CN104894412A - Method for removing impurity during copper and copper alloy melting process - Google Patents
Method for removing impurity during copper and copper alloy melting process Download PDFInfo
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- CN104894412A CN104894412A CN201510178141.7A CN201510178141A CN104894412A CN 104894412 A CN104894412 A CN 104894412A CN 201510178141 A CN201510178141 A CN 201510178141A CN 104894412 A CN104894412 A CN 104894412A
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Abstract
The invention discloses a method for removing impurity during copper and a copper alloy melting process, which comprises the following steps: 1)a micro oxidation phase: introducing oxygen in a copper and copper alloy melt in a cored induction melting furnace, or a coreless induction melting furnace, or a shaft furnace, or a reverberatory furnace, or adding one or more from CuO, MnO2 and KMnO4 as an oxidizing agent for a slagging reaction; 2)a micro reduction phase: using one or more from metal Mg, Cr, Zr, B as a reducing agent, reducing and recovering the valuable metals in the oxidation process; and 3)a harmful impurity element harmlessness processing phase; adding one or more from Li, Ca, Zr, Mn for removing harmful impurity. The method can use the raw materials with low cost and low quality, or uses the outshot which has standard-exceeding impurity and harmful element, a simple micro oxidation-micro reduction-harmlessness processing is carried out on the current cored induction melting furnace, the coreless induction furnace or the shaft furnace, so that products with high quality can be produced.
Description
Technical field
The invention belongs to metallurgical casting technical field, be specifically related to the impurity-removing method in a kind of Copper and its alloy fusion process.
Background technology
Along with deepening continuously of recycling economy, directly reclaim and utilize copper scap as the raw material of Copper fabrication, having become Copper fabrication enterprise and reduced production cost, improve the important means of product competitiveness.And copper scap is often from different industry, the different departments of society, composition is extremely complicated.The copper scap of the different varieties alloying element often containing different sorts, different weight percentage content, trace element and impurity element.Some element is harmful to follow-up Copper fabrication technique, Copper fabrication product.
In fact, the control of Copper fabrication to micro impurity element is strict, and GB/T467-1997 Cu-CATH-1 specifies: impurity element S e, Te, Bi single-element content can not more than 0.00020%.GB/T467-1997 standard cathode copper specifies: impurity element Pb single-element content can not more than 0.002%.Processing Copper and its alloy chemical composition and shape of product GB/T5231-2001 specify, No. two industrial pure copper T2 are to impurity B i upper content limit 0.001%, impurity Sb upper content limit 0.002%, impurity Pb upper content limit 0.005%.The oxygen level upper limit that No. zero oxygen free copper TU0 specifies is 0.0005%, and the upper limit of phosphorus content is 0.0003%.The requirement upper limit of iron white copper BFe10-1-1 and BFe30-1-1 to impurity element S content is no more than 0.01%.Market brass is different and different according to the kind of alloy, purposes to the upper limit of impurity F e content requirement, and the general upper limit is no more than 0.10%-0.30%.Some detrimental impurity element, even if content overproof is atomic, also can produces and have a strong impact on Drawing abillity, use properties.Impurity element Pb, Bi exceed standard, and can make to be easy to cracking during alloy hot-work, and Bi also can make alloy produce cold working fragility.Namely Ti, P, Fe of trace can produce the conductivity of copper and have a strong impact on.Oxygen in Oxygen-Free Copper content overproof can make alloy produce " hydrogen is sick "; Electron tube oxygen free copper, phosphorus content reaches 0.0003%, can peel off by generating device surface epithelium, causing electron tube to leak when carrying out borax treatment.In iron white copper, sulphur exceeds standard and can fall low-alloyed solidity to corrosion and work-ing life.Market brass alloy iron exceeds standard and requirement can be made to produce magnetic without the alloy of magnetic, affects use properties.
In prior art, in order to eliminate the impurity element in copper scap raw material, harmful alloying element, generally adopt two-stage method to be refined by copper scap as electrolytic copper, copper scap is through retailoring of blast furnace or bessemerize, be processed into anode copper through reverberatory furnace again, then obtain electrolytic copper by electrolysis treatment.The technological process of production adopted is long, production energy consumption is high, metal loss is large, production cost is high, environmental pollution is large, this copper scap treatment process, in fact copper scap is processed according to ore, by impurity element, harmful element, valuable metal etc. in copper scap, slag making, discarded.
Summary of the invention
The object of the invention is for prior art Problems existing, the impurity-removing method in a kind of Copper and its alloy fusion process is provided.The present invention is according to the composition characteristic of Copper and its alloy raw material, for single in Copper and its alloy raw material or two kinds or more of impurity element exceed standard-required etc. outer raw material, or for meeting the requirement of alloy substrate sublimate, a kind of low-level oxidation-micro-reduction of proposition and micro-detrimental impurity element method for innocent treatment.The method is on the basis of raw material at the Copper and its alloy liquid that traditional Copper and its alloy melting method obtains, or on the basis that the Copper and its alloy liquid obtained with temperature control-pressure regulation melting method is raw material, have in core induction melting furnace or coreless induction smelting furnace or shaft furnace existing, adopt low-level oxidation slag making technology to remove harmful, impurity element in alloy; Adopt the valuable metal be oxidized in micro-reduction technique reduction-oxidation slagging process, improve the casting yield of valuable metal; To harmful, the impurity element that cannot be removed by low-level oxidation-micro-reduction treatment, adopt innoxious process for treating, eliminate the disadvantageous effect of harmful element.
Concrete scheme is as follows:
An impurity-removing method in Copper and its alloy fusion process, is characterized in that, said method comprising the steps of:
(1) the low-level oxidation stage: pass into oxygen in the Copper and its alloy liquation had in core induction melting furnace or coreless induction smelting furnace or shaft furnace or reverberatory furnace, or add CuO, MnO
2, KMnO
4in one or more as oxygenant, carry out slag making reaction;
(2) micro-reduction phase: use metal M g, one or more in Cr, Zr, B as reductive agent, reduction, reclaims the valuable metal of oxidising process oxidation;
(3) the detrimental impurity element harmless treatment stage: add in Li, Ca, Zr, Mn one or more go out detrimental impurity.
According to above-mentioned method, it is characterized in that, in described step (1), for Si, Sn, Al, Zn, Ni, Fe, As, Sb, Bi, Se, Te impurity, with oxygen as oxygenant, the mode of allocating into of oxygen is the O of the nitrogen+3%-30% of volume accounting 70%-97%
2, or the O of argon gas+3%-30% of volume accounting 70%-97%
2, or volume account for the O of mixed gas+3%-30% of 70%-97% nitrogen, argon gas
2as oxygenant; Or with CuO or MnO
2, or KMnO
4as oxygenant, add-on presses the 0.1%-1.5% of Copper and its alloy liquation.
According to above-mentioned method, it is characterized in that, in described step (2), during using Ti, P, Be as control of deleterious element, one or more in employing metal M g, Cr, Zr are as reductive agent deoxidation; Need the Copper and its alloy preventing " hydrogen is sick ", remove oxygen with the magnesium oxide slag making that Mg or B generates fusing point 2800 DEG C as reductor.
According to above-mentioned method, it is characterized in that, in described step (3), for the low zinc alpha brass containing Pb, Bi, add Zr, make harmful elements Pb, Bi generate Pb
xzr
y, Bi
xzr
y; For containing Sb at brass, adding Li and forming Li
3sb; For the copper-nickel alloy containing Ni, when melting high Alpaka, eliminated the detrimentally affect of carbon by the manganese adding trace.
Beneficial effect of the present invention: use outstanding advantages of the present invention to be, inferior cheap raw material can be utilized, or utilize impurity, the outer raw material such as harmful element exceeds standard, on existing channel induction furnace, coreless induction furnace or shaft furnace, carry out simple low-level oxidation-micro-reduction-harmless treatment, get final product the product of production high-quality.Do not need to increase special large-scale oxidation-reduction equipment, do not have a negative impact, have processing efficiency high to the life-span of existing installation furnace lining, treatment process is simple, the advantage that processing cost is cheap.
Embodiment
Method of the present invention comprises three operational phases such as low-level oxidation stage, micro-reduction phase and detrimental impurity harmless treatment stage:
First stage: low-level oxidation stage
Oxidation stage is with inferior cheap raw material, or impurity, harmful element exceed standard etc. outer raw material be raw material, core induction melting furnace or coreless induction smelting furnace or shaft furnace is had to carry out melting and alloying existing, or the Copper and its alloy liquid obtained with traditional Copper and its alloy melting method is for raw material, or the Copper and its alloy liquid obtained with temperature control-pressure regulation melting method is for raw material, have in core induction melting furnace or coreless induction smelting furnace or shaft furnace or reverberatory furnace existing, carry out low-level oxidation slag making reaction.Before reaction, need according to the content of detrimental impurity element, chemical property, selective oxidation agent and oxygenant add technique (comprise oxygenant feed postition, add temperature, oxidization time).Subsequently, copper liquid is adjusted to oxidizing process temperature, adds oxygenant medium ,-slag making reaction is oxidized to detrimental impurity element.The selection principle of oxygenant is: the least possible oxide alloy matrix and useful alloying element, and to the alloy substrate be oxidized and useful alloying element, oxidation products is wanted be dissolved in aluminium alloy in principle, facilitates follow-up micro-reduction process reduction to reclaim.To the detrimental impurity element for removing, being suspended in aluminium alloy with the form of oxidation sludge in principle, being beneficial to follow-up micro-refining process refining and removing.For guaranteeing oxidation removal effect, according to the equilibrium conditions of oxidizing reaction, can repeatedly be oxidized-slag making reaction.Multiple detrimental impurity element can remove by step-by-step oxidation, also can merge oxidation step and remove.
General impurity, harmful element, as Si, Sn, Al, Zn, Ni, Fe, As, Sb, Bi, Se, Te etc. can remove with oxygen oxidative slagging.The mode of allocating into of oxygen can use the O of nitrogen+(3-30) %
2, or the O of argon gas+(3-30) %
2, or the O of nitrogen+argon gas+(3-30) %
2as oxygenant.Also CuO or MnO can be used
2, or KMnO
4as oxygenant, the add-on of the latter is pressed 0.1%-1.5% and is controlled.Be after oxidizing medium passes into melt with oxygen, oxygen is by dissolving and impurity, the harmful element generation oxidizing reaction in melt; Or copper is oxidized to Red copper oxide, by the Red copper oxide be dissolved in copper liquid and impurity, harmful element be oxidized-slag making reacts.
2Cu+[0]→[Cu
20]
2 [Al]+3 [0] → Al
20
3(Gu), 3 [Cu
20]+2 [Al] → Al
20
3(Gu)+6 [Cu]
[Si]+[0] → Si0
2(Gu), 2 [Cu
20]+[Si] → Si0
2(Gu)+4 [Cu]
[Sn]+2 [0] → Sn0
2(Gu), 2 [Cu
20]+[Sn] → Sn0
2(Gu)+2 [Cu]
[Zn]+[0] → Zn0 (Gu), [Cu
20]+[Zn] → Zn0 (Gu)+2 [Cu]
[Ni]+[0]→[Ni0], [Cu
20]+[Ni]→[Ni0]+2[Cu]
2 [As]+3 [0] → As
20
3(Gu), 3 [Cu
20]+2 [As] → As
20
3(Gu)+4 [Cu]
2Sb+ [0] → Sb
20
3(Gu), 3 [Cu
20]+2Sb → Sb
20
3(Gu)+6 [Cu]
2Bi+3 [0] → Bi
20
3(Gu), 5 [Cu
20]+2Bi → Bi
20
3(Gu)+5 [Cu]
Pb+ [0] → Pb0 (Gu), [Cu
20]+Pb → Pb0 (Gu)+2 [Cu]
Te+2 [0] → Te0
2(Gu), 2 [Cu
20]+Te → Te0
2(Gu)+4 [Cu]
Se+2 [0] → Se0
2(Gu), 2 [Cu
20]+Se → Se0
2(Gu)+4 [Cu]
With CuO or MnO
2, or KMnO
4when adding copper liquid as oxygenant, first there is decomposition reaction in oxygenant, discharges oxygen or Red copper oxide, reacted by oxygen or Red copper oxide and impurity, harmful element generation oxidative slagging.Suboxide MnO, K of generating
2o is removed by slag making and follow-up micro-purifying treatment.
2MnO
2→MnO+2[O]
KMnO
4→4MnO+K
2O+2[O]
CuO→[Cu
2O]+2[O]
With electrolytic copper, electrolytic nickel that sulphide ores is produced, be easy to the phenomenon occurring that harmful element sulphur exceeds standard, Copper and its alloy pickling returns are often with sulfuric acid and copper sulfate raffinate, and copper, nickel electrowinning system tramline, the returns such as long-pending sheet that begin, often with vitriol, can cause sulphur in alloy to exceed standard during use.Copper and its alloy fusion process is often using charcoal as insulating covering agent, and some charcoal sulphur content is higher, and alloy sulphur can be caused during use to exceed standard.The impurity exceeded standard, harmful element sulphur can remove with Mg or boronation magnesia-slag making, simultaneously Footwall drift copper, nickel;
[Cu
2S]+[Mg]→MgS+2[Cu]
[Cu
2S]+[Mg]+4[Cu
2O]→MgSO
4+8[Cu]
[NiS]+[Mg]→MgS+2[Ni]
[NiS]+[Mg]+4[Cu
2O]→MgSO
4+8Cu+[Ni]
5[Cu
2S]+2Mg
3B
2+27[Cu
2O]→MgB
4O
7+5MgSO
4+64[Cu]
5[NiS]+2Mg
3B
2+4[Cu
2O]→MgB
4O
7+5MgSO
4+8Cu+5[Ni]
The feature in low-level oxidation stage is, selects effective oxygenant and feed postition, by slight oxidizing reaction, by impurity, harmful element in alloy, causes limited slag inclusion, slag.When imurity-removal, harmful element, channel can not be caused to block and the blowing-ouf of lines.
Subordinate phase: micro-reduction phase
In the low-level oxidation stage, alloy part matrix element and have valency alloying element to participate in oxidising process, generates oxide compound or ion, is dissolved in aluminium alloy.As, copper is with Cu
2o, nickel are with [Ni]
2+form be dissolved in copper liquid.The object of micro-reduction process is the valuable metal be oxidized in reduction low-level oxidation process, improves the casting yield of metal.Oxygen in copper alloy matrix, with (Cu+Cu
2o) formal distribution of eutectic is in crystal boundary, has a negative impact to the working plasticity of copper and alloy.When aerobic copper heats or works under reducing atmosphere, there will be the phenomenon producing blank cracking because of deoxidation.After low-level oxidation end of processing, need according to alloy characteristic and quality product requirement, determine whether carry out deoxidation-reduction process.
Oxygen in Copper and its alloy with Cu
2the form of O is dissolved in copper liquid, is easy to and Ti, P, Be, Ca, Si, Li, K, B, Al isoreactivity metal reaction, generates dystectic oxide inclusions and remove.React the Vanadium Pentoxide in FLAKES, beryllium and the oxygen that generate fusing point 563 DEG C and react the beryllium oxide, calcium and the oxygen that generate fusing point 2530 DEG C as titanium and oxygen react the titanium oxide, phosphorus and the oxygen that generate fusing point 1825 DEG C and react the calcium oxide, silicon and the oxygen that generate fusing point 2572 DEG C and react the silicon oxide, lithium and the oxygen that generate fusing point 1710 DEG C and react the Lithium Oxide 98min, aluminium and the oxygen that generate fusing point 1700 DEG C and react the aluminum oxide generating fusing point 2050 DEG C, these dystectic oxide compounds can be removed by slag making; Oxygen free copper, industrial pure copper and some copper alloy require higher to specific conductivity, during using Ti, P, Be as control of deleterious element, metal M g, Cr, Zr can be used as reductive agent deoxidation; Need the Copper and its alloy preventing " hydrogen is sick ", oxygen can be removed with the magnesium oxide slag making that Mg or B generates fusing point 2800 DEG C as reductor.Also can with boronation magnesium, carbide of calcium, carbon dust, the deoxidation of boron slag.
The essence of micro-reduction phase is exactly be selected in suitable reductor, removes the oxygen in aluminium alloy, and the valuable metal of reduction, the oxidation of recovery oxidising process, by the metallic reducing in oxide compound, improves the casting yield of metal.The oxide slag inclusion caused after deoxidation still retains in copper liquid, can be removed by follow-up micro-purifying treatment.
5[Cu
2O]+2P→10[Cu]+P
2O
5
2 [Cu
2o]+Ti → 4 [Cu]+TiO
2(Gu)
[ZnO]+K → [Zn]+K
2o(is solid)
[NiO]+Mg → [Ni]+MgO(is solid)
6 [Cu
2o]+Mg
3b
2→ 3MgO(is solid)+B
2o
3+ 12 [Cu]
3[NiO]+CaC
2→CaO+2CO
2+3[Ni]
2[NiO]+C→CO
2+2[Ni]
[Cu
2O]+Na
2B
4O
6·MgO→Na
2B
4O
7·MgO +2[Cu]
The feature of micro-reduction phase is, selects effective reductive agent and feed postition, by slight reduction reaction, removes the oxygen that oxidising process is brought into, and the metal of reduction, the oxidation of recovery oxidising process, improves the casting yield of metal.The limited high-melting-point slag inclusion that deoxidation process causes, is removed by micro-purifying treatment.
By low-level oxidation, micro-reduction treatment, the impurity in alloy, harmful element are with dystectic soild oxide slag inclusion, or the slag form of low melting point, are suspended in alloy melt.By carrier gas conveying refining agent, micro-purifying treatment is carried out to copper liquid, the oxide inclusions in alloy, slag can be removed.
Phase III: detrimental impurity element harmless treatment stage
The performance of different impurity, harmful element alloy produces different harm and impact, though impurity, harmful element can be removed from alloy by low-level oxidation-micro-reduction means, but low-level oxidation, micro-reduction process can consume certain oxidizing medium, reducing medium, increase operation link, certain cost occur.
According to the metallurgical chemistry characteristic of impurity, harmful element, select the chemical element of one or several cheapnesss, join in alloy substrate, make it to react with the impurity in alloy, harmful element generation metallurgical chemistry, generate a kind of pattern, distribution, the diverse cenotype of physics-chem characteristic.By change impurity, harmful element in the alloy there is pattern, distribution, physics-chem characteristic, eliminate impurity, harmful element alloy harmful effect, realize the harmless treatment of impurity, harmful element.
Impurity element As significantly reduces conduction, the heat conductivility of copper, and impurity element S b reduces the corrosion stability of copper, specific conductivity and thermal conductivity, and impurity element Bi is dissolved in copper hardly, and in copper, bismuth be that film like is distributed in crystal boundary, the processing characteristics of serious reduction copper.Low-level oxidation-micro-reduction means imurity-removal harmful element As, Sb, Bi can be passed through, also can remove a part of As, Sb, Bi by low-level oxidation approach, in aluminium alloy, retain certain density Cu
2o, utilizes Cu
2o and detrimental impurity elements A s, Sb, Bi react, and form dystectic spherical particle, are distributed in intra-die.The Copper and its alloy of Bi content overproof, can also add Li, Ca of trace in alloy, utilizes the impurity B i in Li, Ca of trace and copper to react, generates dystectic compound, be distributed in crystal grain in tiny, disperse state, eliminate the disadvantageous effect of Bi.
Utilize As, Sb, Bi in the lithium of the oxygen of trace, trace, the calcium of trace and alloy that metallurgical chemistry occurs to react, change impurity, harmful element As, Sb, Bi pattern in copper and alloy, distribution, eliminate the detrimentally affect of As, Sb, Bi alloy corrosion stability, specific conductivity, thermal conductivity and plasticity, realize the harmless treatment of detrimental impurity.
Oxygen is solid-solution in copper hardly, in copper alloy matrix, with (Cu+Cu
2o) formal distribution of eutectic is in crystal boundary, has a negative impact to the working plasticity of copper and alloy.When aerobic copper heats or works under reducing atmosphere, there will be and produce work brittleness and cracking phenomena because of deoxidation.In oxygen-bearing copper, add As, Sb of trace, utilize the Cu in As, Sb and copper
2o reacts, and generates dystectic cupric arsenate, the copper point of metaantimmonic acid is distributed in intracrystalline, eliminates Copper and its alloy crystal boundary Cu+Cu
2o eutectic, can eliminate the disadvantageous effect of oxygen to Copper and its alloy, eliminates copper " hydrogen embrittlement " phenomenon under reducing atmosphere, improves the plasticity of copper.
Pb, Bi are detrimental impurity in simple brass, and in alpha brass, namely lead content is greater than 0.03% can make alloy occur fragility when hot-work, and Bi is distributed in crystal boundary in continuous print brittle diaphragm in brass, makes brass occur fragility when cold and hot working.Add Zr to containing in the low zinc alpha brass of Pb, Bi, harmful elements Pb, Bi can be made to generate high melting compound Pb
xzr
y(fusing point 2000 DEG C), Bi
xzr
y(fusing point 2200 DEG C), eliminates the harm of Pb, Bi.As, to containing the Zr adding 0.22% in the H70 brass of 0.14%Pb, the red brittleness of alloy can be eliminated.Sb when content reaches 0.1% in brass, makes the cold-forming property of alloy significantly decline, and Sb also makes alloy produce red brittleness, and the Li adding trace in alloy can form tiny, disperse, particulate state, dystectic Li
3sb(fusing point 1145 DEG C) be distributed in intracrystalline, eliminate the disadvantageous effect of Sb.
White brass alloy is nickeliferous, and temperature of fusion is higher, and White brass alloy is insulating covering agent with charcoal in fusing often, and carbon can be solid-solution in nickel, and along with the rising of temperature, solid solubility increases.Carbon is harmful element to White brass alloy, and the carbon content in alloy is generally no more than 0.05%.When melting high Alpaka, eliminated the detrimentally affect of carbon by the manganese adding trace.
Use low-level oxidation of the present invention-micro-reduction and micro impurity element method for innocent treatment, when the copper raw material that process impurity, harmful element exceed standard, treating processes does not need to carry out the reduction reaction of strong oxidizing reaction-strong in reverberatory furnace or blast furnace, and not needing additionally increases special large-scale oxidation-reduction equipment.Can utilize existingly has the smelting equipments such as core induction melting furnace, coreless induction smelting furnace, shaft furnace, when production operation, carries out simple low-level oxidation, micro-reduction and harmless treatment, can produce the copper alloy products of high-quality.Treatment process is simple, and processing cost is cheap, and treating processes neither loses valuable metal, does not have a negative impact again to the life-span of furnace lining.The method can simplify the treating processes of low-grade raw material, enhances productivity, and by removing harmful element or carrying out harmless treatment to harmful element, improves the added value of product of low-grade raw material.
Embodiment 1
With the copper raw material that exceeds standard that Pb content is 0.30%, melting HNi65-5 brass alloys.
Having in core induction melting furnace, by the copper raw material of Pb content overproof, the Cu being 65% according to mass percent is placed with in core stove and melts, temperature of fusion 1150-1180 DEG C.Treat that copper material melts, with the O of nitrogen+8%
2as oxygenant, in copper liquid, pass into oxygen, lead to when oxygen blows it should be noted that limit, to angle, do not stay blowing dead band, blind area, duration of blast was advisable with 3-5 minute.Converting process terminates, and alloy melt is left standstill 10-15 minute, makes the Red copper oxide in copper liquid and Pb that oxidizing reaction occur, and generates plumbous oxide.Oxygen in sampling analysis alloy and lead content, treat that lead content meets the requirement of HNi65-5 alloying ingredient, then according to analytical results, in copper liquid, add Al as reductor, reduction, the Red copper oxide reclaimed in copper liquid.Do carrier gas with argon gas, using the mixture of sodium aluminum fluoride, aluminum fluoride, calcium carbonate as refining deslagging agent, refining removes plumbous oxide, aluminum oxide slag.Sampling analysis, treat that lead in copper liquid, aluminium, oxygen level reach the requirement of HNi65-5 alloying ingredient, copper liquid temperature is adjusted to 1130-1180 DEG C, the nickel that mass percent is 5.5% is added in copper liquid, treat that metallic nickel fusing terminates, in the copper-nickel alloy liquid of fusing, add the Zn that mass percent is 32 %, after copper, nickel, the complete alloying of zinc, according to processing requirement, carry out refining, except Slag treatment.
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 66.5%, the nickel of 6.3%, the Pb of 0.013%, surplus is zinc.
Embodiment 2
With the copper raw material that exceeds standard that Al content is 0.15%, melting QSn6.5-0.1 bell metal.
Having in core induction melting furnace, by the copper raw material of Al content overproof, the Cu being 93.5% according to mass percent is placed with in core stove and melts, temperature of fusion 1150-1180 DEG C.Treat that copper material melts, with the O of nitrogen+9%
2as oxygenant, in copper liquid, pass into oxygen, duration of blast was advisable with 2-5 minute.Converting process terminates, and alloy melt is left standstill 10-15 minute, makes the Red copper oxide in copper liquid and Al that oxidizing reaction occur, and generates aluminum oxide.Oxygen in sampling analysis alloy and aluminium content, treat that aluminium content meets the requirement of QSn6.5-0.1 bell metal.Again according to analytical results, in copper liquid, add the phosphorus of 0.1% as reductor, reduction, the Red copper oxide reclaimed in copper liquid.Do carrier gas with argon gas, using the mixture of sodium aluminum fluoride, aluminum fluoride, Sodium Fluoride as refining deslagging agent, refining removes aluminum oxide slag.Sampling analysis, treat aluminium in copper liquid, oxygen level reaches the requirement of QSn6.5-0.1 alloying ingredient, copper liquid temperature is adjusted to 1180-1230 DEG C, in copper liquid, add the nickel that mass percent is 0.15%, treat that metallic nickel fusing terminates, in copper liquid, add the zinc of 0.25%, the tin of 6.5%, the phosphorus that mass percent is 0.20 % is added in copper-tin alloy liquid subsequently to fusing, after copper, tin, nickel, zinc, the complete alloying of phosphorus, according to processing requirement, carry out refining, except Slag treatment.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1180-1230 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Sn of 6.53%, the P of 0.23%, the Ni of 0.18%, the Zn of 0.26%, the Fe of 0.04%, the Pb of 0.01%, the Al of 0.001%, surplus is copper.
Embodiment 3
With the copper raw material that exceeds standard that Fe content is 0.35%, melting H65 brass alloys.
Having in core induction melting furnace, by the copper raw material of Fe content overproof, the Cu being 65% according to mass percent is placed with in core stove and melts, temperature of fusion 1150-1180 DEG C.Treat that copper material melts, in copper liquid, evenly add CuO, add-on is 0.10%, with nitrogen as agitated medium, in copper liquid, passes into nitrogen, and the Red copper oxide of generation is spread rapidly in copper liquid, and duration of blast was advisable with 2-4 minute.Converting process terminates, and alloy melt is left standstill 10-15 minute, makes the Red copper oxide in copper liquid and Fe that oxidizing reaction occur, and generates ferric oxide.Oxygen in sampling analysis alloy and iron level, treat that iron level meets the requirement of H65 brass alloys.Again according to analytical results, in copper liquid, add the phosphorus of 0.1% as reductor, reduction, the Red copper oxide reclaimed in copper liquid.Do carrier gas with argon gas, using the mixture of fluorite, borax, calcium carbonate as refining deslagging agent, refining removes the gred.
Sampling analysis, treat Fe in copper liquid, oxygen level reaches the requirement of H65 alloying ingredient, copper liquid temperature is adjusted to 1150-1180 DEG C, the nickel that mass percent is 0.45% is added in copper liquid, treat that metallic nickel fusing terminates, in copper liquid, add the zinc of 35%, after copper, nickel, the complete alloying of zinc, according to processing requirement, carry out refining, except Slag treatment.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1040-1060 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Cu of 64.9%, the Ni of 0.48%, the Fe of 0.06%, the Pb of 0.011%, surplus is zinc.
Embodiment 4
With the old material of the copper-nickel alloy that exceeds standard that C content is 0.16%, melting BFe30-1-1 White brass alloy.
In coreless induction smelting furnace, the old material of the copper-nickel alloy that C content is exceeded standard, according to batching total amount 70% furnace charge amount put into coreless furnace and melt, temperature of fusion 1300-1350 DEG C.Treat the old material fusing of copper-nickel alloy, nickel, copper, iron, the manganese of the food ingredient of remaining 30% is added in copper liquid, treat the complete alloying of nickel, copper, iron, manganese, sampling analysis alloying constituent, again according to analytical results, in copper liquid, add the Mg of 0.3%, utilize MAGNESIUM METAL to eliminate the harmful effect of impurity element carbon, according to processing requirement, carry out refining, except Slag treatment.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1300-1330 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Ni of 29.6%, the Mn of 1.1%, the Fe of 0.96%, carbon has carried out harmless treatment, and surplus is copper.
Embodiment 5
With the copper raw material that exceeds standard that Pb content is 0.19%, melting H70 brass alloys.
Having in core induction melting furnace, by the copper raw material of Pb content overproof, the Cu being 70% according to mass percent is placed with in core stove and melts, temperature of fusion 1150-1180 DEG C, treat that copper raw material melts, in copper liquid, add the zinc of 31%, treat the complete alloying of copper, zinc, copper liquid temperature is adjusted to 1100-1130 DEG C, sampling analysis alloying constituent, again according to analytical results, add the Zr of 0.23% in copper liquid, utilizing metallic Z r and Pb to generate fusing point is the Pb of 2000 DEG C
xzr
ychange plumbous in the alloy there is pattern and distribution, reach the object of harmful effect eliminating impurity, harmful element lead, according to processing requirement, carry out refining, except Slag treatment.
Sampling analysis, after alloying constituent conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1100-1130 DEG C, comes out of the stove.
Copper alloy composition prepared is in this way (mass percent): the Cu of 70.3%, the Ni of 0.35%, the Fe of 0.04%, lead has carried out harmless treatment, and surplus is zinc.
Embodiment 6
With the copper raw material that exceeds standard that Bi content is 0.019%, melting T2 forges red copper.
Having in core induction melting furnace, the copper raw material of Bi content overproof is placed with in core stove and melts, temperature of fusion 1150-1180 DEG C, treat that copper raw material melts, copper liquid temperature is adjusted to 1160-1180 DEG C, sampling analysis copper liquid composition, again according to analytical results, in copper liquid, add the Li of 0.3%, utilize the Li of trace and impurity B i to react, generate dystectic compound, be distributed in crystal grain in tiny, disperse state, eliminate the disadvantageous effect of Bi, reach the object of harmful effect eliminating impurity, harmful element bismuth, according to processing requirement, carry out refining, except Slag treatment.
Sampling analysis, after copper liquid composition conformance with standard requires, by the temperature adjustment of copper liquid to casting temp 1160-1180 DEG C, comes out of the stove.
It is (mass percent) that T2 prepared in this way forges red copper copper component: the Cu of 99.93%, Bi have carried out harmless treatment.
Claims (4)
1. the impurity-removing method in Copper and its alloy fusion process, is characterized in that, said method comprising the steps of:
(1) the low-level oxidation stage: pass into oxygen in the Copper and its alloy liquation had in core induction melting furnace or coreless induction smelting furnace or shaft furnace or reverberatory furnace, or add CuO, MnO
2, KMnO
4in one or more as oxygenant, carry out slag making reaction;
(2) micro-reduction phase: use metal M g, one or more in Cr, Zr, B as reductive agent, reduction, reclaims the valuable metal of oxidising process oxidation;
(3) the detrimental impurity element harmless treatment stage: add in Li, Ca, Zr, Mn one or more go out detrimental impurity.
2. method according to claim 1, it is characterized in that, in described step (1), for Si, Sn, Al, Zn, Ni, Fe, As, Sb, Bi, Se, Te impurity, with oxygen as oxygenant, the mode of allocating into of oxygen is the O of the nitrogen+3%-30% of volume accounting 70%-97%
2, or the O of argon gas+3%-30% of volume accounting 70%-97%
2, or volume account for the O of mixed gas+3%-30% of 70%-97% nitrogen, argon gas
2as oxygenant; Or with CuO or MnO
2, or KMnO
4as oxygenant, add-on presses the 0.1%-1.5% of Copper and its alloy liquation.
3. method according to claim 1, is characterized in that, in described step (2), during using Ti, P, Be as control of deleterious element, one or more in employing metal M g, Cr, Zr are as reductive agent deoxidation; Need the Copper and its alloy preventing " hydrogen is sick ", remove oxygen with the magnesium oxide slag making that Mg or B generates fusing point 2800 DEG C as reductor.
4. method according to claim 1, is characterized in that, in described step (3), for the low zinc alpha brass containing Pb, Bi, adds Zr, makes harmful elements Pb, Bi generate Pb
xzr
y, Bi
xzr
y; For containing Sb at brass, adding Li and forming Li
3sb; For the copper-nickel alloy containing Ni, when melting high Alpaka, eliminated the detrimentally affect of carbon by the manganese adding trace.
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| CN106244839A (en) * | 2016-09-27 | 2016-12-21 | 绵阳铜鑫铜业有限公司 | A kind of copper deoxidizer |
| CN107058777A (en) * | 2017-04-18 | 2017-08-18 | 中南大学 | It is a kind of to remove Bi, Pb refining agent and preparation method thereof in waste and old Bi brass |
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| CN105586555A (en) * | 2016-01-04 | 2016-05-18 | 厦门火炬特种金属材料有限公司 | Reduction medium for bright annealing of Cu-Mn-Ni series precision resistance alloy strip and annealing method thereof |
| CN106167861A (en) * | 2016-08-09 | 2016-11-30 | 洛阳名力科技开发有限公司 | A kind of copper alloy for electronic material |
| CN106191503A (en) * | 2016-08-30 | 2016-12-07 | 江西理工大学 | A kind of reduce the method for bi content in pyrite |
| CN106191503B (en) * | 2016-08-30 | 2017-09-19 | 江西理工大学 | A kind of method of bi content in reduction brass |
| CN106244839A (en) * | 2016-09-27 | 2016-12-21 | 绵阳铜鑫铜业有限公司 | A kind of copper deoxidizer |
| CN107058777A (en) * | 2017-04-18 | 2017-08-18 | 中南大学 | It is a kind of to remove Bi, Pb refining agent and preparation method thereof in waste and old Bi brass |
| CN110117725A (en) * | 2019-05-17 | 2019-08-13 | 北京科技大学 | A kind of low temperature pyro-refining method of the useless ash metal of Fast Purification |
| CN110629038A (en) * | 2019-10-28 | 2019-12-31 | 河南科技大学 | Deoxidation and desulfurization method for copper or copper alloy, high-purity copper or copper alloy and preparation method thereof |
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