CN110983080B - Method for preparing ultra-low sulfur cupronickel by adopting vacuum melting equipment - Google Patents
Method for preparing ultra-low sulfur cupronickel by adopting vacuum melting equipment Download PDFInfo
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Abstract
The invention belongs to the technical field of nonferrous metal processing, and particularly relates to a method for preparing ultralow-sulfur cupronickel by adopting vacuum melting equipment. By controlling the raw materials, the desulfurizer is added in the vacuum induction melting process for desulfurization, and then refining is carried out, so that high-efficiency controllable desulfurization is realized. Has the advantages that: the vacuum melting process is adopted for desulfurization, so that the resulfurization problem is avoided, and the low impurity content in the cupronickel alloy is ensured; the nickel-calcium alloy is adopted for desulfurization, the desulfurization effect is good, and the desulfurization time is shortened; compared with gas desulfurization, the nickel-calcium alloy is convenient to weigh and control, and is convenient to control the stability of alloy components.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal processing, and particularly relates to a method for preparing ultralow-sulfur cupronickel by adopting vacuum melting equipment.
Background
The cupronickel alloy is a copper-based alloy which takes nickel as a main alloy element, and has stronger erosion corrosion resistance, especially excellent erosion corrosion resistance to high-speed flowing seawater, so the cupronickel alloy is widely applied to the industries of thermal power generation, petrochemical industry, marine industry, naval vessels and the like, is particularly used in a large amount on certain key marine anti-corrosion components, and has continuously expanded application range and gradually increased dosage year by year. With the development of technology, materials with better performance are needed to meet the requirements of more severe use environments.
Sulfur and oxygen have a similar "vapor reaction" in the copper bath and form a eutectic with copper. After solidification, the sulfur and oxygen react with 6Cu + SO2==2Cu2O+Cu2S, forming a compound Cu2O and Cu2S co-exists. Sulfur does not greatly affect the electrical and thermal conductivity of copper, but can greatly reduce the processing plasticity of copper. Due to Cu2S is hard and brittle, causing the copper rod to "cold shortness". The normal range of sulfur content in copper should be 10-15 ppm, and when its content is relatively high, a centerline is generatedThe problem of porosity.
With respect to the few methods currently available for producing ultra-low sulfur cupronickel in vacuum melting facilities, patent application No. 99803556.4, a process for desulfurizing blister copper, discloses a desulfurization process that is improved by introducing a mixture of an inert gas and an oxygen-containing gas, such as a mixture of nitrogen and oxygen, into the blister copper melt during the process, and varying the amount of oxygen or oxygen-containing gas in the mixture. The article 'influence of impurity elements on SCR production process and copper rod quality' is published in 2008 'Chinese metal report' and proposes 1) to ensure the quality of electrolytic copper; 2) the iron sheet binding the electrolytic copper is removed completely; 3) the added waste wire has clear components, is prepared according to specifications and is matched in order, and the invasion of harmful elements such as nickel, lead, iron, phosphorus and the like is strictly prevented; 4) the components of the melt are carefully and timely monitored, and the feedback adjustment is timely carried out; 5) basically, the operability is poor by methods such as planned overhaul of main equipment. The influence of shallow impurity elements on the quality of copper rods is published in the nonferrous metal processing in 2012, and requirements are provided for raw materials, production processes and equipment maintenance. The article "influence of sulfur on the performance of round copper rod and its control" published in "Jiangsu metallurgy" in 1991 proposes methods of enhancing the purification and sulfur removal by using fuel gas, enhancing the boiling and washing of electrolytic copper, controlling the sulfur content of anode, selecting reasonable additives and the like to remove sulfur.
Neither of the above patents nor the literature relates to a method for preparing ultra-low sulfur cupronickel by using a vacuum melting device, and neither method can be applied to a vacuum induction melting process.
Disclosure of Invention
The invention aims to solve the technical problem that the sulfur content in the cupronickel alloy is increased or cannot be removed in the cupronickel smelting process, and provides a set of finished methods for reducing the sulfur content in the cupronickel alloy.
The method specifically comprises the following steps: a method for preparing ultra-low sulfur cupronickel by adopting vacuum melting equipment is characterized by comprising the following steps:
(1) and (4) theoretical calculation: calculating the addition of the desulfurizer according to a calculation formula according to the parameters of the addition of the raw materials, the mass percent of sulfur in the molten metal, the mass percent of calcium metal in the desulfurizer and the utilization coefficient of the desulfurizer;
(2) preparation of raw materials: carrying out shot blasting and polishing treatment on electrolytic copper, electrolytic nickel, pure iron and electrolytic manganese used for smelting to remove an oxide layer or a corrosion layer on the surface, cleaning by using alcohol as a medium through ultrasonic waves, and drying for later use after cleaning;
(3) and (3) drying the casting mold: putting the cast iron mould into a drying furnace for heating;
(4) charging: sequentially loading electrolytic nickel, pure iron and electrolytic copper into a crucible of a smelting furnace, loading electrolytic manganese into a No. 1 upper material bin, and loading a desulfurizer into a No. 2 upper material bin;
(5) vacuumizing: vacuum induction melting of alloy is adopted, and the vacuum degree is firstly pumped to 1 x 10-3Pa, then filling argon to 0.8-1.0 x 105Pa, then vacuumized to 1X 10-3Pa, repeating the steps for three times; is prepared from
(6) Smelting: smelting in a vacuum induction furnace, refining for 10 minutes after the alloy in the crucible is completely melted, reducing power, and filling argon to 0.8-1.0 multiplied by 10 after the alloy liquid surface forms a film5Pa, adding manganese alloy into the No. 1 upper bin, and adding a desulfurizing agent into the No. 2 upper bin after the metal liquid level is stable;
(7) refining: increasing the smelting power until the liquid level rolls, and maintaining for 5-15 minutes after the oxide film is broken;
(8) adjusting the temperature: adjusting the power to stabilize the temperature of the molten metal at 1300-1400 ℃;
(9) casting: casting molten metal, and vacuumizing to 1 × 10-3And Pa, after 1-4 hours, taking out the mold and the ingot after the molten metal is completely solidified, and cooling in air to room temperature.
Further, the calculation formula in step (1) is as follows:
Wdesulfurizing agent=WMolten metal×W[S]÷（W[Ca]）÷K
WDesulfurizing agent: the weight of the desulfurizer added in the heat is kg;
Wmolten metal: the weight of the raw materials, kg, is added in the heat;
W[S]: weight of metal before refining, kg;
mass percent of sulfur in the liquid,%;
W[Ca]: the mass percent of metallic calcium in the desulfurizer is percent;
k: the utilization coefficient of the desulfurizing agent;
further, K is controlled to be 60-65%.
Further, the heating temperature in the step 3 is 800-1000 ℃, and the drying time is 0.5-4 hours.
Further, the desulfurizer adopted in the step (1) is nickel-calcium alloy.
Further, the argon gas used in the step (5) was 99.99% high purity argon.
Compared with the prior art, the invention has the advantages that:
(1) the vacuum melting process is adopted for desulfurization, so that the resulfurization problem is avoided, and the low impurity content in the cupronickel alloy is ensured;
(2) the nickel-calcium alloy is adopted for desulfurization, the desulfurization effect is good, and the desulfurization time is shortened;
(3) compared with gas desulfurization, the nickel-calcium alloy is convenient to weigh and control, and is convenient to control the stability of alloy components.
Drawings
FIG. 1 is a flow chart of a method for preparing ultra-low sulfur cupronickel by using vacuum melting equipment.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) According to the addition amount W of raw materialsMolten metal: 2000kg, mass percent W of sulfur in molten metal before refining[S]: 0.0080% and the mass percentage W of metallic calcium in the desulfurizer[Ca]:6 percent and the utilization coefficient K of the desulfurizer is 60 percent, and the adding amount W of the desulfurizer is calculatedDesulfurizing agent：4.45kg；
(2) Preparation of raw materials: carrying out shot blasting and polishing treatment on electrolytic copper, electrolytic nickel, pure iron and electrolytic manganese used for smelting to remove an oxide layer or a corrosion layer on the surface, cleaning by using alcohol as a medium through ultrasonic waves, and drying for later use after cleaning;
(3) and (3) drying the casting mold: putting the cast iron mould into a drying furnace, heating to 800 ℃, and drying for 0.5 hour;
(4) charging: sequentially loading electrolytic nickel, pure iron and electrolytic copper into a crucible of a smelting furnace, loading electrolytic manganese into a No. 1 upper material bin, and loading a desulfurizer into a No. 2 upper material bin;
(5) vacuumizing: vacuum induction melting of alloy is adopted, and the vacuum degree is firstly pumped to 1 x 10-3Pa, then filling argon to 0.8X 105Pa, then vacuumized to 1X 10-3Pa, repeating the steps for three times;
(6) smelting: smelting in a vacuum induction furnace, refining for 10 min after the alloy in the crucible is completely melted, reducing power, and filling argon to 0.8 × 10 after the surface of the alloy liquid forms a film5Pa, adding manganese alloy into the No. 1 upper bin, and adding a desulfurizing agent into the No. 2 upper bin after the metal liquid level is stable;
(7) refining: increasing the smelting power until the liquid level rolls, and maintaining for 5 minutes after the oxide film is crushed;
(8) adjusting the temperature: adjusting power to stabilize the temperature of molten metal at 1300 ℃;
(9) casting: casting the molten metal, vacuumizing to 1 x 10 < -3 > Pa after the casting is finished, taking out the mold and the cast ingot after the molten metal is completely solidified after 1 hour, and cooling to room temperature in air;
the sampling analysis found that the sulfur content in the cupronickel alloy was 0.0003%.
Example 2
(1) Calculating the addition of the desulfurizer to be 3.64kg according to the addition of the raw materials of 1000kg, the mass percent of sulfur in the molten metal before refining to be 0.0060%, the mass percent of metallic calcium in the desulfurizer to be 5.5% and the utilization coefficient of the desulfurizer to be 60%;
(2) preparation of raw materials: carrying out shot blasting and polishing treatment on electrolytic copper, electrolytic nickel, pure iron and electrolytic manganese used for smelting to remove an oxide layer or a corrosion layer on the surface, cleaning by using alcohol as a medium through ultrasonic waves, and drying for later use after cleaning;
(3) and (3) drying the casting mold: putting the cast iron mould into a drying furnace, heating to 900 ℃, and drying for 2 hours;
(4) charging: sequentially loading electrolytic nickel, pure iron and electrolytic copper into a crucible of a smelting furnace, loading electrolytic manganese into a No. 1 upper material bin, and loading a desulfurizer into a No. 2 upper material bin;
(5) vacuumizing: vacuum induction melting of alloy is adopted, and the vacuum degree is firstly pumped to 1 x 10-3Pa, then filling argon to 0.9X 105Pa, then vacuumized to 1X 10-3Pa, repeating the steps for three times;
(6) smelting: smelting in a vacuum induction furnace, refining for 10 min after the alloy in the crucible is completely melted, reducing power, and filling argon to 0.9 × 10 after the surface of the alloy liquid forms a film5Pa, adding manganese alloy into the No. 1 upper bin, and adding a desulfurizing agent into the No. 2 upper bin after the metal liquid level is stable;
(7) refining: increasing the smelting power until the liquid level rolls, and maintaining for 10 minutes after the oxide film is crushed;
(8) adjusting the temperature: adjusting power to stabilize the temperature of the molten metal at 1350 ℃;
(9) casting: casting molten metal, and vacuumizing to 1 × 10-3After Pa and 2 hours, taking out the mold and the ingot casting after the molten metal is completely solidified, and cooling to room temperature in air;
the sampling analysis found that the sulfur content in the cupronickel alloy was 0.0004%.
Example 3
(1) Calculating the addition of the desulfurizer to be 15.56kg according to the addition of raw materials of 8000kg, the mass percent of sulfur in the molten metal before refining to be 0.0070, the mass percent of metallic calcium in the desulfurizer to be 6 percent and the utilization coefficient of the desulfurizer to be 60 percent;
(2) preparation of raw materials: carrying out shot blasting and polishing treatment on electrolytic copper, electrolytic nickel, pure iron and electrolytic manganese used for smelting to remove an oxide layer or a corrosion layer on the surface, cleaning by using alcohol as a medium through ultrasonic waves, and drying for later use after cleaning;
(3) and (3) drying the casting mold: putting the cast iron mould into a drying furnace, heating to 1000 ℃, and drying for 0.5 hour;
(4) charging: sequentially loading electrolytic nickel, pure iron and electrolytic copper into a crucible of a smelting furnace, loading electrolytic manganese into a No. 1 upper material bin, and loading a desulfurizer into a No. 2 upper material bin;
(5) vacuumizing: vacuum induction is adopted to smelt the alloy, the vacuum degree is firstly pumped to 1 multiplied by 10 < -3 > Pa, then argon is filled to 1.0 multiplied by 105Pa, then the vacuum is pumped to 1 multiplied by 10 < -3 > Pa, and the process is repeated for three times;
(6) smelting: smelting by using a vacuum induction furnace, refining for 10 minutes after the alloy in the crucible is completely melted, reducing power, filling argon to 1.0 multiplied by 105Pa after the surface of alloy liquid is filmed, adding manganese alloy into the No. 1 upper bin, and adding a desulfurizing agent into the No. 2 upper bin after the metal liquid level is stable;
(7) refining: increasing the smelting power until the liquid level rolls, and maintaining for 15 minutes after the oxide film is crushed;
(8) adjusting the temperature: adjusting power to stabilize the temperature of the molten metal at 1400 ℃;
(9) casting: casting the molten metal, vacuumizing to 1 x 10 < -3 > Pa after the casting is finished, taking out the mold and the cast ingot after the molten metal is completely solidified after 4 hours, and cooling to room temperature in air;
the sampling analysis found that the sulfur content in the cupronickel alloy was 0.0002%.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that various modifications and equivalent arrangements can be made within the spirit and scope of the present invention without departing from the spirit and scope thereof.
Claims (2)
1. A method for preparing ultra-low sulfur cupronickel by adopting vacuum melting equipment is characterized by comprising the following steps:
(1) and (4) theoretical calculation: according to the parameters of the addition of raw materials, the mass percent of sulfur in the molten metal, the mass percent of calcium metal in the desulfurizer and the utilization coefficient of the desulfurizer, the addition of the desulfurizer is calculated according to a calculation formula, wherein the desulfurizer is nickel-calcium alloy, and the calculation formula is as follows:
Wdesulfurizing agent=WMolten metal×W[S]÷（W[Ca]）÷K
WDesulfurizing agent: the weight of the desulfurizer added in the heat is kg;
Wmolten metal: the weight of the raw materials, kg, is added in the heat;
W[S]: weight of metal before refining, kg;
mass percent of sulfur in the liquid,%;
W[Ca]: the mass percent of metallic calcium in the desulfurizer is percent;
k: the utilization coefficient of the desulfurizer is controlled, and K is controlled to be 60-65%;
(2) preparation of raw materials: carrying out shot blasting and polishing treatment on electrolytic copper, electrolytic nickel, pure iron and electrolytic manganese used for smelting to remove an oxide layer or a corrosion layer on the surface, cleaning by using alcohol as a medium through ultrasonic waves, and drying for later use after cleaning;
(3) and (3) drying the casting mold: putting the cast iron mould into a drying furnace for heating, wherein the heating temperature is 800-1000 ℃, and the drying time is 0.5-4 hours;
(4) charging: sequentially loading electrolytic nickel, pure iron and electrolytic copper into a crucible of a smelting furnace, loading electrolytic manganese into a No. 1 upper material bin, and loading a desulfurizer into a No. 2 upper material bin;
(5) vacuumizing: vacuum induction melting of alloy is adopted, and the vacuum degree is firstly pumped to 1 x 10-3Pa, then filling argon to 0.8-1.0 x 105Pa, then vacuumized to 1X 10-3Pa, repeating the steps for three times;
(6) smelting: smelting in a vacuum induction furnace, refining for 10 minutes after the alloy in the crucible is completely melted, reducing power, and filling argon to 0.8-1.0 multiplied by 10 after the alloy liquid surface forms a film5Pa, adding manganese alloy into No. 1 upper bin, and filling metal levelAfter stabilization, adding a desulfurizing agent through a No. 2 upper bunker;
(7) refining: increasing the smelting power until the liquid level rolls, and maintaining for 5-15 minutes after the oxide film is broken;
(8) adjusting the temperature: adjusting the power to stabilize the temperature of the molten metal at 1300-1400 ℃;
(9) casting: casting molten metal, and vacuumizing to 1 × 10-3And Pa, after 1-4 hours, taking out the mold and the ingot after the molten metal is completely solidified, and cooling in air to room temperature.
2. The method for preparing the ultra-low sulfur cupronickel by using the vacuum melting equipment as claimed in claim 1, wherein the argon gas used in the step (5) is 99.99% high purity argon.
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| CN101705339A (en) * | 2009-11-13 | 2010-05-12 | 江苏大学 | External desulfurizer for induction furnace and steel-making furnace and desulfurization method |
| CN110144472A (en) * | 2019-04-30 | 2019-08-20 | 中国科学院合肥物质科学研究院 | A kind of vacuum induction melting method of Manganese Copper Shock-absorption Alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101705339A (en) * | 2009-11-13 | 2010-05-12 | 江苏大学 | External desulfurizer for induction furnace and steel-making furnace and desulfurization method |
| CN110144472A (en) * | 2019-04-30 | 2019-08-20 | 中国科学院合肥物质科学研究院 | A kind of vacuum induction melting method of Manganese Copper Shock-absorption Alloy |
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