CN110629038B - Deoxidation and desulfurization method for copper or copper alloy, high-purity copper or copper alloy and preparation method thereof - Google Patents
Deoxidation and desulfurization method for copper or copper alloy, high-purity copper or copper alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a deoxidation and desulfurization method for copper or copper alloy, high-purity copper or copper alloy and a preparation method thereof, belonging to the technical field of copper and copper alloy preparation. The invention provides a deoxidation and desulfurization method for copper or copper alloy, which comprises the following steps: introducing carrier gas carrying a deoxidizing and desulfurizing agent to the bottom of the copper or copper alloy melt; the deoxidizing and desulfurizing agent is calcium hexaboride, or the combination of the calcium hexaboride and one or two of boron and carbon; the carrier gas is an inert gas and/or a reducing gas. The deoxidizing and desulfurizing agent can effectively remove oxygen and sulfur in a melt to form low-density oxides and sulfides which are easy to float, carrier gas is introduced from the bottom of the melt to help carry the deoxidizing and desulfurizing agent to float, the deoxidizing and desulfurizing effect is enhanced, automatic control in the deoxidizing and desulfurizing process is facilitated, the carrier gas not only plays a role in carrying the deoxidizing and desulfurizing agent, but also serves as protective gas to avoid the copper or copper alloy melt from being oxidized, and the deoxidizing and desulfurizing agent has the functions of stirring and carrying the deoxidizing and desulfurizing product to float.
Description
Technical Field
The invention relates to a deoxidation and desulfurization method for copper or copper alloy, high-purity copper or copper alloy and a preparation method thereof, belonging to the technical field of copper and copper alloy preparation.
Background
Oxygen and sulfur are harmful to varying degrees in pure copper and copper alloys. Oxygen is hardly dissolved in copper, and when oxygen-containing copper is solidified, oxygen is precipitated in the form of eutectic and distributed on the grain boundary of copper. When the oxygen content in the cast oxygen-containing copper is extremely low, the Cu content appears along with the increase of the oxygen content2Hypo-, co-and hypereutectic of O. In copper alloys, the influence of oxygen in the presence of other elements is extremely complex, and the mechanical properties, electrical conductivity and other properties of the alloy are affected to different degrees. The solubility of sulfur in room temperature copper is zero, with Cu2Dispersed particles of S exist, and the electrical conductivity and the thermal conductivity of copper are reduced.
At present, copper and copper alloy are generally smelted in an induction furnace, and in order to prevent a melt from being polluted, smelting and refining are generally carried out in a mode of not adopting any additive, but the surface of a molten pool is covered with charcoal and protected in a protective gas atmosphere; however, charcoal is apt to absorb moist air and even directly absorb moisture, and thus it becomes a channel that makes it possible for the copper bath to absorb a large amount of hydrogen, and therefore it is difficult to smelt high-quality copper and copper alloys using an induction furnace. CN107858528A discloses a pure copper smelting method. Preheating a graphite crucible to dark red, adding a layer of dry charcoal or covering agent (60% of borax and 37% of cullet) with the thickness of 30-50 mm at the bottom of the crucible, sequentially adding leftover materials, waste blocks and bar materials, and finally adding pure copper; adding the preheated supplemented alloy elements into a crucible, heating to completely melt the alloy elements, adding phosphorus copper accounting for 0.3-0.4% of the mass of the alloy liquid to deoxidize when the temperature is raised to 1200-1220 ℃, removing slag after full reaction, and casting to obtain pure copper. CN101104889A discloses a method for smelting pure copper or high copper-containing alloy raw materials. The method uses N in the alloy smelting process2And H2、CO、C2H2The mixed gas (containing nitrogen gas of 95% or more) is used as a protective gas to inhibit the oxidation of the copper alloy melt. CN106086444B discloses a method for preparing a high-purity oxygen-free copper rod by an up-drawing method. The methodThe method comprises the steps of firstly adding electrolytic copper into a smelting furnace to be melted to obtain copper liquid, adding premelted molten salt (in percentage by weight, 60-65% of sodium borate, 10-15% of sodium fluosilicate, 10-15% of cryolite, 5-10% of calcium fluoride, 1-5% of titanium dioxide and 5-10% of sodium chloride), continuously introducing high-purity nitrogen into the copper liquid, then adding a deoxidizer consisting of a Cu-Re alloy and lithium oxide into the copper liquid at 1190-1210 ℃, stirring the deoxidizer in a medium-frequency electromagnetic field until the deoxidizer is uniformly distributed, and preserving heat for 10-30 min to obtain a high-purity copper melt.
The pure copper and copper alloy melt obtained by the process has high oxygen content, and no specific measures are provided for desulfurization in the copper and copper alloy smelting process.
Disclosure of Invention
The invention provides a deoxidation and desulfurization method for copper or copper alloy, which has high efficiency and simple operation and can effectively reduce the oxygen content and the sulfur content in the copper or copper alloy.
The invention provides a preparation method of high-purity copper or copper alloy.
The invention provides high-purity copper or copper alloy.
The technical scheme of the invention is as follows:
a deoxidation and desulphurization method for copper or copper alloy is characterized by comprising the following steps:
introducing carrier gas carrying a deoxidizing and desulfurizing agent to the bottom of the copper or copper alloy melt; the deoxidizing and desulfurizing agent is calcium hexaboride, or the combination of the calcium hexaboride and one or two of boron and carbon; the carrier gas is an inert gas and/or a reducing gas.
The copper alloy can be various copper alloys conventional in the field, for example, a Cu-Ni-Al alloy, wherein the mass fraction of Ni is 12.0-15.0%, the mass fraction of Al is 2.3-3.0%, and the balance is copper; or Cu-Zn-Al alloy, wherein the mass fraction of Cu is 66.0-68.0%, the mass fraction of Al is 2.0-3.0%, and the balance is zinc; the alloy can also be Cu-Al alloy, wherein the mass fraction of Al is 4.0-6.0%, and the balance is copper.
The deoxidation and desulfurization method of the copper or the copper alloy has the advantages that the carrier gas carrying the deoxidation and desulfurization agent is introduced to the bottom of the melt of the copper or the copper alloy to carry out deoxidation and desulfurization, the efficiency is high, and the operation is simple. The method has the advantages that the deoxidizing and desulfurizing agent can effectively remove oxygen and sulfur in the melt to form low-density oxides and sulfides which are easy to float upwards, the upward floating of the deoxidizing and desulfurizing agent is facilitated by introducing carrier gas carrying the deoxidizing and desulfurizing agent from the bottom of the melt, the utilization rate of the deoxidizing and desulfurizing agent is improved, the deoxidizing and desulfurizing effect is enhanced, the automatic control of the deoxidizing and desulfurizing process is facilitated, the carrier gas not only plays a role in carrying the deoxidizing and desulfurizing agent, but also serves as protective gas to prevent the copper or copper alloy melt from being oxidized, and the stirring and carrying effects of upward floating of deoxidizing and desulfurizing products are achieved, so that the deoxidizing and desulfurizing are thorough.
Preferably, the upper surface of the melt is covered with a covering agent. The covering agent has the function of isolating oxygen and can prevent the melt of copper or copper alloy from being oxidized.
Preferably, the covering agent mainly comprises the following raw materials in percentage by mass: 60-75% of sodium tetraborate, 10-20% of alkali metal oxide, 5-15% of sodium fluoroaluminate and 5-15% of sodium fluoride; the alkali metal oxide is sodium oxide and/or potassium oxide. The covering agent can absorb deoxidation and desulfurization products, improve deoxidation and desulfurization efficiency and effectively prevent melt from being oxidized.
Preferably, the covering agent mainly comprises the following raw materials in percentage by mass: 60-75% of sodium tetraborate, 15-20% of alkali metal oxide, 5-10% of sodium fluoroaluminate and 5-10% of sodium fluoride; the alkali metal oxide is sodium oxide and/or potassium oxide. The covering agent can absorb deoxidation and desulfurization products, further improve the deoxidation and desulfurization efficiency and effectively prevent the melt from being oxidized.
Preferably, the melt with the upper surface covered with the covering agent is prepared by a method comprising the following steps: and adding a covering agent into the metal material of the copper or the copper alloy in the atmosphere of inert gas and/or reducing gas, and heating to melt the metal material and the covering agent to obtain the copper-copper alloy. The atmosphere of inert gas and/or reducing gas can prevent the copper or copper alloy from being oxidized in the melting process, and after the metal material of the copper or copper alloy and the covering agent are melted, the covering agent is positioned on the surface of the copper or copper alloy melt, so that the copper or copper alloy melt can be further prevented from being oxidized.
It should be noted that the metal material of copper or copper alloy is dried by pretreatment, and the pretreatment drying process is to preheat and dry the copper or copper alloy at 300-550 ℃. The covering agent is mixed and dried, and the mixture can be mixed by ball milling for 3-6 h on a ball mill, and then dried for 5-15 h at 180-300 ℃ to remove water.
It can be understood that the atmosphere of the protective gas can be realized by introducing the protective gas into the reaction device, and the flow rate of the protective gas is 0.6-2 m3The preferred time is 5-10 min.
Preferably, the weight of the covering agent is 0.5-1.2% of the weight of the metal material. The covering agent accounts for 0.5 to 1.2 percent of the weight of the metal material, can effectively give consideration to the cost and the oxygen isolation effect, and can effectively adsorb the deoxidation and desulfurization products.
Preferably, the weight of the covering agent is 0.8-1% of the weight of the metal material. Better considers the cost and the oxygen isolation effect and effectively adsorbs the deoxidation desulfurization products.
Preferably, the deoxidizing and desulfurizing agent is calcium hexaboride, or a combination of 75wt% -95 wt% of calcium hexaboride and 5wt% -25 wt% of boron, or a combination of 75wt% -95 wt% of calcium hexaboride and 5wt% -25 wt% of carbon, or a combination of 35wt% -45 wt% of calcium hexaboride, 40wt% -60 wt% of boron and 5wt% -15 wt% of carbon.
The calcium hexaboride, the deoxidizing and desulfurizing agent consisting of the calcium hexaboride and boron, the deoxidizing and desulfurizing agent consisting of the calcium hexaboride and carbon or the deoxidizing and desulfurizing agent consisting of the calcium hexaboride, the boron and the carbon can effectively and deeply remove oxygen and sulfur in copper or copper alloy melt, and form low-density oxides and sulfides.
Preferably, the weight of the deoxidizing and desulfurizing agent is 0.1-0.8% of the weight of the melt. Can effectively give consideration to the cost and the deoxidation and desulfurization effects.
Preferably, the weight of the deoxidizing and desulfurizing agent is 0.5-0.7% of the weight of the melt. Can more effectively give consideration to the cost and the deoxidation and desulfurization effects.
Preferably, the carrier gas is a reducing gas; the reducing gas is one or more than two of carbon monoxide, hydrogen, acetylene or methane. The reducing gas is used as carrier gas to carry the deoxidizing and desulfurizing agent to enter the melt from the bottom of the melt, is used as protective gas to prevent the copper or copper alloy melt from being oxidized, has the functions of stirring and carrying the deoxidizing and desulfurizing product to float, can also be used as a deoxidizing agent, and can effectively remove oxygen in the melt. One or more than two of carbon monoxide, hydrogen, acetylene or methane are used as carrier gas, which is beneficial to removing oxygen in the melt, and simultaneously, the carrier gas also is used as carrier gas to carry the deoxidizing and desulfurizing agent to enter the melt from the bottom of the melt, thereby avoiding the copper or copper alloy melt from being oxidized, and having the functions of stirring and carrying the deoxidizing and desulfurizing product to float.
Preferably, the pressure of the carrier gas is 0.5-2 MPa. The protective gas with the pressure of 0.5-2 MPa has a good stirring effect, and has the effects of carrying the deoxidizing and desulfurizing agent and floating the deoxidizing product.
Preferably, the flow rate of the carrier gas is 3-8 m3H is used as the reference value. The flow rate is 3-8 m3The carrier gas has good stirring effect, and the carrier gas carries the deoxidation and desulfurization agent and the deoxidation and desulfurization product to float upwards.
Preferably, the flow rate of the carrier gas is 4-6 m3H is used as the reference value. The flow of the carrier gas is reasonably adjusted and optimized to be 4-6 m3And/h, the catalyst has good stirring effect and the functions of carrying the deoxidizing and desulfurizing agent and floating the deoxidizing and desulfurizing product while considering the cost.
Preferably, the temperature of the melt is 1200-1280 ℃, and the time for introducing the carrier gas carrying the deoxidizing and desulfurizing agent is 2-8 min. The temperature and time are effective to remove oxygen and sulfur.
Preferably, the temperature of the melt is 1250-1280 ℃, and the time for introducing the carrier gas carrying the deoxidizing and desulfurizing agent is 4-6 min. By reasonably adjusting and optimizing the temperature and time, the deoxidation and desulfurization efficiency is further improved, and the oxygen and sulfur content is reduced.
Preferably, after the introduction of the carrier gas carrying the deoxidizing and desulfurizing agent is finished, the carrier gas continues to flow to the bottom of the copper or copper alloy meltThe flow rate of the gas is 0.6-2 m3The carrier gas is carried for 10-20 min. After the carrier gas carrying the deoxidizing and desulfurizing agent is introduced, the carrier gas is continuously introduced into the melt, so that the carrier gas carrying the deoxidizing and desulfurizing product floats upwards.
Preferably, after the introduction of the carrier gas carrying the deoxidizing and desulfurizing agent is finished, the flow of the carrier gas continuously introduced to the bottom of the copper or copper alloy melt is 0.7-0.9 m3/h。
Preferably, the deoxidation and desulfurization are carried out in an induction furnace, and the frequency of the induction furnace is 1000-2500 Hz. The magnetic field generated in the induction furnace with the frequency of 1000-2500 Hz has a stirring effect, and is beneficial to aggregation, growth and floating of deoxidation products.
A preparation method of high-purity copper or copper alloy comprises the following steps:
and (2) deoxidizing and desulfurizing the melt of the copper or the copper alloy by adopting a deoxidizing and desulfurizing method of the copper or the copper alloy, then cooling to 1150-1200 ℃, casting, and removing slag to obtain the alloy.
The oxygen content and the sulfur content of the melt of the copper or the copper alloy are low and the purity is high after the melt of the copper or the copper alloy is deoxidized and desulfurized by adopting the deoxidizing and desulfurizing method of the copper or the copper alloy.
A high-purity copper or copper alloy is prepared by a preparation method of the high-purity copper or copper alloy.
The copper or copper alloy obtained by the preparation method of the high-purity copper or copper alloy has low oxygen content and sulfur content, high purity, better mechanical property, conductivity and other properties.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Na used in the examples of the present invention2B4O7The purity is more than or equal to 99.98 percent, and the granularity is 100-300 meshes.
The NaF adopted in the embodiment of the invention has the purity of more than or equal to 99.98% and the granularity of 100-300 meshes.
Na used in the examples of the present invention2O、K2The purity of O is more than or equal to 99.98 percent, and the granularity is 100-300 meshes.
Na used in the examples of the present invention3AlF6The purity is more than or equal to 99.98 percent, and the granularity is 100-300 meshes.
CaB adopted in the embodiment of the invention6The granularity of the powder, the boron powder and the carbon powder is less than 300 meshes.
The deoxidation device of the embodiment of the invention is a medium-frequency induction furnace which is provided with a high-purity graphite lining crucible with a bottom blowing air brick. The slit of the air brick is less than or equal to 0.1mm, and the purity of the graphite is more than 99.99 percent.
The mould for casting in the embodiment of the invention is a high-purity graphite casting mould, and the purity of graphite used by the high-purity graphite casting mould is more than 99.99%.
The purity of the carrier gas used in the embodiment of the invention is more than 99.99%.
The first embodiment of the deoxidation and desulfurization method for copper or copper alloy of the invention is as follows:
example 1
The deoxidation and desulfurization method for copper of the embodiment comprises the following steps:
(1) pretreatment of copper metal material and covering agent
The covering agent comprises the following components in percentage by mass: na (Na)2B4O7 60％、Na2O 20％、Na3AlF610% and 10% of NaF. Firstly, mixing Na according to the above proportion2B4O7、NaF、Na3AlF6And Na2And (3) weighing O respectively, putting the weighed O into a mixing tank, then ball-milling the O for 3 hours on a ball mill, and then putting the O into a drying box, and drying the O for 8 hours at 180 ℃ to remove water.
The copper metal material is preheated at 400 ℃ to remove moisture.
(2) Melting of the metal charge and the covering agent
Introducing CO gas from the bottom of the medium-frequency induction furnace, wherein the gas flow is 0.8m3H, the time is 10min, and then the furnace is preheated to 550 ℃; then adding the pretreated copper metal material, and adding a covering agent with the weight of 0.8% of that of the metal material into the upper layer of the metal material; and then heating to completely melt the metal material and the covering agent to obtain a melt with the surface covered with the covering agent.
(3) Deoxidation and desulfurization
Increasing the furnace temperature to 1250 ℃, and increasing the flow of the injected reducing gas to 4m3Blowing solid powdery deoxidizing and desulfurizing agent CaB by taking the solid powdery deoxidizing and desulfurizing agent as carrier gas6And (3) carrying out deoxidation and desulfurization on the powder, wherein the weight of the deoxidation and desulfurization agent is 0.6 percent of the weight of the melt, and the time is 5 min.
(4) Post-treatment
After the removal reaction is finished, reducing gas flow is reduced to 0.8m3H, and keeping the temperature for 15 min. Adjusting the furnace temperature to 1150 ℃, discharging, casting into a high-purity graphite casting mold, and removing slag to obtain a pure copper ingot with the oxygen content of 4.6ppm and the sulfur content of 0.25 ppm.
Example 2
The deoxidation and desulfurization method for copper of the embodiment comprises the following steps:
(1) pretreatment of copper metal material and covering agent
The covering agent comprises the following components in percentage by mass: na (Na)2B4O7 70％、K2O 15％、Na3AlF610% and NaF 5%. Firstly, mixing Na according to the above proportion2B4O7、NaF、Na3AlF6And K2And (3) weighing O respectively, putting the weighed O into a mixing tank, then ball-milling the O for 4 hours on a ball mill, and then putting the O into a drying box, and drying the O for 10 hours at the temperature of 200 ℃ to remove water.
The copper metal material is preheated at 450 ℃ to remove moisture.
(2) Melting of the metal charge and the covering agent
Introducing H from the bottom of the medium-frequency induction furnace2Gas with a gas flow rate of 0.9m3H, the time is 10min, and then the furnace is preheated to 550 ℃; then adding the pretreated copper metal material, and adding a covering agent with the weight of 1.0% of the metal material into the upper layer of the metal material to ensure that the thickness of the molten casting powder reaches 25 mm; and then heating to completely melt the metal material and the covering agent to obtain a melt with the surface covered with the covering agent.
(3) Deoxidation and desulfurization
Increasing the furnace temperature to 1260 ℃, and increasing the flow of the injected reducing gas to 6m3H, and blowing CaB with the carrier gas6And boron powderMixed solid desulfurizing and deoxidizing agent, CaB690 percent of powder by weight percent, and carrying out deoxidation and desulfurization, wherein the weight of the deoxidation and desulfurization agent is 0.5 percent of the weight of the melt, and the time is 6 min.
(4) Post-treatment
After the removal reaction is finished, reducing gas flow is reduced to 0.9m3H, and keeping the temperature for 15 min. And adjusting the furnace temperature to 1180 ℃, discharging, casting into a high-purity graphite casting mold, and removing slag to obtain a pure copper ingot with the oxygen content of 3.5ppm and the sulfur content of 0.32 ppm.
Example 3
The deoxidation and desulfurization method for copper of the embodiment comprises the following steps:
(1) pretreatment of copper metal material and covering agent
The covering agent comprises the following components in percentage by mass: na (Na)2B4O7 75％、Na2O 15％、Na3AlF65% and NaF 5%. Firstly, mixing Na according to the above proportion2B4O7、NaF、Na3AlF6And Na2And (3) weighing O respectively, putting the weighed O into a mixing tank, then ball-milling the O for 5 hours on a ball mill, and then putting the O into a drying box, and drying the O for 12 hours at 250 ℃ to remove water.
The copper metal material is preheated at 550 ℃ to remove moisture.
(2) Melting of the metal charge and the covering agent
Introducing H from the bottom of the medium-frequency induction furnace2(or C)2H2、CH4) Gas with a gas flow rate of 0.8m3H, the time is 8min, and then the furnace is preheated to 650 ℃; then adding the pretreated copper metal material, and adding a covering agent with the weight of 0.8% of that of the metal material into the upper layer of the metal material to ensure that the thickness of the molten casting powder reaches 18 mm; and then heating to completely melt the metal material and the covering agent to obtain a melt with the surface covered with the covering agent.
(3) Deoxidation and desulfurization
Increasing the furnace temperature to 1250 ℃, and increasing the flow of the injected reducing gas to 5m3H, and blowing CaB with the carrier gas6Mixed solid deoxidating and desulfurizing agent CaB comprising carbon powder6The powder accounts for 92 percent by weight, and the deoxidation and desulfurization are carried out, wherein the weight of the deoxidation and desulfurization agent is 0.6 percent of the weight of the melt, and the time is 5 min.
(4) Post-treatment
After the removal reaction is finished, reducing gas flow is reduced to 0.8m3H, and keeping the temperature for 15 min. Adjusting the furnace temperature to 1160 ℃, discharging, casting into a high-purity graphite casting mold, and removing slag to obtain a pure copper ingot with the oxygen content of 3.2ppm and the sulfur content of 0.30 ppm.
Example 4
The deoxidation and desulfurization method for copper of the embodiment comprises the following steps:
(1) pretreatment of copper metal material and covering agent
The covering agent comprises the following components in percentage by mass: na (Na)2B4O7 70％、K2O 20％、Na3AlF65% and NaF 5%. Firstly, mixing Na according to the above proportion2B4O7、NaF、Na3AlF6And K2And (3) weighing O respectively, putting the weighed O into a mixing tank, then ball-milling the O for 4 hours on a ball mill, and then putting the O into a drying box, and drying the O for 12 hours at 250 ℃ to remove water.
The copper metal material is preheated at 550 ℃ to remove moisture.
(2) Melting of the metal charge and the covering agent
Introducing CO gas from the bottom of the medium-frequency induction furnace, wherein the gas flow is 0.7m3H, the time is 6min, and then the furnace is preheated to 600 ℃; then adding a pretreated metal material of pure copper, and adding a covering agent with the weight of 0.9% of that of the metal material into the upper layer of the metal material to ensure that the thickness of the molten casting powder reaches 22 mm; and then heating to completely melt the metal material and the covering agent to obtain a melt with the surface covered with the covering agent.
(3) Deoxidation and desulfurization
Increasing the furnace temperature to 1280 ℃, and increasing the flow of the injected reducing gas to 6m3Blowing mixed solid powdery deoxidizing and desulfurizing agent by taking the solid powdery deoxidizing and desulfurizing agent as a carrier gas, wherein the solid powdery deoxidizing and desulfurizing agent is CaB640 percent of powder, 45 percent of boron powder and 15 percent of carbon powder, and the weight of the deoxidizing and desulfurizing agent is 0.7 percent of the weight of the meltThe time is 7 min.
(4) Post-treatment
After the removal reaction is finished, reducing gas flow is reduced to 0.7m3H, and keeping the temperature for 18 min. And adjusting the furnace temperature to 1180 ℃, discharging, casting into a high-purity graphite casting mold, and removing slag to obtain a pure copper ingot with the oxygen content of 3.8ppm and the sulfur content of 0.41 ppm.
Example 5
The method for deoxidizing and desulfurizing copper of the present embodiment is different from the method of embodiment 4 only in that the deoxidizing and desulfurizing conditions in step (3) are different, specifically:
CO gas was introduced into the melt coated with the covering agent obtained in step (2) of example 1 at a furnace temperature of 1250 ℃ at a gas flow rate of 4m3Blowing solid powdery deoxidizing and desulfurizing agent CaB by taking the solid powdery deoxidizing and desulfurizing agent as carrier gas6And (3) carrying out deoxidation and desulfurization on the powder, wherein the weight of the deoxidation and desulfurization agent is 0.6 percent of the weight of the melt, and the time is 5 min.
After the post-treatment, the oxygen content of the obtained pure copper ingot is 3.5ppm, and the sulfur content is 0.33 ppm.
Example 6
The deoxidation and desulfurization method for copper in the embodiment is different from the embodiment 1 in that the covering agent is different, the rest steps and the method are the same as the embodiment 1, and the covering agent in the embodiment comprises the following components in percentage by mass: na (Na)2B4O7 60％、Na2O 10％、NaF 15％、Na3AlF6 15％。
The obtained pure copper ingot had an oxygen content of 2.6ppm and a sulfur content of 0.37 ppm.
Example 7
The method for deoxidizing and desulfurizing a copper alloy in this example is different from example 1 in that copper is replaced with a Cu — Zn — Al alloy (67.0% by mass of Cu, 2.5% by mass of Al, and the balance Zn), and the steps and method are the same as those in example 1, so that a copper-chromium alloy ingot is obtained, the oxygen content of which is 3.5ppm, and the sulfur content of which is 0.63 ppm.
Example 8
The method for deoxidizing and desulfurizing a copper alloy in this example is different from example 1 in that copper is replaced by Cu — Al (5.0% by mass of Al, and the balance being Cu), and the steps and method are the same as example 1, so that a copper-chromium alloy ingot is obtained, the oxygen content of which is 3.6ppm, and the sulfur content of which is 0.40 ppm.
Example 9
The method for deoxidizing and desulfurizing a copper alloy in this example is different from example 1 in that copper is replaced with a Cu — Ni — Al alloy (Ni is 13.0% by mass, Al is 2.2% by mass, and the balance is Cu), and the steps and method are the same as those in example 1, whereby a copper-chromium alloy ingot having an oxygen content of 2.6ppm and a sulfur content of 0.32ppm is obtained.
Second, examples of the method for producing high purity copper or copper alloy of the present invention correspond to examples 1 to 9 of the method for deoxidizing copper or copper alloy, respectively.
Third, the examples of copper or copper alloy of the present invention correspond to the final products of the deoxidation and desulfurization methods of copper or copper alloy examples 1 to 9, respectively.
Fourth, related test example
Test example 1
The oxygen content and sulfur content before and after the deoxidation and desulfurization of copper or copper alloys were measured in the copper or copper alloys according to the deoxidation and desulfurization method for copper or copper alloys of examples 1 to 9 by analyzing the metal oxide content with a nitrogen/hydrogen/oxygen analyzer and the alloy sulfur content with a carbon/sulfur analyzer. The results obtained are shown in table 1.
TABLE 1 method for deoxidizing and desulfurizing copper or copper alloy of examples 1 to 9
Experimental results show that the deoxidation and desulfurization method for copper or copper alloy in the embodiments 1-9 of the invention has good deoxidation and desulfurization effects, can be used for smelting pure copper and copper alloy with the oxygen content less than 5ppm and the sulfur content less than 1ppm under the non-vacuum condition, and has the advantages of thorough deoxidation and desulfurization, high efficiency, simple operation, easy realization of automation and the like.
Claims (10)
1. A deoxidation and desulphurization method for copper or copper alloy is characterized by comprising the following steps:
introducing carrier gas carrying a deoxidizing and desulfurizing agent to the bottom of the copper or copper alloy melt;
the deoxidizing and desulfurizing agent is calcium hexaboride, or a combination of 75-95 wt% of calcium hexaboride and 5-25 wt% of boron, or a combination of 75-95 wt% of calcium hexaboride and 5-25 wt% of carbon, or a combination of 35-45 wt% of calcium hexaboride, 40-60 wt% of boron and 5-15 wt% of carbon;
the carrier gas is a reducing gas; the reducing gas is one or more than two of carbon monoxide, hydrogen, acetylene or methane;
the upper surface of the melt is covered with a covering agent; the covering agent mainly comprises the following raw materials in percentage by mass: 60-75% of sodium tetraborate, 10-20% of alkali metal oxide, 5-15% of sodium fluoroaluminate and 5-15% of sodium fluoride; the alkali metal oxide is sodium oxide and/or potassium oxide.
2. The deoxidation and desulfurization method for copper or copper alloy according to claim 1, wherein the melt whose upper surface is covered with the covering agent is prepared by a method comprising the steps of:
and adding a covering agent into the metal material of the copper or the copper alloy in the atmosphere of inert gas and/or reducing gas, and heating to melt the metal material and the covering agent to obtain the copper-copper alloy.
3. The method for deoxidation and desulfurization of copper or copper alloys according to claim 2, wherein the weight of said covering agent is 0.5% to 1.2% of the weight of the metal charge.
4. The method for deoxidizing and desulfurizing copper or a copper alloy as set forth in any one of claims 1 to 3, wherein the weight of said deoxidizing and desulfurizing agent is 0.1% to 0.8% of the weight of the melt.
5. The method for deoxidation and desulfurization of copper or copper alloys according to any one of claims 1 to 3, wherein the pressure of the carrier gas is 0.5 to 2 MPa; the flow rate of the carrier gas is 3-8 m3/h。
6. The method for deoxidizing and desulfurizing copper or a copper alloy as set forth in any one of claims 1 to 3, wherein the temperature of said melt is 1200 to 1280 ℃, and the time for which said carrier gas carrying said deoxidizing and desulfurizing agent is introduced is 2 to 8 min.
7. The deoxidation and desulfurization method for copper or copper alloy as claimed in any one of claims 1 to 3, wherein after the introduction of the carrier gas carrying the deoxidation and desulfurization agent is completed, the flow rate of the carrier gas is continuously introduced into the bottom of the copper or copper alloy melt at 0.6-2 m3The carrier gas is carried for 10-20 min.
8. The method for deoxidation and desulfurization of copper or copper alloys according to any one of claims 1 to 3, wherein the deoxidation and desulfurization is carried out in an induction furnace having a frequency of 1000 to 2500 Hz.
9. The preparation method of the high-purity copper or the copper alloy is characterized by comprising the following steps of:
the method for deoxidizing and desulfurizing the copper or the copper alloy is used for deoxidizing and desulfurizing the melt of the copper or the copper alloy according to any one of claims 1 to 8, then the melt is cooled to 1150-1200 ℃, casting is carried out, and slag removal is carried out to obtain the alloy.
10. A high purity copper or copper alloy obtained by the method for producing high purity copper or copper alloy according to claim 9.
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