Material laboratory homogeneous corrosion total immersion test method》It is required that, sample is placed on to the H of 150 DEG C of 98% concentration2SO4Soaked in solution Bubble 7 days, specimen surface does not have significant change, does not occur local corrosion phenomenon, and average corrosion rate is 0.064mm/, can See, high silicon stainless steel of the present invention has good decay resistance.
Embodiment 3:Φ 560mm high silicon stainless steel electric slag refusion ingot.
The first step, using " Medium frequency induction+AOD refinings " technique smelt consutrode, electrode specification be Φ 420mm × 3000mm, the chemical composition of electrode is as shown in table 3.
The electrode chemical composition of table 3(Weight %)
Alloy C Si Mn S P Cr Ni Mo Cu Al Ce Nb O N
Electrode 0.015 5.5 0.6 0.01 0.017 18.05 21.5 0.66 2.2 0.04 0.04 0.04 0.006 0.007
Second step, consutrode surface polished clean.
3rd step, is calculated according to the method for implementing 1Activity value be:=0.05, then design in slag system SiO2Theoretical molar concentration be 0.05, mass percent is 4%.
3rd step, prepare slag charge.Slag system uses CaF2、Al2O3、CaO、SiO2Quaternary slag system, the percentage by weight of each constituent element Respectively 61%, 20%, 15%, 4%, quantity of slag 120kg.Slag charge is separated and inserted in electric furnace, temperature control is at 850 DEG C, and baking 8 is small When.
4th step, protective cover is placed on crystallizer, connects the inlet and outlet of argon gas;
5th step, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order add crystallizer in, using graphite electricity Slag charge is fused into liquid by pole, and liquid slag temperature control system is at 1650-1700 DEG C, it is ensured that slag system is melted, changed clearly;
6th step, preheated consutrode is moved in liquid slag bath, starts electroslag remelting, voltage is 54-62V, and electric current is 7-16KA, electrode melting speed is 450kg/h, and the flow of argon gas is 35m3Argon gas in/h, protective cover passes through on its inwall Aperture flows out, and collects to form protective layer in fire door, and the oxygen reduced in air enters in liquid slag bath.Electroslag remelting starts, The addition frequency of silicon calcium powder is m1=30g/min.When electrode weight is smelted to half, the addition frequency meter of silicon calcium powder is m2 = 15g/min.Electroslag remelting feeding phase, the addition frequency m of silicon calcium powder3=10g/min;
7th step, after electrode melting is finished, steel ingot Slow cooling 70 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
A diameter of Φ 560mm high silicon stainless steel Ingot Surface Quality is good, without defects such as pipe, slag inclusion, ripples.Root According to GB/T 1979-2001《Structural steel macrostructure defect judge picture》Standard, is detected to embodiment steel ingot internal soundness, Loose, segregation, white band, rimhole, Residual hole, skull patch, white point, cracks in crystal boundary, air entrapment, non-gold are not found Belong to the defect such as field trash and slag inclusion, Non-metallic inclusion thing, steel ingot internal soundness is good.After steel ingot is forged, with good heat Processing characteristics.
According to GB/T 4334.6-2015《The sulfuric acid corrosion test method of stainless steel 5%》、JB/T 7901-1999 《Metal Material laboratory homogeneous corrosion total immersion test method》It is required that, sample is placed on to the H of 150 DEG C of 98% concentration2SO4Soaked in solution Bubble 7 days, specimen surface does not have significant change, does not occur local corrosion phenomenon, and average corrosion rate is 0.06mm/, it is seen then that High silicon stainless steel of the present invention has good decay resistance.
Embodiment 4:Φ 700mm high silicon stainless steel electric slag refusion ingot.
The first step, using " Medium frequency induction+AOD refinings " technique smelt consutrode, electrode specification be Φ 500mm × 3200mm, the chemical composition of electrode is as shown in table 3.
The electrode chemical composition of table 3(Weight %)
Alloy C Si Mn S P Cr Ni Mo Cu Al Ce Nb O N
Electrode 0.025 5.4 0.3 0.01 0.02 17.8 21.6 0.9 2.3 0.05 0.03 0.03 0.006 0.007
Second step, consutrode surface polished clean.
3rd step, is calculated according to the method for implementing 1Activity value be:=0.06, then design in slag system SiO2Theoretical molar concentration be 0.06, mass percent is 5%.
3rd step, prepare slag charge.Slag system uses CaF2、Al2O3、CaO、SiO2Quaternary slag system, the percentage by weight of each constituent element Respectively 60%, 20%, 15%, 5%, quantity of slag 200kg.Slag charge is separated and inserted in electric furnace, temperature control is at 850 DEG C, and baking 8 is small When.
4th step, protective cover is placed on crystallizer, connects the inlet and outlet of argon gas;
5th step, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order add crystallizer in, using graphite electricity Slag charge is fused into liquid by pole, and liquid slag temperature control system is at 1650-1700 DEG C, it is ensured that slag system is melted, changed clearly;
6th step, preheated consutrode is moved in liquid slag bath, starts electroslag remelting, voltage is 33-78V, and electric current is 8-17KA, electrode melting speed is 560kg/h, and the flow of argon gas is 38m3Argon gas in/h, protective cover passes through on its inwall Aperture flows out, and collects to form protective layer in fire door, and the oxygen reduced in air enters in liquid slag bath.Electroslag remelting starts, The addition frequency of silicon calcium powder is m1=35g/min.When electrode weight is smelted to half, the addition frequency meter of silicon calcium powder is m2 = 20g/min.Electroslag remelting feeding phase, the addition frequency m of silicon calcium powder3=10g/min;
7th step, after electrode melting is finished, steel ingot Slow cooling 70 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
A diameter of Φ 700mm high silicon stainless steel Ingot Surface Quality is good, without defects such as pipe, slag inclusion, ripples.Root According to GB/T 1979-2001《Structural steel macrostructure defect judge picture》Standard, is detected to embodiment steel ingot internal soundness, Loose, segregation, white band, rimhole, Residual hole, skull patch, white point, cracks in crystal boundary, air entrapment, non-gold are not found Belong to the defect such as field trash and slag inclusion, Non-metallic inclusion thing, steel ingot internal soundness is good.After steel ingot is forged, with good heat Processing characteristics.
According to GB/T 4334.6-2015《The sulfuric acid corrosion test method of stainless steel 5%》、JB/T 7901-1999 《Metal Material laboratory homogeneous corrosion total immersion test method》It is required that, sample is placed on to the H of 150 DEG C of 98% concentration2SO4Soaked in solution Bubble 7 days, specimen surface does not have significant change, does not occur local corrosion phenomenon, and average corrosion rate is 0.068mm/, can See, high silicon stainless steel of the present invention has good decay resistance.

Claims (3)

1. a kind of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method, it is characterised in that:Comprise the following steps:
(One)By simulating phasor, the content of each element is matched, the chemical composition composition of steel ingot is designed, it is ensured that high silicon stainless steel In stable austenitic area, the delta ferrite level in steel ingot is reduced, uniform austenite structure is obtained;Each element constitute and Mass percentage content is:C≤0.03;Si:5.2-5.8;Mn≤1.0;P≤0.025;S≤0.01;Cr:17.5-18.5;Ni: 21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:≤0.05;Ce:≤0.05;Nb:0.02-0.05;O:≤0.006;N:≤ 0.01;Remaining is inevitable impurity and Fe;
(Two), pass through refining at the beginning of intermediate frequency furnace+argon oxygen decarburizing furnace refinery practice and smelt circular electrode;
The element of the electrode is constituted and percentage by weight is:C≤0.03;Si:5.8-6.0;Mn≤1.0;P≤0.025;S≤ 0.01;Cr:17.5-18.5;Ni:21-22;Mo:0.5-1.3;Cu:2.0-2.5;Al:0.04-0.06;Ce≤0.05;Nb: 0.02-0.05;O:≤0.006;N:≤0.01;Remaining is inevitable impurity and Fe;The diameter d and the diameter of steel ingot of electrode D ratio is 0.7-0.8;
(Three), pass through electroslag remelting(ESR)Technique smelts steel ingot.
2. high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method as claimed in claim 1, it is characterised in that:Step(Three)Middle institute State electroslag remelting(ESR)Technique, comprises the following steps:
(1), the oxide skin of electrode surface cleaned out, and be welded on dummy electrode, in feeding well formula resistance-heated furnace, Electrode is preheated to 500-600 DEG C, is incubated 5-6 hours, removes the moisture of electrode surface;
(2), select slag charge constituent element and percentage by weight be:CaF260%~70%, Al2O315%~20%, CaO 10%~ 20%, SiO22%~5%, slag charge is 50-200kg, and slag charge baking temperature is 800 DEG C, and baking time is 8-10 hours;
(3), using graphite electrode striking slag making, by baked slag system according to CaF2、SiO2、CaO、Al2O3Order be added to In crystallizer, slag charge is fused into liquid, liquid slag temperature control is at 1650-1700 DEG C;
(4), consutrode moved in liquid slag bath, under atmospheric environment, start electroslag remelting, the diameter D tables of ESR ingot Show, corresponding electrode melting speed V is selected according to steel ingot diameter D size, wherein, V=(0.7-0.8) × D, ESR ingot diameter D Unit be mm, electrode melting speed V unit is kg/h;
(5), into slag bath, the uniform silicon calcium powder that adds carries out deoxidation, oxygen of the silicon calcium powder in the top of the slag and air in smelting process Reaction generation CaO and SiO2, reduce air in oxygen enter liquid slag bath in, oxidation molten steel in Si elements;The weight of electrode Amount is expressed as W, and W unit is kg, and the addition of silicon calcium powder is expressed as W1, and W1 unit is g, and the addition of silicon calcium powder is:W1= (3-4)×W;Electric slag refusion and smelting process average is divided into two stages, electroslag remelting starts, the addition frequency representation of silicon calcium powder For m1, m1 unit is g/min, and the addition frequency of silicon calcium powder is:m1=(3-4)×V/60;When electrode weight is smelted to half When, the addition frequency representation of silicon calcium powder is m2, and m2 unit is g/min, and the addition frequency of silicon calcium powder is:m2=(1-3)×V/ 60;The electroslag remelting feeding phase, the addition frequency representation of silicon calcium powder is m3, and m3 unit is g/min, the addition frequency of silicon calcium powder For:m3=(0.5-2)×V/60;The silicon calcium powder Si:Ca=1:1;
(6), in smelting process, fire door is placed and argon gas is passed through in protective cover, protection device, and the flow of argon gas is controlled in 20-40m3/ h;Argon gas in protective cover is flowed out by the aperture on its inwall, is collected to form protective layer in fire door, is reduced the oxygen in air Gas enters in liquid slag bath;
(7), after electrode melting finishes, steel ingot is Slow cooling 40-90 minutes in crystallizer, it is ensured that liquid metal and slag solidification Fully, it is air-cooled to room temperature after the steel ingot demoulding.
3. for the equipment of high temperature resistant concentrated sulfuric acid high silicon stainless steel manufacture method described in claim 1 or 2, including electrode and liquid State slag bath, it is characterised in that:Protective cover is provided with above liquid slag bath(3), the protective cover(3)Provided with inner chamber, set in inner chamber There is electrode(2);Protective cover(3)Bottom is provided with the inwall venthole of inert gas(32), side lower section is provided with the master of inert gas Air admission hole(31), side top is provided with the primary inlet port of inert gas(33).
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