CN104775042A - Low-metal-loss smelting method of copper alloy - Google Patents
Low-metal-loss smelting method of copper alloy Download PDFInfo
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Abstract
The invention discloses a low-metal-loss smelting method of a copper alloy, which comprises the following steps: (1) adding all the raw materials except fusible and oxidable raw metals into a smelting furnace according to the components contained in the target alloy; after the raw materials are molten, introducing nitrogen or air into the smelting furnace, raising the pressure of the smelting furnace to 1-50 atm, and adding the low-melting raw metals into the smelting furnace; cooling the alloy melt, lowering the pressure of the hearth, and recovering valuable metals by using a micro reducing medium; using high-purity nitrogen, argon or carbon dioxide as a carrier gas, and adding a refining agent into the melt; introducing high-purity nitrogen or argon into the melt by using a rotary sprayer; adding a reducer-slag former mixture into the smelting furnace; and after removing all the furnace slag, adding a covering agent on the surface of the molten metal. The smelting method of the copper alloy can lower the metal loss, effectively remove impurity elements and gas inclusions in the alloy in the smelting process and enhance the refining effect.
Description
Technical field
The present invention relates to field of metallurgy, be specifically related to the low metal loss melting method of an Albatra metal-.
Background technology
In smelting copper alloy process, founding cost is mainly from the loss of metal.Traditional smelting copper alloy generally adopts in atmospheric conditions, smelting temperature system based on copper fusing point, the subject matter that this melting system exists is: in melting containing the brass of zinc, leaded brass, leaded bronze, bronze, stanniferous bronze containing cadmium and when there is the copper alloys such as easy scaling loss element aluminum, magnesium, beryllium, silicon, manganese, zirconium, chromium, there is strong burning and volatilization loss.Although take some technological measures, by the restriction of alloy melting characteristic, often produce little effect.As brass melting adopts low temperature zincification, flame melting, high temperature slag skimming process.The fusing point of zinc is only 419.5 DEG C, and the fusing point of copper is 1083.5 DEG C, and the fusing point of two clock metals differs 664 DEG C.So-called low temperature adds zinc technology, and service temperature, generally at about 1150 DEG C, certainly exists vigorous oxidation and the volatilization loss of zinc in zincification process.So-called flame melting technology, essence utilizes the low-boiling feature of metallic zinc in copper zinc alloy, and raised temperature makes metallic zinc seethe with excitement, evaporates, burns, and there is the strong oxidational losses of metallic zinc.Skimming in process at high temperature, there is strong burning, volatilization loss in the alloyed copper liquid surface unprotect of high temperature equally.Modern smelting copper alloy technique, makes the volatilization of the low melting points such as a large amount of metallic zinc, cadmium, lead, tin, aluminium, magnesium, beryllium, zirconium, silicon, manganese, oxidizable alloying element, oxidation, slag making, causes metal loss high.
ZL201210076603.0 proposes a kind of melting method reducing the brass alloys of zinc loss, but its one only proposed with regard to Mock platina and complex brass exempts from flame method of refining, to zinc yellow copper, low brass, cadmium bronze, leaded brass, leaded bronze, tinbronze in how reducing and the metal loss of the copper alloy such as aluminium, magnesium, beryllium, silicon, manganese, zirconium, chromium that there is easy scaling loss element, any measures and methods is not proposed.Meanwhile, copper alloy casting ingot quality is most important to subsequent production process, is necessary to further investigate the formation mechenism of the oxide slag inclusion and gas inclusions that affect ingot quality and removal methods, and develops degassed, deslagging method efficiently targetedly.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides the low metal loss melting method of an Albatra metal-, the method is applicable to all smelting copper alloy methods containing low melting point, easily scaling loss alloy constituent element, fusion process interalloy constituent element casting yield can be improved, again can effectively degassed, slagging-off, improve refining effect.
Above-mentioned purpose is realized by following proposal:
The low metal loss melting method of one Albatra metal-, is characterized in that, said method comprising the steps of:
(1) constituent element contained by subject alloy, in smelting furnace, add the raw material except meltable, oxidizable raw metal, after melting sources, in smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then adds meltable, oxidizable raw metal in smelting furnace;
(2) pass in melt and be heated to the nitrogen of 150 DEG C-400 DEG C and the mixed gas of oxygen, wherein the volume percent of oxygen is less than 15%;
(3) in melt, pass into high pure nitrogen and add reduction components, or passing into high pure nitrogen and Co mixed gas, or passing into carbon monoxide and carbon dioxide gas mixture, and slowly reducing smelting furnace pressure, making material in smelting furnace that flame and combustion phenomena not occur;
(4) with high pure nitrogen, argon gas or carbonic acid gas for carrier gas, in melt, add refining agent;
(5) by rotary nozzle, high pure nitrogen or argon gas are passed in melt;
(6) in smelting furnace, add the mixture of reductive agent and slag former, fully stir bath surface;
(7), after scratching clean slag, insulating covering agent is added on molten metal surface.
According to above-mentioned melting method, it is characterized in that, in step (1), when using fine copper as raw material: add fine copper in smelting furnace, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
According to above-mentioned melting method, it is characterized in that, in step (1), when using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add fine copper, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
According to above-mentioned melting method, it is characterized in that, in step (1), when using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
According to above-mentioned melting method, it is characterized in that, in step (1), when using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: in smelting furnace, add the old material of copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
According to above-mentioned melting method, it is characterized in that, in step (1), when using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add the old material of pure copper and copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
According to above-mentioned melting method, it is characterized in that, the component of the refining agent used in step (4) comprises sodium aluminum fluoride, aluminum fluoride, Sodium Fluoride, sodium carbonate, calcium carbonate.
According to above-mentioned melting method, it is characterized in that, the component of the reductive agent used in step (6) comprises carbon dust, carbide of calcium, boronation magnesium, boron slag, and the component of the slag former used in step (6) comprises SiO2, calcium carbonate, sodium carbonate, sodium-chlor, Repone K, aluminum oxide.
According to above-mentioned melting method, it is characterized in that, the component of the insulating covering agent used in step (7) comprises borax, glass, phosphorus powder.
Beneficial effect of the present invention:
Use the low metal loss melting method of copper alloy of the present invention, can the fusion process of strengthened copper alloy, shorten melting cycle, enhance productivity; Alloy oxidation loss can be reduced, reduce alloy volatilization loss, eliminate flame combustion loss; Can impurity element in efficient removal alloy and gas inclusions, improve metal casting yield; By making low viscous, powdery, dryness slag, significantly reducing slag and to skim metal loss.Cancel charcoal to cover, reduce charcoal consumption 20-25kg/t copper.Adopt this technology to reduce environmental pollution, improve work situation, the investment of cancellation environmental protection equipment and place take, and reduce investment in fixed assets and dust collection device working cost.
Embodiment
The present invention is according in smelting copper alloy process, and the loss such as burning loss, metal volatilization loss, flame combustion loss, metal slag making loss link, proposes a kind of low-loss smelting copper alloy method.Meanwhile, in fusion process, the impurity element in energy effective elimination alloy and gas inclusions.
This melting method comprises the following steps:
Smelting furnace body of heater is seated in the adjustable enclosed space of furnace pressure (furnace pressure regulation range is 0-50atm); Or install sealing bonnet additional at the oral area of common smelting furnace, form the adjustable space of furnace pressure on metal pool top.
(1) constituent element contained by subject alloy, in smelting furnace, add the raw material except meltable, oxidizable raw metal, after melting sources, in smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in smelting furnace, adds low melting point, oxidizable raw metal;
Wherein, " meltable, oxidizable raw metal " refers to the pure metal raw material (as metals such as Zn, Mn, Zr, Sn) that fusing point is low or more oxidizable than copper, and the main old material of copper alloy containing meltable easy oxidation metal component.These pure metal and alloy are at high temperature oxidizable, volatile." raw material except except meltable, oxidizable raw metal " refers to that fusing point is more than or equal to copper and is not easy the pure metal raw material (as metals such as Cu, Fe, Ni) of oxidation, and the main old material of copper alloy containing refractory metal component.The present invention adopts high temperature melting fine copper, refractory metal raw material and the main old material of copper alloy containing refractory metal component to have two advantages: one is to shorten the melting sources phase, improves melting sources efficiency.Two is utilize the high temperature oxygen uptake of alloy to be inclined to, for follow-up oxidation degassing process creates conditions.After the raw material except meltable, oxidizable raw metal melts completely, nitrogen or air is passed in smelting furnace, smelting furnace pressure is elevated to 1-50atm, constituent element contained by subject alloy again, the pure metal raw material that fusing point is low or more oxidizable than copper is added in molten metal, and the main old material of copper alloy containing meltable easy oxidation metal component, carry out the fusing of the old material raw material of copper alloy mainly containing meltable easy oxidation metal component, and low melting point, oxidizable, volatile alloy constituent element rapid alloying.The alloying of the fusing of the copper alloy old material raw material mainly containing meltable easy oxidation metal component and the oxidizable pure metal raw material of low melting point is carried out under high-temperature pressurizing condition, the volatilization loss of meltable, volatile constituent element can be reduced, prevent volatile constituent element (as metallic zinc, tin etc.) boiling, flame, burning, shorten the melting period of low melting point, oxidizable, volatile alloy constituent element.Add meltable, oxidizable alloy constituent element under the high temperature conditions, utilize the oxygen in oxidizable alloy constituent element and alloy melt (oxygen that the high temperature melting phase absorbs) that low-level oxidation occurs and react, the metal of reduction pliotherm period oxidation, improves the rate of recovery of infusibility, high-valency metal.
The copper material used according to melting and the chemical composition of subject alloy, this step has several different situations:
When using fine copper as raw material: add fine copper in smelting furnace, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.High melting point alloy constituent element refers to that fusing point is more than or equal to copper and is not easy the metal component (as metal components such as Fe, Ni) of oxidation in subject alloy, and meltable oxidizable alloy constituent element refers to the metal component (as metal components such as Zn, Mn, Zr, Sn) that fusing point is low or more oxidizable than copper in subject alloy.
When using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add fine copper, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
When using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
When using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: in smelting furnace, add the old material of copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
When using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add the old material of pure copper and copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
Other situations do not repeat one by one, as long as follow the principle that meltable oxidizable raw metal adds after boosting, other raw metal adds prior pressure application.Wherein, according to the chemical composition of copper raw material and target copper alloy, when not needing to add high melting point alloy constituent element in smelting furnace (not containing high melting point alloy constituent element etc. in such as subject alloy), the step adding high melting point alloy constituent element in smelting furnace is only needed to omit.
When fine copper and/or containing the old material of copper alloy of high melting point alloy constituent element and high melting point alloy constituent element for reaction institute required time, need first to heat up fusing by fine copper and/or containing the old material of copper alloy of high melting point alloy constituent element, and then add high melting point alloy constituent element in smelting furnace.Simultaneously its reason adds in smelting furnace when fine copper and/or containing the old material of copper alloy of high melting point alloy constituent element and high melting point alloy constituent element, then the fusing that heats up, and high melting point alloy constituent element can be caused oxidized.
(2) pass in melt and be heated to the nitrogen of 150 DEG C-400 DEG C and the mixed gas of oxygen, wherein the volume percent of oxygen is less than 15%.
This step is carrier gas low-level oxidation-removal of impurities, dehydrogenation step, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as lead impurity element, bismuth, iron in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
(3) in melt, pass into high pure nitrogen and add reduction components, or passing into high pure nitrogen and Co mixed gas, or passing into carbon monoxide and carbon dioxide gas mixture, and slowly reducing smelting furnace pressure, making material in smelting furnace that flame and combustion phenomena not occur.
The object of this step is to alloy melt cooling, to burner hearth step-down, reclaims valuable metal with micro-reducing medium, improves metal casting yield.The gaseous media of cold conditions is utilized to take away energy unnecessary in melt, to melt cooling, and synchronously suitably reduce furnace pressure (not produce flame, burning, metal volatilization not occurring for degree), object reduces the vapour pressure of alloying element, reduces the metal volatilization loss of subsequent processes.Reductibility constituent element in refining medium and the metal oxide generation reduction reaction in melt, by the metallic reducing in oxide compound, improve the casting yield of metal.
(4) with high pure nitrogen, argon gas or carbonic acid gas for carrier gas, in melt, add refining agent.
The object of this step is the oxide inclusion removed in alloy.Wherein the main component of refining agent comprises sodium aluminum fluoride, aluminum fluoride, Sodium Fluoride, sodium carbonate, calcium carbonate.Refining agent is inputted alloy melt by carrier gas, and refining agent is with bubble Dispersed precipitate in alloy melt, and refining agent meets high-temperature fusant fusing, and the refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Good wettability is had due to the slag in refining agent and melt with between being mingled with, slag is adsorbed on drop or bubble surface with being mingled with, under the buoyancy of density difference and bubble, removed by the mechanism of absorption-flotation, form metallurgical slag, swim in aluminium alloy surface.
(5) by rotary nozzle, high pure nitrogen or argon gas are passed in melt.This is the diffusion degassing stage of copper alloy.
Utilize the crushing effect of rotary nozzle, High Purity Nitrogen or argon gas are broken into the bubble of disperse, are evenly distributed in alloy melt.The hydrogen dissolved in alloy melt, under the effect of concentration difference and pressure difference, diffuses in bubble, rises, discharges, reach dehydrogenation effect with bubble.
(6) in smelting furnace, add the mixture of reductive agent and slag former, fully stir bath surface.
The active princlple of reductive agent is carbon dust, carbide of calcium, boronation magnesium, boron slag, and the main component of slag former is SiO2, calcium carbonate, sodium carbonate, sodium-chlor, Repone K, aluminum oxide.Add in smelting furnace by the mixture of reductive agent and slag former, stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent, by Reduction of Oxides such as Cu2O, CuO, NiO, the ZnO in scum silica frost, converges into molten drop and flows back to metal pool.Nonwetting between the slag former that the present invention adopts and molten metal, make the dryness slag of the low or powdering of the slag viscosity produced, reduce the metal loss that slag causes.
(7), after scratching clean slag, insulating covering agent is added on molten metal surface.The component of insulating covering agent comprises borax, glass, phosphorus powder, forms P2O5ZnO protective membrane and borax-glass precursor solution protective layer, prevents metal to be again oxidized, air-breathing on molten metal surface.
Embodiment 1
HNi65-5 smelting copper alloy
In the line-frequency induction smelting furnace that furnace pressure is adjustable, be that the Cu of 65% puts into main frequency furnace and melts by mass percent, temperature of fusion is copper fusing point height 100-190 DEG C comparatively.Treat that copper material melts, in copper liquid, add the nickel that mass percent is 5.5%, rapid melting metallic nickel under high temperature, air atmosphere condition.Treat that metallic nickel fusing terminates, furnace pressure is adjusted to 3atm, under high temperature, condition with pressure, in the copper-nickel alloy liquid of fusing, adds the Zn that mass percent is 32 %, rapid melting low melting point, oxidizable, volatile metallic zinc.
The mixed gas (oxygen level is lower than 15%) of nitrogen and oxygen is heated to 300-350 DEG C, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as lead impurity element, bismuth, iron in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
By the high pure nitrogen of room temperature and Mg
3b
2the mixture of powder, is passed in alloy melt, utilizes cupric oxide, Red copper oxide, nickel protoxide, nickel oxide in boronation magnesium reduction molten metal, reduces the loss of cupronickel element oxide, utilizes boronation magnesium to remove harmful element sulphur in alloy simultaneously.Reduce smelting furnace power input, and utilize the gaseous media of cold conditions to take away energy unnecessary in alloy melt, lower the temperature to alloy melt, and synchronously suitably reduce furnace pressure (not produce flame, burning, there is not metal volatilization for degree), object reduces the vapour pressure of zinc, reduces the metal volatilization loss of subsequent processes.
Take high pure nitrogen as carrier gas, copper alloy refining agent is passed into alloy melt.The refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Slag and be mingled with and be adsorbed on drop or bubble surface, under the buoyancy of density difference and bubble, is removed by the mechanism of absorption-flotation, formation metallurgical slag, swims in aluminium alloy surface.
By rotary nozzle, high pure nitrogen is passed in alloy melt, utilize the crushing effect of rotary nozzle, High Purity Nitrogen is broken into the bubble of disperse, the hydrogen dissolved in alloy melt is under the effect of concentration difference and pressure difference, diffuse in bubble, rise with bubble, discharge, reach dehydrogenation effect.
The mixture of reductive agent, slag former is added dross surface, and stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent is by the Cu in scum silica frost
2the Reduction of Oxides such as O, CuO, NiO, ZnO, converge into molten drop and flow back to metal pool.Remaining slag is caused the dryness slag of nonwetting between molten metal, low viscous slag or powdering by slag former, reduces the metal loss that slag causes.
Add covering protection agent on the molten metal surface scratching clean slag, the component of insulating covering agent comprises: borax, glass, phosphorus powder etc., forms P on molten metal surface
2o
5znO protective membrane and borax-glass precursor solution protective layer, prevent metal to be again oxidized, air-breathing.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1070-1100 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Cu of 65.3%, the nickel of 5.9%, surplus is zinc.
Embodiment 2
HFe59-1-1 smelting copper alloy
In the line-frequency induction smelting furnace that furnace pressure is adjustable, be that the Cu of 59% puts into main frequency furnace and melts by mass percent, temperature of fusion is copper fusing point height 90-150 DEG C comparatively.Treat that copper material melts, in copper liquid, add mass percent is the iron of 1.2% and the nickel of 0.5%, rapid melting metallic copper, iron, nickelalloy under high temperature, air atmosphere condition.Treat that metallic copper-iron-nickel fusing terminates, furnace pressure is adjusted to 4atm, under high temperature, condition with pressure, add mass percent in the copper-iron nickel alloy liquid of fusing is the Al of 0.8%, Mn, the Sn of 0.9%, the Zn of 37 % of 0.9%, rapid melting low melting point, oxidizable, volatile metallic aluminium, manganese, tin, zinc.
The mixed gas (oxygen level is 2%-3%) of nitrogen and oxygen is heated to 200-250 DEG C, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as impurity element bismuth, sulphur in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
By the high pure nitrogen of room temperature and carbon dust, Mg
3b
2the mixture of powder, be passed in alloy melt, utilize cupric oxide, Red copper oxide, zinc oxide, aluminum oxide, manganese oxide, the ferric oxide in boronation magnesium reduction molten metal, reduce the oxidational losses of copper alloy valuable element, utilize boronation magnesium to remove harmful element sulphur in alloy simultaneously.Reduce smelting furnace power input, and utilize the gaseous media of cold conditions to take away energy unnecessary in alloy melt, lower the temperature to alloy melt, and synchronously suitably reduce furnace pressure (not produce flame, burning, there is not metal volatilization for degree), object reduces the vapour pressure of zinc, reduces the metal volatilization loss of subsequent processes.
Take High Purity Nitrogen as carrier gas, the copper alloy refining agent containing sodium aluminum fluoride component is passed into alloy melt.The refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Slag and be mingled with and be adsorbed on drop or bubble surface, under the buoyancy of density difference and bubble, is removed by the mechanism of absorption-flotation, formation metallurgical slag, swims in aluminium alloy surface.
By rotary nozzle, high pure nitrogen is passed in alloy melt, utilize the crushing effect of rotary nozzle, High Purity Nitrogen is broken into the bubble of disperse, the hydrogen dissolved in alloy melt is under the effect of concentration difference and pressure difference, diffuse in bubble, rise with bubble, discharge, reach dehydrogenation effect.
The mixture of reductive agent, slag former is added dross surface, and stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent, by Reduction of Oxides such as Cu2O, CuO, the ZnO in scum silica frost, converges into molten drop and flows back to metal pool.Remaining slag is caused the dryness slag of nonwetting between molten metal, low viscous slag or powdering by slag former, reduces the metal loss that slag causes.
Add covering protection agent on the molten metal surface scratching clean slag, the component of insulating covering agent comprises: borax, glass, phosphorus powder etc., forms P2O5ZnO protective membrane and borax-glass precursor solution protective layer, prevents metal to be again oxidized, air-breathing on molten metal surface.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1000-1040 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Cu of 59.6%, the Fe of 1.1%, the Al of 0.35%, the Mn of 0.69%, the Sn of 0.63%, the nickel of 0.45%, surplus is zinc.
Embodiment 3
H59 smelting copper alloy
In the line-frequency induction smelting furnace that furnace pressure is adjustable, be that the Cu of 59% puts into main frequency furnace and melts by mass percent, temperature of fusion is copper fusing point height 60-120 DEG C comparatively.Treat that metallic copper fusing terminates, furnace pressure is adjusted to 5atm, under high temperature, condition with pressure, in the copper liquid of fusing, adds the Zn that mass percent is 43%, rapid melting low melting point, oxidizable, volatile metallic zinc.
The mixed gas (oxygen level is lower than 15%) of nitrogen and oxygen is heated to 200-250 DEG C, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as lead impurity element, bismuth, iron in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
By the high pure nitrogen of room temperature and the mixture of activated carbon powder, be passed in alloy melt, utilize cupric oxide, Red copper oxide, zinc oxide in the liquid of activated carbon powder reducing metal, reduce the loss of copper zinc alloy element oxide.Reduce smelting furnace power input, and utilize the gaseous media of cold conditions to take away energy unnecessary in alloy melt, lower the temperature to alloy melt, and synchronously suitably reduce furnace pressure (not produce flame, burning, there is not metal volatilization for degree), object reduces the vapour pressure of zinc, reduces the metal volatilization loss of subsequent processes.
Take High Purity Nitrogen as carrier gas, copper alloy refining agent is passed into alloy melt.The refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Slag and be mingled with and be adsorbed on drop or bubble surface, under the buoyancy of density difference and bubble, is removed by the mechanism of absorption-flotation, formation metallurgical slag, swims in aluminium alloy surface.
By rotary nozzle, high pure nitrogen is passed in alloy melt, utilize the crushing effect of rotary nozzle, High Purity Nitrogen is broken into the bubble of disperse, the hydrogen dissolved in alloy melt is under the effect of concentration difference and pressure difference, diffuse in bubble, rise with bubble, discharge, reach dehydrogenation effect.
The mixture of reductive agent, slag former is added dross surface, and stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent, by Reduction of Oxides such as Cu2O, CuO, the ZnO in scum silica frost, converges into molten drop and flows back to metal pool.Remaining slag is caused the dryness slag of nonwetting between molten metal, low viscous slag or powdering by slag former, reduces the metal loss that slag causes.
Add covering protection agent on the molten metal surface scratching clean slag, the component of insulating covering agent comprises: borax, glass, phosphorus powder etc., forms P2O5ZnO protective membrane and borax-glass precursor solution protective layer, prevents metal to be again oxidized, air-breathing on molten metal surface.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting warm 1010-1030 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Cu of 59.1%, surplus is zinc.
Embodiment 4
H59 copper alloy old material melting H70
In the line-frequency induction smelting furnace that furnace pressure is adjustable, be that the Cu of 35% puts into main frequency furnace and melts by mass percent, temperature of fusion is copper fusing point height 60-120 DEG C comparatively.Treat that metallic copper fusing terminates, furnace pressure is adjusted to 5atm, in the copper liquid of fusing, the old material of H59 copper alloy that mass percent is 50% is added under high temperature, condition with pressure, according to H70 brass dispensing requirements, consider that the old material strip of H59 copper alloy enters the Zn amount that smelting furnace brought into by copper alloy, supplement to smelting furnace and add Zn, rapid melting low melting point, oxidizable, volatile metallic zinc.
The mixed gas (oxygen level is lower than 15%) of nitrogen and oxygen is heated to 200-250 DEG C, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as lead impurity element, bismuth, iron in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
By the high pure nitrogen of room temperature and the mixture of activated carbon powder, be passed in alloy melt, utilize cupric oxide, Red copper oxide, zinc oxide in the liquid of activated carbon powder reducing metal, reduce the loss of copper zinc alloy element oxide.Reduce smelting furnace power input, and utilize the gaseous media of cold conditions to take away energy unnecessary in alloy melt, lower the temperature to alloy melt, and synchronously suitably reduce furnace pressure (not produce flame, burning, there is not metal volatilization for degree), object reduces the vapour pressure of zinc, reduces the metal volatilization loss of subsequent processes.
Take High Purity Nitrogen as carrier gas, copper alloy refining agent is passed into alloy melt.The refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Slag and be mingled with and be adsorbed on drop or bubble surface, under the buoyancy of density difference and bubble, is removed by the mechanism of absorption-flotation, formation metallurgical slag, swims in aluminium alloy surface.
By rotary nozzle, high pure nitrogen is passed in alloy melt, utilize the crushing effect of rotary nozzle, High Purity Nitrogen is broken into the bubble of disperse, the hydrogen dissolved in alloy melt is under the effect of concentration difference and pressure difference, diffuse in bubble, rise with bubble, discharge, reach dehydrogenation effect.
The mixture of reductive agent, slag former is added dross surface, and stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent, by Reduction of Oxides such as Cu2O, CuO, the ZnO in scum silica frost, converges into molten drop and flows back to metal pool.Remaining slag is caused the dryness slag of nonwetting between molten metal, low viscous slag or powdering by slag former, reduces the metal loss that slag causes.
Add covering protection agent on the molten metal surface scratching clean slag, the component of insulating covering agent comprises: borax, glass, phosphorus powder etc., forms P2O5ZnO protective membrane and borax-glass precursor solution protective layer, prevents metal to be again oxidized, air-breathing on molten metal surface.
Sampling analysis, after alloying constituent conformance with standard requires, comes out of the stove the temperature adjustment of copper liquid to routine casting temperature.
Copper alloy composition prepared is in this way (mass percent): the Cu of 70.051%, surplus is zinc.
Embodiment 5
H90 copper alloy old material melting H59
In the line-frequency induction smelting furnace that furnace pressure is adjustable, be that main frequency furnace put into by the old material of H90 copper alloy of 60% by mass percent, furnace pressure adjusted to 5atm, heat up old for copper alloy material fusing.According to H59 brass dispensing requirements, consider that the old material strip of H90 copper alloy enters the Zn amount that smelting furnace brought into by copper alloy, under high temperature, condition with pressure, supplement to smelting furnace and add Zn, rapid melting low melting point, oxidizable, volatile metallic zinc.
The mixed gas (oxygen level is lower than 15%) of nitrogen and oxygen is heated to 200-250 DEG C, mixed gas that is appropriate, that pass through nitrogen and the oxygen heated is passed in alloy melt, utilize the stirring action uniform alloy composition of gas, utilize oxidizing medium to remove the slag making such as lead impurity element, bismuth, iron in alloy, utilize the oxygen passed into remove hydrogen in alloy further.
By the high pure nitrogen of room temperature and the mixture of activated carbon powder, be passed in alloy melt, utilize cupric oxide, Red copper oxide, zinc oxide in the liquid of activated carbon powder reducing metal, reduce the loss of copper zinc alloy element oxide.Reduce smelting furnace power input, and utilize the gaseous media of cold conditions to take away energy unnecessary in alloy melt, lower the temperature to alloy melt, and synchronously suitably reduce furnace pressure (not produce flame, burning, there is not metal volatilization for degree), object reduces the vapour pressure of zinc, reduces the metal volatilization loss of subsequent processes.
Take High Purity Nitrogen as carrier gas, copper alloy refining agent is passed into alloy melt.The refining agent of fusing is dispersed in alloy melt with the form of drop, or film-like is coated on bubble surface.Slag and be mingled with and be adsorbed on drop or bubble surface, under the buoyancy of density difference and bubble, is removed by the mechanism of absorption-flotation, formation metallurgical slag, swims in aluminium alloy surface.
By rotary nozzle, high pure nitrogen is passed in alloy melt, utilize the crushing effect of rotary nozzle, High Purity Nitrogen is broken into the bubble of disperse, the hydrogen dissolved in alloy melt is under the effect of concentration difference and pressure difference, diffuse in bubble, rise with bubble, discharge, reach dehydrogenation effect.
The mixture of reductive agent, slag former is added dross surface, and stir bath surface, slag former is fully contacted with scum silica frost, reacts, reductive agent, by Reduction of Oxides such as Cu2O, CuO, the ZnO in scum silica frost, converges into molten drop and flows back to metal pool.Remaining slag is caused the dryness slag of nonwetting between molten metal, low viscous slag or powdering by slag former, reduces the metal loss that slag causes.
Add covering protection agent on the molten metal surface scratching clean slag, the component of insulating covering agent comprises: borax, glass, phosphorus powder etc., forms P2O5ZnO protective membrane and borax-glass precursor solution protective layer, prevents metal to be again oxidized, air-breathing on molten metal surface.
Sampling analysis, after alloying constituent conformance with standard requires, comes out of the stove the temperature adjustment of copper liquid to routine casting temperature.
Copper alloy composition prepared is in this way (mass percent): the Cu of 58.9%, surplus is zinc.
Claims (9)
1. the low metal loss melting method of an Albatra metal-, is characterized in that, said method comprising the steps of:
(1) constituent element contained by subject alloy, in smelting furnace, add the raw material except meltable, oxidizable raw metal, after melting sources, in smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then adds meltable, oxidizable raw metal in smelting furnace;
(2) pass in melt and be heated to the nitrogen of 150 DEG C-400 DEG C and the mixed gas of oxygen, wherein the volume percent of oxygen is less than 15%;
(3) in melt, pass into high pure nitrogen and add reduction components, or passing into high pure nitrogen and Co mixed gas, or passing into carbon monoxide and carbon dioxide gas mixture, and slowly reducing smelting furnace pressure, making material in smelting furnace that flame and combustion phenomena not occur;
(4) with high pure nitrogen, argon gas or carbonic acid gas for carrier gas, in melt, add refining agent;
(5) by rotary nozzle, high pure nitrogen or argon gas are passed in melt;
(6) in smelting furnace, add the mixture of reductive agent and slag former, fully stir bath surface;
(7), after scratching clean slag, insulating covering agent is added on molten metal surface.
2. melting method according to claim 1, is characterized in that, in step (1), when using fine copper as raw material: add fine copper in smelting furnace, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
3. melting method according to claim 1, it is characterized in that, in step (1), when using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add fine copper, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; When after fine copper fusing, in smelting furnace, add high melting point alloy constituent element; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
4. melting method according to claim 1, it is characterized in that, in step (1), when using the main old material of copper alloy containing meltable easy oxidation metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add the old material of copper alloy, or in molten metal, add the old material of copper alloy and meltable oxidizable alloy constituent element.
5. melting method according to claim 1, it is characterized in that, in step (1), when using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content higher than in subject alloy during copper content: in smelting furnace, add the old material of copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
6. melting method according to claim 1, it is characterized in that, in step (1), when using the main old material of copper alloy containing refractory metal component as melting raw material, and in the old material of copper alloy copper content lower than in subject alloy during copper content: in smelting furnace, add the old material of pure copper and copper alloy, be warming up to comparatively copper fusing point high 0 DEG C-200 DEG C; High melting point alloy constituent element is added in smelting furnace; In smelting furnace, pass into nitrogen or air, smelting furnace pressure is elevated to 1-50atm, then in molten metal, add meltable oxidizable alloy constituent element.
7. melting method according to claim 1, is characterized in that, the component of the refining agent used in step (4) comprises sodium aluminum fluoride, aluminum fluoride, Sodium Fluoride, sodium carbonate, calcium carbonate.
8. melting method according to claim 1, it is characterized in that, the component of the reductive agent used in step (6) comprises carbon dust, carbide of calcium, boronation magnesium, boron slag, and the component of the slag former used in step (6) comprises SiO2, calcium carbonate, sodium carbonate, sodium-chlor, Repone K, aluminum oxide.
9. melting method according to claim 1, is characterized in that, the component of the insulating covering agent used in step (7) comprises borax, glass, phosphorus powder.
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