CN100500908C - Technique for alloying steel making directly from tungsten ore - Google Patents

Technique for alloying steel making directly from tungsten ore Download PDF

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Publication number
CN100500908C
CN100500908C CNB2007100993368A CN200710099336A CN100500908C CN 100500908 C CN100500908 C CN 100500908C CN B2007100993368 A CNB2007100993368 A CN B2007100993368A CN 200710099336 A CN200710099336 A CN 200710099336A CN 100500908 C CN100500908 C CN 100500908C
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tungsten ore
tungsten
steel
ore
carbon containing
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CN101050506A (en
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李正邦
周勇
张家雯
杨海森
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Central Iron and Steel Research Institute
China Iron and Steel Research Institute Group
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

This invention discloses a process for direct alloying steelmaking from tungsten ore. The tungsten ore pellet is composed of: tungsten ore 80-85.5%, reducer 13-16.5%, catalyst 1-2%, and binder 0.5-1.5%. The process comprises: pulverizing tungsten ore, reducer and catalyst, grinding into 200 mesh powder, mixing uniformly, adding binder, and pressing into tungsten ore pellet, loading into an electric oven, melting, and performing solid-state reduction until the reduction rate is higher than 90%. The tungsten recovery rate is higher than 95%. The process solves the problems of low reduction speed and rate, low tungsten recovery rate, and large slag amount faced by direct alloying of tungsten ore in an electric oven. The process is a single-step process, and has lowered investment and energy consumption.

Description

A kind of technique for alloying steel making directly from tungsten ore
Technical field
The present invention relates to the steel alloy technical field of smelting, particularly adopt tungsten ore directly to carry out alloying and smelt tungsten-containing alloy steel technology.
Background technology
One of critical process link of tungsten-containing alloy steel production is the alloying technology in the smelting steel.The smelting tungsten-containing alloy steel carries out general the employing at when filling with substance adding ferrotungsten of alloying of W elements at present, and the production cost of this technology and energy consumption are directly related with consumption, production cost and the energy consumption of iron alloy.Investigate the ferro-tungsten production status and can find that the production energy consumption of iron alloy is big, yield of alloy is low, and environmental pollution is serious, and labour intensity is big, deficiency in economic performance.Iron-extraction process is produced one ton of about 4000kWh of ferrotungsten (tungstenic 70%) power consumption, pitch coke 120kg, coke 116kg.Smelt ferrotungsten from tungsten concentrate, owing to smelting equipment, technology etc. are all multifactor, the rate of recovery of W has only about 95% in the tungsten concentrate.And with ferrotungsten and molybdenum-iron alloy smelting steel, owing to vaporization at high temperature, with factors such as slag losses, the rate of recovery of ferrotungsten and molybdenum-iron generally also has only about 90%～95%.So then to the alloy smelting steel, W element total yield has only about 85%～90% from the tungsten concentrate smelting ferro-tungsten alloy.As seen, there is 10%～15% tungsten resource in smelting process, to be wasted.Produce ferrotungsten, produce volume of smoke and NO xGas also needs to use carcinogenic substances such as Al grain, nitre, ferrosilicon in smelting process, and working condition is abominable.Iron-extraction process is smelted ferrotungsten, because complicated smelting process has increased the weight of labor strength.
The physicochemical change of steelmaking process also possesses reductive condition.The oxide compound or the mineral that in steelmaking process, add alloying element, reductive condition by steelmaking process enters the alloying element reduction in the steel, reach the purpose of alloying, compare with the method for iron alloy alloying, can be without the whole plant of ferroalloy smelting, be equivalent to a kind of single step process technology, thereby investment and energy consumption obtain all saving, reduced the alloying cost of steel.Replace ferrotungsten to smelt with sheelite and contain wolfram steel, just attempt as far back as the beginning of the forties, later on the U.S., Germany, Japan is studied in succession and use, to the sixties, USSR (Union of Soviet Socialist Republics) research is more, in electric furnace, open hearth, induction furnace, use, use the tungsten concentrate kind more abroad, natural white tungsten fine ore, synthetic scheelite concentrate, autoreduction white tungsten fine ore, white tungsten and black tungsten collective concentrate and wolframite etc. are arranged.Reductive agent generally uses materials such as aluminium, silicon, carbon.Mixture pelletizing and block each weight are 2～10kg.Generally all use pressure forming, drying treatment.The autoreduction sheelite generally is added in ladle bottom, allows the molten steel after the deoxidation fully stir, and the add-on of tungsten is about 1%.The adding method has in stove: 1. sheelite is packed into furnace charge, 2. add the liquid material and add sheelite (acid open-hearth furnace) before, 3. in smelting process sheelite is added in the stove.The add-on of external sheelite is 3%[W] about, the DIRECT ALLOYING rate is low.External tungsten ore DIRECT ALLOYING technology mainly relies on the reduction reaction that takes place between solid-state tungsten ore and solid, liquid attitude reductive agent to carry out alloying, so speed of response is slow, does not match with steel-making rhythm, and recovery rate is lower than 90%, and the quantity of slag is big.
China's tungsten ore standing stock and annual production occupy first place in the world, but that research replaces ferrotungsten to smelt containing wolfram steel with sheelite is later relatively.The eighties, Dalian special steel plant and Iron and Steel Research Geueral Inst are to replacing ferrotungsten steel-making having carried out laboratory test and industrial test with white tungsten fine ore.The sheelite add-on generally maintains about 3%, and recovery rate is below 90%.Taiyuan Iron ﹠ Steel Corp has carried out on the electric arc furnace of 18.5～20t adopting white tungsten fine ore to smelt the commerical test of 3Cr2W8V.Adopt the high quality white tungsten ore, make reductive agent with ferrosilicon, the sheelite add-on reaches 6%W, fusing is during the end of term, the recovery rate of tungsten has only about 80%, so sheelite DIRECT ALLOYING process related to whole electrosmelting process, comprises melting period, oxidation period and reduction period, the smelting process complexity, labor strength is big.Because the quantity of slag is excessive, many slags drop down fire door automatically, cause in the sheelite rate of recovery of tungsten to have only about 90%.
From domestic and international existing tungsten ore DIRECT ALLOYING technology as can be seen, because the fusing point height of tungsten ore, solid state reduction speed is slow, the solid state reduction rate is low, and furnace melting end of term recovery rate only has about 80%, still have a large amount of tungsten ores not to be reduced, need continue reduction at follow-up reduction period, influence normal electric arc furnace operation, and generally adopt ferrosilicon to make reductive agent, the quantity of slag is big, hold free-running slag, cause final recovery rate low, have only about 90%.
Summary of the invention
When the objective of the invention is to solve electric furnace with the tungsten ore DIRECT ALLOYING, the problem that tungsten ore solid state reduction speed is slow, solid state reduction rate recovery rate low, tungsten is low, the DIRECT ALLOYING quantity of slag is big.
For achieving the above object, the present invention proposes a kind of process of oxide ore being carried out alloying directly into stove, be about to technique for alloying steel making directly from tungsten ore, its characteristics are tungsten ore is mixed with carbon containing tungsten ore pelletizing, the electric furnace when filling with substance is packed stove into furnace charge in, at melting period carbon containing tungsten ore pelletizing generation solid state reduction, the catalyzer that utilizes carbon containing tungsten ore pelletizing to allocate into is strengthened solid state reduction.The catalyzer of allocating into can invade between the base plane of carbon, make lattice distortion and weaken bond energy between carbon atom, thereby promote the desorption of surface mass, quicken the gasification reaction of carbon, help the reaction of carbon reduction tungsten ore, reach and quicken the reductive effect, thereby improve the solid state reduction rate, improve the recovery rate of furnace melting end of term tungsten.Do not finish reductive WO as yet at solid state reduction 3Enter in the slag, when filling with substance adds silicon carbide SiC or ferrosilicon powder enters molten steel, with it with slag in WO 3Generation liquid-liquid reacts the WO in the reducing slag 3Reduction period carries out dilution to slag, adds reductive agent SiC, with the WO in the abundant reducing slag 3
Carbon containing tungsten ore pelletizing solid state reduction mechanism of the present invention is: be solid-state WO in the carbon containing tungsten ore pelletizing 3Can following direct reduction reactor take place with solid carbon:
CaWO 4(s)+3C(s)＝W(s)+CaO(s)+3CO(g) △G 0＝638800—502.11T (1)
Because reaction (1) is to carry out on solid-affixed contact, contact area is little, so speed is slower.The CO gas that produces in the reaction (1) can continue and WO 3Generation indirect reduction reaction:
WO 3(s)+3CO(g)＝W(s)+3CO 2(g) △G 0＝—9350+5.26T (2)
The dividing potential drop of higher CO helps the carrying out of reaction (2) in the atmosphere.React the CO that produces above 2The gasification reaction of carbon at high temperature can take place:
CO 2(g)+C(s)＝2CO(g) △G 0＝166550—171T (3)
The dividing potential drop of CO is higher in the mixed gas that this reaction at high temperature produces, and therefore reaction (2) can be gone on.As seen at WO 3And CO gas is arranged between the carbon granule surface, exist the stack of the gasification reaction (3) of indirect reduction reaction (2) and C in the reaction system, thereby realize the direct reduction reactor function of oxide compound.The limiting element of this reaction system is the gasification reaction of reaction (3) carbon.In carbon containing tungsten ore pelletizing, add catalyzer, quicken the gasification reaction of carbon, reach the effect of the reaction of quickening the carbon reduction tungsten ore, thereby improve the solid state reduction rate, improve the recovery rate of furnace melting end of term tungsten, reduce the WO in the reduction period slag 3Content, the recovery rate of raising tungsten.
The present invention finishes its purpose by the following technical solutions: technique for alloying steel making directly from tungsten ore mainly comprises A and B two big steps:
A, at first tungsten ore is mixed with carbon containing tungsten ore pelletizing, method is as follows:
A) carbon containing tungsten ore pelletizing comprises 80%～85.5% tungsten ore, 13%～16.5% reductive agent, 1～2% catalyzer, 0.5%～1.5% binding agent;
B) tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form powder;
C) above powder is mixed;
D) the adding binding agent bonds together briquetting with powder and makes carbon containing tungsten ore pelletizing;
B, with technique for alloying steel making directly from tungsten ore, processing method is as follows:
1) steel scrap, carbon containing tungsten ore pelletizing, silicon carbide or ferrosilicon are packed into smelting furnace, and smelt;
2) oxygen blast is fluxed control, select late oxygen blast in melting period;
3) adopt low basicity slag technology in melting period and oxidation period;
4) carry out desulfurizing and refining+vacuum outgas after coming out of the stove, pour into a mould at last.
The main component of the tungsten ore described in the present invention is CaOWO3, and WO3 content is more than 65%; Used reductive agent be coal or coal with addition of 20%～30% coke powder, wherein the fixed carbon content of coal is more than 80%; Described catalyzer is any one among borate Na2B4O7, B2O3 or muriate NaCl, CaCl2, the KCl; Used binding agent is a water glass etc.; The broken powder particle that also grinds is about 200 orders; The oxygen blast in evening is meant that needs wait furnace charge fusing 90% oxygen blast more later on; Low basicity slag technology be meant melting period and oxidation period basicity of slag be controlled at smelting technology below 1.5.
The invention has the advantages that:
(1) compares with domestic and international existing tungsten ore DIRECT ALLOYING technology, the present invention strengthens the solid state reduction process, improved reduction reaction speed, the reduction ratio of tungsten ore is reached more than 90%, add the further dilution of reductive agent SiC by reduction period, the recovery rate of tungsten is reached more than 95%.And the slag gold reaction that conventional tungsten ore DIRECT ALLOYING technology mainly relies on, contact area is little, and only all just take place after the fusing at steel scrap, therefore do not utilize the still unfused electric arc furnace smelting stage of steel scrap, speed of response is lower than the two-step approach reduction that includes gas-solid reaction prereduction that the present invention proposes, and conventional tungsten ore DIRECT ALLOYING technology reduction period has 50% not reduction of tungsten ore, rely on the slag gold reaction reduction of reduction period, reduction period is long, be 50～70min, the present invention is in reduction period pre reduction rate 90%, therefore the reduction period time is short, shorten reduction period 20min than conventional tungsten ore DIRECT ALLOYING technology, and suitable with common ferro-tungsten metallization processes, reduction period is 30～50min.
(2) reductive agent in solid state reduction stage of the present invention is a carbon dust, and melting period tungsten ore reduction reaction has taken place, therefore the quantity of slag of smelting process is less, the quantity of slag of ferroalloy smelting just commonly used is the 50Kg/t steel, this technology quantity of slag is lower than the 55Kg/t steel, therefore can not bring any influence to electric arc furnace smelting, easy to operation.And with conventional tungsten ore DIRECT ALLOYING technology because the main slag gold reaction that relies on reduction period, need join high basicity slag, so the reduction period quantity of slag is big, the quantity of slag surpasses the 70Kg/t steel, bring difficulty to smelting operation, so this technology is better than conventional tungsten ore DIRECT ALLOYING technology in operation.
(3) tungsten ore DIRECT ALLOYING method of the present invention is compared with the method for ferro-tungsten alloying, recovery rate of iron level of the present invention is more than 95%, the recovery rate of iron level of ferro-tungsten alloyage process is about 90%～95%, so the present invention can reach or be higher than the recovery rate of iron level of ferro-tungsten alloyage process.Tungsten ore DIRECT ALLOYING method of the present invention can be equivalent to a kind of single step process technology without the whole plant of ferroalloy smelting, thereby investment and energy consumption all obtain saving, and the tungstenalloy that has reduced steel changes into this, has alleviated environmental pollution.The same rapid tool steel of producing one ton of tungstenic 6%, aspect resource consumption, the sheelite of DIRECT ALLOYING processes expend of the present invention is 99% of a traditional technology.The comprehensive power consumption (having counted the power consumption of used reductive agent) of smelting one ton of ferrotungsten is 4349.5kwh, comprehensive power consumption with the ferro-tungsten metallization processes is 860.6kwh, and the power consumption of DIRECT ALLOYING technology of the present invention is 517kwh, and DIRECT ALLOYING technology of the present invention has only 60% of ferro-tungsten metallization processes power consumption.DIRECT ALLOYING technology of the present invention is respectively 62.0%, 64.0%, 62.2%, 65.8% of traditional technology aspect atmosphere acidifying, Greenhouse effect, photo-chemical smog formation, this four classes carrying capacity of environment of aquatic organism toxicity.From aspect the quantity of slag, DIRECT ALLOYING technology of the present invention is 55.8% of traditional technology.The wastewater flow rate of DIRECT ALLOYING technology of the present invention is 46.2% of a traditional technology wastewater flow rate.
Embodiment
Carbon containing tungsten ore pelletizing is by 80%～85.5% tungsten ore, 13%～16.5% reductive agent, 1～2% catalyzer, 0.5%～1.5% binding agent is formed, earlier tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form 200 powder materials, then mixing and add the binding agent briquetting and make carbon containing tungsten ore pelletizing.The content of tungsten ore tungsten about 50%, reductive agent be coal or coal with addition of 20%～30% coke powder, wherein coal fixed carbon content is more than 80%, binding agent is a water glass, catalyzer is borate Na 2B 4O 7, B 2O 3With muriate NaCl, CaCl 2, among the KCl any one.
The electric arc furnace when filling with substance is adorned raw scrap material and silicon carbide SiC earlier, then carbon containing tungsten ore pelletizing is placed on the high-temperature electric arc zone of action of electric arc furnace.Carbon containing tungsten ore pelletizing add-on is determined according to the content of smelting steel grade and carbon containing tungsten ore pelletizing tungsten.
Processing requirement during smelting: oxygen blast fluxed control, select late oxygen blast as far as possible in melting period, oxygen blast again after the fusing 90% of furnace charges such as needs is in order to avoid the tungsten that is reduced out is oxidized again.
Oxidation period and reduction period adopt melting period and oxidation period basicity of slag be controlled at low basicity slag technology 1.5 below, continue to reduce WO to utilize reductive agent in the molten steel 3
Embodiment:
Embodiment 1: be to use tungsten ore DIRECT ALLOYING smelting high-speed tool steel M2 (W6Mo5Cr4V2) fully on 20 tons the electric arc furnace at Intake Quantity, the operational path of employing is: the low-phosphorous P steel scrap of electric furnace cold charge, carbon containing tungsten ore pelletizing, silicon carbide SiC, add molybdenum-iron → enter melting period → enter the oxidation period → enter reduction period → add vanadium iron → add slag depletion agent silicon carbide SiC → come out of the stove → carry out desulfurizing and refining → carry out VD vacuum-treat → pour into a mould at the LF stove.In this operational path, prepare carbon containing tungsten ore pelletizing earlier, it is made up of 85% tungsten ore, 13% reductive agent, 1% catalyzer, 1% binding agent, earlier tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form 200 powder materials, then mixing and add the binding agent briquetting and make carbon containing tungsten ore pelletizing.Tungsten ore W content 50.4%, reductive agent are that fixed carbon content is 85% coal, and binding agent is a water glass, and catalyzer is Na 2B 4O 7Carbon containing tungsten ore pelletizing tungstenic amount is 42.8%, increases tungsten 6% in the steel, and the ton steel need add carbon containing tungsten ore pelletizing 140.2Kg, and every stove adds carbon containing tungsten ore pelletizing 2804Kg altogether, and when filling with substance adds SiC 20kg, adds SiC 20kg during slag depletion.Result of implementation shows, adopt the inventive method can obtain good metallurgical effect, not only tungstenalloy element recovery rate reaches 95.25%, be higher than the ferro-tungsten alloyage process, and fluctuation is also little, stable operation, the finished steel quality is with suitable with the steel of ferro-tungstenization, can also obtain considerable economic, compare with using the ferro-tungsten alloyage process, the ton steel reduces cost 2061 yuan.
Embodiment 2: be to use tungsten ore DIRECT ALLOYING smelting high-speed tool steel M2Al (W6Mo5Cr4V2Al) fully on 15 tons the electric arc furnace at Intake Quantity, operational path is: the low-phosphorous steel scrap of electric furnace cold charge, carbon containing tungsten ore pelletizing, silicon carbide SiC, add molybdenum-iron → enter melting period → enter the oxidation period → enter reduction period → add vanadium iron → add slag depletion agent SiC → add aluminium ingot, the LF stove of coming out of the stove → carry out carries out desulfurizing and refining → carry out VD vacuum-treat → pour into a mould.The carbon containing tungsten ore pelletizing of preparation is made up of 82.5% tungsten ore, 15% reductive agent, 1.5% catalyzer, 1% binding agent, earlier tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form 200 powder materials, then mixing and add the binding agent briquetting and make carbon containing tungsten ore pelletizing.Tungsten ore W content 49.6%, reductive agent be 80% coal with addition of 20% coke powder, the fixed carbon content of coal is 82.5%, the fixed carbon content of coke powder is 80%, binding agent is a water glass, catalyzer is NaCl.Carbon containing tungsten ore pelletizing tungstenic amount is 40.9%, increases tungsten 6% in the steel, and the ton steel need add carbon containing tungsten ore pelletizing 146.7Kg, and every stove adds carbon containing tungsten ore pelletizing 2200Kg altogether, and when filling with substance adds SiC 10kg, adds SiC 10kg during slag depletion.Result of implementation shows, adopt the inventive method can obtain good metallurgical effect, not only tungstenalloy element recovery rate reaches 96.08%, be higher than the ferro-tungsten alloyage process, and fluctuation is also little, stable operation, the finished steel quality is with suitable with the steel of ferro-tungstenization, can also obtain considerable economic, compare with using the ferro-tungsten alloyage process, the ton steel reduces cost 2073 yuan.
Embodiment 3: be to use tungsten ore DIRECT ALLOYING smelting high-speed tool steel M2Al (W6Mo5Cr4V2Al) fully on 10 tons the electric arc furnace at Intake Quantity, the operational path of employing is: the low-phosphorous steel scrap of electric furnace cold charge, carbon containing tungsten ore pelletizing, silicon carbide SiC, add molybdenum-iron → enter melting period → enter the oxidation period → enter reduction period → add vanadium iron → add slag depletion agent SiC → add aluminium ingot, the LF stove of coming out of the stove → carry out carries out desulfurizing and refining → carry out VD vacuum-treat → pour into a mould.The carbon containing tungsten ore pelletizing of preparation is made up of 80% tungsten ore, 16.5% reductive agent, 2% catalyzer, 1.5% binding agent, earlier tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form 200 powder materials, then mixing and add the binding agent briquetting and make carbon containing tungsten ore pelletizing.Tungsten ore W content 48.1%, reductive agent be 70% coal with addition of 30% coke powder, the fixed carbon content of coal is 80%, the fixed carbon content of coke powder is 78%, binding agent is a water glass, catalyzer is CaCl 2Carbon containing tungsten ore pelletizing tungstenic amount is 38.5%, increases tungsten 6% in the steel, and the ton steel need add carbon containing tungsten ore pelletizing 155.9Kg, and every stove adds carbon containing tungsten ore pelletizing 1559Kg altogether, and when filling with substance adds SiC 10kg, adds SiC 10kg during slag depletion.Result of implementation shows, adopt the inventive method can obtain good metallurgical effect, not only tungstenalloy element recovery rate reaches 96.08%, be higher than the ferro-tungsten alloyage process, and fluctuation is also little, stable operation, the finished steel quality is with suitable with the steel of ferro-tungstenization, can also obtain considerable economic, compare with using the ferro-tungsten alloyage process, the ton steel reduces cost 2089 yuan.

Claims (2)

1, a kind of technique for alloying steel making directly from tungsten ore is characterized in that comprising the steps:
A, at first tungsten ore is mixed with carbon containing tungsten ore pelletizing, method is as follows:
A) carbon containing tungsten ore pelletizing comprises 80%～85.5% tungsten ore, 13%～16.5% reductive agent, 1～2% catalyzer, 0.5%～1.5% binding agent; Wherein: the main component of tungsten ore is CaOWO 3, WO 3Content is more than 65%; Reductive agent be coal or coal with addition of 20%～30% coke powder, wherein the fixed carbon content of coal is more than 80%; Catalyzer is borate Na 2B 4O 7, B 2O 3Or muriate NaCl, CaCl 2, among the KCl any one; Binding agent is a water glass;
B) tungsten ore, reductive agent, catalyzer are carried out fragmentation and grind to form powder;
C) above powder is mixed;
D) the adding binding agent bonds together briquetting with powder and makes carbon containing tungsten ore pelletizing;
B, with tungsten ore DIRECT ALLOYING steel-making, processing method is as follows:
1) steel scrap, carbon containing tungsten ore pelletizing, silicon carbide or ferrosilicon are packed into smelting furnace, and smelt;
2) oxygen blast is fluxed control, after melting period is chosen in furnace charge fusing 90%, carry out oxygen blast again;
3) adopt control basicity at the smelting technology below 1.5 in melting period and oxidation period;
4) carry out desulfurizing and refining+vacuum outgas after coming out of the stove, pour into a mould at last.
2, technique for alloying steel making directly from tungsten ore according to claim 1, the particle that it is characterized in that described powder is about 200 orders.
CNB2007100993368A 2007-05-17 2007-05-17 Technique for alloying steel making directly from tungsten ore Expired - Fee Related CN100500908C (en)

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CN106893925A (en) * 2017-04-02 2017-06-27 首钢总公司 A kind of method that tungsten is added in steelmaking process
CN109913644B (en) * 2019-03-11 2021-10-26 江苏大学 Process for alloying smelting steel for semi-high speed steel roller in black tungsten concentrate intermediate frequency furnace
CN109762958B (en) * 2019-03-28 2021-07-23 丹阳市曙光特钢有限公司 Process for smelting tungsten-containing high-speed steel

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1042571A (en) * 1988-11-11 1990-05-30 浙江大学 A kind of technology for alloying of cast-iron
CN1147561A (en) * 1995-10-10 1997-04-16 樊钢集团钢城企业总公司 Smelting process of high-speed tool steel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042571A (en) * 1988-11-11 1990-05-30 浙江大学 A kind of technology for alloying of cast-iron
CN1147561A (en) * 1995-10-10 1997-04-16 樊钢集团钢城企业总公司 Smelting process of high-speed tool steel

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