WO2023217164A1 - 利用电极分步插入制备低杂再生黄铜合金的装置及方法 - Google Patents

利用电极分步插入制备低杂再生黄铜合金的装置及方法 Download PDF

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WO2023217164A1
WO2023217164A1 PCT/CN2023/093154 CN2023093154W WO2023217164A1 WO 2023217164 A1 WO2023217164 A1 WO 2023217164A1 CN 2023093154 W CN2023093154 W CN 2023093154W WO 2023217164 A1 WO2023217164 A1 WO 2023217164A1
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melt
impurity
pulse current
electrode
sliding plate
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PCT/CN2023/093154
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English (en)
French (fr)
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张新房
张宝雨
黄孝山
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北京科技大学
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Priority to US18/379,213 priority Critical patent/US20240043964A1/en
Publication of WO2023217164A1 publication Critical patent/WO2023217164A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/08—Alloys based on copper with lead as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D11/00—Arrangement of elements for electric heating in or on furnaces
    • F27D11/08—Heating by electric discharge, e.g. arc discharge
    • F27D11/10—Disposition of electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to the technical field of metal melt purification, and in particular refers to a device and method for preparing low-impurity recycled brass alloy by step-by-step insertion of electrodes.
  • Copper and its alloy materials are widely used in electrical, automotive, construction industry, defense industry and other fields, and are second only to aluminum in the consumption of non-ferrous metal materials in China. Copper and its alloys are key basic materials for the vigorous development of engineering, and are also important industrial materials in the fields of industrial equipment, electronic information, electrical appliances and other fields. Our country’s primary copper ore resources are seriously insufficient and we are highly dependent on foreign countries.
  • an electrolytic cell for producing copper powder from scrap copper materials which includes: a cell body, an annular anode jacket and a cathode copper column located in the cell body; the annular anode jacket is placed outside the cathode copper column ; The tank body is filled with electrolyte; the ring anode jacket is used to place the copper material to be electrolyzed.
  • This electrolytic cell can electrolyze lower-grade scrap copper materials into electrolytic copper powder products that meet national standards.
  • the equipment requirements are high, the electrolytic copper liquid needs to be replaced regularly, the operation is cumbersome, the DC electric field energy consumption is high, and the production cost is high, which does not meet the requirements of the current industrial green development plan.
  • the prior art also mentions a method for comprehensive recovery of valuable metals from copper-based solid waste, which includes the following steps: uniformly mixing the copper-based solid waste, coal and flux and then performing reduction smelting to produce blister copper, Reduction of slag and soot; the produced blister copper is subjected to anode refining with a fuel rate of 5-15% and a slagging rate of 3-30% to obtain copper anode plates, refining slag and soot; the produced refining slag is acid leached. Electric copper and leaching slag are obtained.
  • This method can not only efficiently separate copper from copper-based solid waste, but also process heavy metal solid waste such as scrap copper, sub-zinc oxide dust, tin slag and other heavy metal solid waste, achieving the purpose of comprehensive and efficient cascade recovery of copper, zinc, lead and tin throughout the entire process.
  • the regeneration process is long and the parameter variables are complex, so the effect of purifying and removing impurities from the alloy melt in a short process cannot be achieved.
  • the main processes include raw material pretreatment-magnetic separation-smelting-casting.
  • the scrap copper raw materials are first pre-processed, dismantling the easily separated iron products, crushing them using metal shears and then magnetically separating them. Physically separate the iron products in one step, and then add the refining agent copper chloride or cuprous chloride wrapped in copper foil after complete melting in the induction furnace.
  • the melting temperature is 950°C-1500°C; stir and keep for 15-60 minutes, and cast into ingots.
  • the iron content in the ingot copper alloy is reduced to less than 0.1%, and the iron content in the treated copper alloy is greatly reduced, achieving the purpose of purifying the regenerated copper melt.
  • the technical problem to be solved by the present invention is to provide a device and method for preparing low-impurity regenerated brass alloy by step-by-step insertion of electrodes.
  • it can solve the problem of avoiding the introduction of new impurities by slagging and removing impurities in the refining agent.
  • the impurity removal using the electromigration effect is not obvious (elements migrate in the horizontal direction).
  • the impurity elements in the melt are generated.
  • the device includes a melt heating device, an electrode displacement device and a pulse current generating device.
  • the melt heating device includes a heating source, a metal melt and a molten pool;
  • the electrode displacement device includes a graphite electrode plate, a connector, a connecting rod, and a fixed knob.
  • telescopic rod hydraulic device, motor, sliding plate, parallel metal sliding plate base, fixed base and fixed nut, used to control the position of the electrode and realize the step-by-step insertion of the electrode into the melt;
  • the pulse current generating device and metal wires are used to provide pulse current.
  • the connector is connected to the connecting rod through a fixed nut.
  • a fixed knob is used to adjust and control the forward and backward movement of the graphite electrode plate.
  • the telescopic rod The hydraulic device and motor are used to control the up and down movement of the graphite electrode plate; the hydraulic device and motor are installed on the sliding plate, the sliding plate is connected to the parallel metal sliding plate base, and the sliding plate and the parallel metal sliding plate base control the left and right movement of the graphite electrode plate.
  • the parallel metal sliding plate base is installed on the fixed base, and the metal wires connect the connector and the pulse current generating device.
  • the telescopic rod and the hydraulic device are combined into an automatic electrode lifting device.
  • the application method of the device includes the following steps:
  • S3 The automatic lifting device of the electrode is controlled to reduce the insertion depth of the graphite electrode plate in the melt.
  • the descending distance is consistent with the distance between the graphite electrode plate and the metal melt surface in S2.
  • Pulse current processing is performed and the processing time is the same as S2;
  • the melt heating temperature in S1 is 1000 ⁇ 1200°C
  • the stirring time is 1 ⁇ 60min
  • the melt holding temperature is 900 ⁇ 1200°C
  • the holding time is 1 ⁇ 500min.
  • the current of the pulse current in S2 is 1 ⁇ 5000A
  • the electric pulse frequency is 1Hz ⁇ 120kHz
  • the pulse width is 1 ⁇ s ⁇ 1000ms
  • the voltage is 1 ⁇ 36V
  • the depth of the electrode inserted into the melt each time accounts for 20% ⁇ 25% of the total height of the melt.
  • the application time of each pulse current is 1-60min
  • the distance between the bottom of the electrode and the bottom of the molten pool is 2-30cm.
  • the melt temperature is controlled from 850°C to 1100°C before coming out of the furnace.
  • the multi-component impurity elements in the above-mentioned high-impurity recycled brass raw materials include one or more of the following components: Pb0.001-7.0wt.%, Bi 0.001-6.0wt.%, Fe 0.1-2.5wt.%, Al 0.01- 2.45wt.%, Si 0.01-2.5wt.%, Sn0.1-2.0wt.%.
  • the removal rate efficiency range of the multiple impurity elements in the above-mentioned low-impurity recycled brass alloy is Pb 60 ⁇ 90%, Bi 50 ⁇ 90%, Fe 55 ⁇ 85%, Al 50 ⁇ 82%, Si 50 ⁇ 80%, Sn 50 ⁇ 70%.
  • the heating source in the melt heating device includes but is not limited to a power frequency induction furnace.
  • the combination of the regenerated brass heating and smelting device, the electrode displacement device and the pulse current generating device can realize the integrated production of impurity reduction and alloying preparation of regenerated brass, and successfully combine the electric field-assisted melt purification technology with regenerated brass.
  • Gold preparation is organically combined and has the capability of large-scale continuous production.
  • the device and production method prepare low-impurity recycled brass alloys with short production process, simple operation, low equipment energy consumption and high impurity removal efficiency. They meet the requirements of the current industrial green development plan and are suitable for various non-ferrous metal alloy recycling and large-scale applications. Large-scale continuous production.
  • the present invention can achieve the impurity reduction effect of regenerating brass melt with large-volume multi-element impurity elements through an electrode displacement device, and organically combines the electric field-assisted melt purification technology with the regenerated brass alloy production system to prepare low-impurity brass alloy.
  • the electrode displacement device can achieve an impurity reduction effect on large-volume brass melts.
  • Figure 1 is a schematic structural diagram of a device for preparing low-impurity recycled brass alloy by step-by-step insertion of electrodes according to the present invention
  • Figure 2 is a comparison of the Bi element between the electrodes after the brass is solidified with or without pulse current treatment in the embodiment of the present invention, where (a) means no pulse current is applied, and (b) means pulse current is applied.
  • 1-heating source 2-metal melt; 3-melt pool; 4-graphite electrode plate; 5-fixing nut; 6-connector; 7-connecting rod; 8-fixing knob; 9-telescopic rod; 10 -Hydraulic device; 11-motor; 12-sliding plate; 13-parallel metal sliding plate base; 14-fixed base; 15-metal wire; 16-pulse current generating device.
  • the invention provides a device and method for preparing low-impurity recycled brass alloy by step-by-step insertion of electrodes.
  • the device includes a melt heating device, an electrode displacement device and a pulse current generating device 16.
  • the melt heating device includes a heating source 1, a metal melt 2 and a molten pool 3;
  • the electrode displacement device includes a graphite electrode. Plate 4, connector 5, connecting rod 7, fixed knob 8, telescopic rod 9, hydraulic device 10, motor 11, sliding plate 12, parallel metal sliding plate base 13, fixed base 14 and fixed nut 5;
  • the graphite electrode plate 4 is inserted into the metal melt 2, and the other end is connected to the connector 6.
  • the connector 6 is connected to the connecting rod 7 through the fixing nut 5.
  • the connecting rod 7 passes through the telescopic rod 9 and is used for adjustment control through the fixed knob 8.
  • the graphite electrode plate 4 moves forward and backward, and the telescopic rod 9 is used to control the up and down movement of the graphite electrode plate 4 through the hydraulic device 10 and the motor 11; the hydraulic device 10 and the motor 11 are installed on the sliding plate 12, and the sliding plate 12 is connected to the parallel metal sliding plate.
  • the base 13, the sliding plate 12 and the parallel metal sliding plate base 13 control the left and right movement of the graphite electrode plate 4.
  • the parallel metal sliding plate base 13 is installed on the fixed base 14, and the metal wire 15 connects the connector 6 and the pulse current generating device 16.
  • the telescopic rod 9 and the hydraulic device 10 are combined into an automatic electrode lifting device.
  • a strong magnetic device is provided inside the sliding plate 12 for fixing the sliding plate 12 and the parallel metal sliding plate base 13 .
  • the specific process parameters of the device are: the quality of the high impurity brass melt processed is 100-5000kg, graphite electrode: rectangular electrode (length 5-200cm, width 1-20cm, height 80-300cm).
  • the application method of the device includes the following steps:
  • S3 The automatic lifting device of the electrode is controlled to reduce the insertion depth of the graphite electrode plate in the melt.
  • the descending distance is consistent with the distance between the graphite electrode plate and the metal melt surface in S2.
  • Pulse current processing is performed and the processing time is the same as S2;
  • the present invention applies pulse current to the highly impure brass melt by inserting electrodes step by step.
  • the automatic lifting device of the electrode controls the depth of the electrode in the melt to gradually drop from the top to the bottom of the melt over time. Changing the electrode position multiple times causes the melt to melt.
  • the current lines in the body are more densely distributed and have stronger electrical driving force, which promotes the directional migration of impurity elements in the melt.
  • the mechanism is: due to the difference in relative matrix density of impurity elements (Cu 8.96g/cm -3 , Zn 7.14g/cm -3 ), this device is used to change the electrode position in stages to create a stronger current density gradient, which promotes the flow of electricity in the melt. Impurity elements migrate vertically.
  • impurity elements Pb and Bi Pb 11.343g/cm -3 , Bi 9.8g/cm -3
  • stronger electric driving force forces dense impurities to eventually accumulate at the bottom of the molten pool. It is removed by shutting down the furnace regularly and breaking the furnace wall; impurity elements such as Si and Fe (Si 2.33g/cm -3 , Fe 7.86g/cm -3 ), which have a lower density than the brass matrix elements, move and accumulate inside the melt. Go to the surface of the melt and remove it after slag removal.
  • the content of multiple impurity elements inside the melt can be reduced, the cleanliness of the recycled brass alloy can be improved, and a low-impurity recycled brass alloy can be produced.
  • the device includes a melt heating device, an electrode displacement device, and a pulse current generating device.
  • the heating device includes a heating source 1, a metal melt 2, and a molten pool 3 for heating the melt;
  • the electrode displacement device includes: graphite electrode plate 4, fixing nut 5, connector 6, connecting rod 7, fixing knob 8, telescopic Rod 9, hydraulic device 10, motor 11, sliding plate 12, parallel metal sliding plate base 13, fixed base 14, used to control the position of the electrode to achieve step-by-step insertion of the electrode into the melt; metal wire 15 and pulse current generating device Set to 16 to provide pulse current.
  • the raw material in this example uses high-contamination Bi brass raw material (Bi 5.983wt.%).
  • the specific steps are as follows:
  • the first step Place the high-contamination brass raw material into the molten pool in the shape of a block of scrap copper weighing about 100kg. Use a heating source to heat the melt to 1100°C, stir for 1 minute, keep the temperature at 1000°C, and hold for 10 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the columnar graphite electrode plate (length ⁇ width ⁇ height 5cm ⁇ 1cm ⁇ 100cm) to the pulse current generating device through a metal wire, start the automatic lifting device of the electrode, insert the electrode into the melt, and insert the electrode into the melt to the depth 2cm, start the pulse current generating device, and process the pulse current for 10 minutes;
  • the specific parameters of the pulse current generating device are: voltage 17V, pulse current 150A, frequency 2000Hz, pulse width 500 ⁇ s.
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the average mass concentration of the impurity element Bi after pulse treatment was measured to be 0.633wt.%, and the corresponding removal rate reached 89.42%. It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area. The result comparison is shown in Figure 2.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 6.83wt.%, Bi 3.482wt.%, Fe 2.51wt.%, Al 1.56wt.%, Si 0.1wt.%, Sn 0.2wt.%).
  • the specific steps are: as follows:
  • the first step place the scrap copper scrap of high impurity brass material weighing about 500kg into the molten pool. Use a heating source to heat the melt to 1100°C, stir for 5 minutes, keep the temperature at 900°C, and hold for 20 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 10cm ⁇ 5cm ⁇ 100cm) to the pulse current generating device through a metal wire, start the electrode automatic lifting device, insert the electrode into the melt, and insert the electrode into the melt to a depth of 10cm , start the pulse current generating device, and process the pulse current for 15 minutes;
  • the specific parameters of the pulse current generating device are: voltage 24V, pulse current 1500A, frequency 10000Hz, pulse width 100 ⁇ s.
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt is consistent with the pulse current processing time, pulse current
  • the parameters of the flow generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si and Sn after pulse treatment were measured to be 2.675wt.% respectively. , 0.514wt.%, 0.612wt.%, 0.2652wt.%, 0.0196wt.%, 0.0585wt.%, their corresponding removal rates reach 60.84%, 85.24%, 75.6%, 83%, 80.45%, 70.74% respectively . It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 5.3wt.%, Bi 3.269wt.%, Fe1.0wt.%, Al 0.01wt.%, Si 0.374wt.%, Sn 1.2wt.%).
  • the specific steps are: as follows:
  • the first step place the scrap copper scrap of high impurity brass material weighing about 500kg into the molten pool. Use a heating source to heat the melt to 1050°C, stir for 5 minutes, keep the temperature at 900°C, and hold for 15 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 10cm ⁇ 5cm ⁇ 100cm) to the pulse current generating device through a metal wire, start the electrode automatic lifting device, insert the electrode into the melt, and insert the electrode into the melt to a depth of 1cm , start the pulse current generating device and process the pulse current for 5 minutes;
  • the specific parameters of the pulse current generating device are: voltage 12V, pulse current 1500A, frequency 1Hz, pulse width 1000ms.
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si and Sn after pulse treatment were measured to be 2.125wt.% respectively. , 1.308wt.%, 0.45wt.%, 0.005wt.%, 0.187wt.%, 0.6wt.%, the corresponding removal rates reach 59.89%, 60%, 55%, 52.3%, 50%, 50% respectively . It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 3.93wt.%, Bi 0.001wt.%, Fe 0.1wt.%, Al 2.45wt.%, Si 2.578wt.%, Sn 0.3wt.%).
  • the specific steps are: as follows:
  • Step 1 Load the scrap copper scrap with high impurity brass raw material weighing about 1000kg into the molten pool of the power frequency induction furnace. Start the heating device, heat the power frequency induction furnace to 1100°C, stir for 10 minutes, keep the temperature at 980°C, and keep the temperature for 20 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 70cm ⁇ 15cm ⁇ 200cm) to the pulse current generating device through a metal wire, start the electrode automatic lifting device, insert the electrode into the melt, and insert the electrode into the melt depth 10cm, start the pulse current generating device, and process the pulse current for 20 minutes;
  • the specific parameters of the pulse current generating device are: voltage 36V, pulse current 2000A, frequency 10000Hz, pulse width 100 ⁇ s.
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si and Sn after pulse treatment were measured to be 0.573wt.% respectively. , 0.00013wt.%, 0.0146wt.%, 0.473wt.%, 0.516wt.%, 0.0861wt.%, the corresponding removal rates reach 85.43%, 86.82%, 85.4%, 80.71%, 80%, 71.3% respectively . It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 0.001wt.%, Bi 5.471wt.%, Fe 1.5wt.%, Al 0.3wt.%, Si 2.478wt.%, Sn 0.14wt.%).
  • the specific steps are: as follows:
  • Step 1 Load the scrap copper scrap of high impurity brass material weighing about 2000kg into the molten pool of the power frequency induction furnace. Start the heating device, heat the power frequency induction furnace to 1100°C, stir for 15 minutes, keep the temperature at 1000°C, and keep the temperature for 30 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 70cm ⁇ 20cm ⁇ 250cm) through the metal wire and the pulse electrode Connect the flow generating device, start the electrode automatic lifting device, insert the electrode into the melt, the electrode is inserted into the melt to a depth of 10cm, start the pulse current generating device, and process the pulse current for 10 minutes;
  • the specific parameters of the pulse current generating device are: voltage 36V, pulse Current 2500A, frequency 20000Hz, pulse width 50 ⁇ s.
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si and Sn after pulse treatment were measured to be 0.00013wt.% respectively. , 2.210wt.%, 0.366wt.%, 0.063wt.%, 0.6442wt.%, 0.0308wt.%, the corresponding removal rates reach 87%, 59.6%, 75.6%, 79%, 74%, 78% respectively . It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 4.587wt.%, Bi 3.412wt.%, Fe 0.745wt.%, Al0.01wt.%, Si 0.01wt.%, Sn 2.00wt.%).
  • the specific steps are as follows:
  • Step 1 Load the scrap copper scrap with high impurity brass raw material weighing about 2500kg into the molten pool of the power frequency induction furnace. Start the heating device, heat the power frequency induction furnace to 1100°C, stir for 20 minutes, keep the temperature at 1000°C, and keep the temperature for 40 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 200cm ⁇ 10cm ⁇ 300cm) to the pulse current generating device through a metal wire, start the electrode automatic lifting device, insert the electrode into the melt, and insert the electrode into the melt depth 20cm, start the pulse current generating device and process the pulse current for 20 minutes;
  • the specific parameters of the pulse current generating device are: voltage 36V, pulse current 3000A, frequency 100000Hz, pulse width 1 ⁇ s;
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the composition of the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF), and the copper alloy after pulse treatment was measured.
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si, and Sn are respectively 1.335wt.%, 0.839wt.%, 0.193wt.%, 0.002wt.%, 0.002wt.%, and 0.896wt.%, and their corresponding The removal rates reached 70.89%, 75.41%, 74.1%, 80.71%, 80%, and 55.2% respectively. It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.
  • the invention is suitable for purifying a multi-component impurity element brass alloy melt to prepare a low-impurity regenerated brass alloy.
  • a multi-component impurity element regenerated brass alloy is used as the raw material.
  • the raw materials of this embodiment are high impurity brass raw materials (Pb 7.0wt.%, Bi 5.947wt.%, Fe 0.15wt.%, Al 2.41wt.%, Si 0.374wt.%, Sn 0.1wt.%).
  • the specific steps are: as follows:
  • Step 1 Load the scrap copper scrap with high impurity brass raw material weighing about 5000kg into the molten pool of the power frequency induction furnace. Start the heating device, heat the power frequency induction furnace to 1200°C, stir for 20 minutes, keep the temperature at 1000°C, and keep the temperature for 60 minutes to completely melt the melt and obtain a regenerated brass melt with uniform composition;
  • Step 2 Connect the rectangular graphite electrode (length ⁇ width ⁇ height 200cm ⁇ 20cm ⁇ 300cm) to the pulse current generating device through a metal wire, start the electrode automatic lifting device, insert the electrode into the melt, and insert the electrode into the melt depth 10cm, start the pulse current generating device, and process the pulse current for 10 minutes;
  • the specific parameters of the pulse current generating device are: voltage 36V, pulse current 4500A, frequency 120000Hz, pulse width 500ms;
  • Step 3 Control the electrode lifting device so that the descending distance of the electrode inserted into the melt, the pulse current processing time, and the parameters of the pulse current generating device are the same as in the second step;
  • Step 4 Cyclic operation The steps in step 3 are applied to the melt with pulse current until the electrode insertion depth is close to the bottom of the crucible.
  • Step 5 After the pulse current treatment, heat preservation, slag removal, and ingot casting are performed to obtain low impurity regenerated brass alloy.
  • the copper alloy between the electrodes after pulse treatment was analyzed using an X-ray fluorescence analyzer (XRF).
  • XRF X-ray fluorescence analyzer
  • the mass concentrations of impurity elements Pb, Bi, Fe, Al, Si and Sn after pulse treatment were measured to be 2.625wt.% respectively. , 2.289wt.%, 0.0225wt.%, 1.205wt.%, 0.097wt.%, 0.03wt.%, the corresponding removal rates reach 62.5%, 61.5%, 85%, 50%, 74%, 70% respectively . It can be found that pulse current treatment by inserting electrodes step by step can effectively reduce the content of multi-element impurities in scrap copper over a large area.

Abstract

本发明提供一种利用电极分步插入制备低杂再生黄铜合金的装置及方法，属于金属熔体净化技术领域。该装置包括熔体加热装置、电极位移装置和脉冲电流发生装置，具体包括加热源、金属熔体、熔池、石墨电极板、连接器、连接杆、固定旋钮、伸缩杆、电机、滑动板、平行金属滑动板底座、固定底座。石墨电极板一端插入熔体，一端连接连接器，连接器连接连接杆，连接杆穿过伸缩杆，伸缩杆控制电极上下移动，滑动板与平行金属滑动板底座控制电极左右移动，平行金属滑动板底座连接固定底座，金属导线连接连接器和脉冲电流发生装置。本发明制备低杂再生黄铜合金生产流程短、操作简易、能耗低、除杂效率高，适用于有色金属合金再生和大规模连续生产。

Description

利用电极分步插入制备低杂再生黄铜合金的装置及方法 技术领域
本发明涉及金属熔体净化技术领域，特别是指一种利用电极分步插入制备低杂再生黄铜合金的装置及方法。
背景技术
铜及其合金材料广泛运用于电气、汽车、建筑工业、国防工业等领域，在中国有色金属材料的消费中仅次于铝。且铜及其合金是工程大力发展的关键基础材料，也是工业装备、电子信息、电器等领域重要的工业用材料。我国原生铜矿资源严重不足，对外依存度高。
相比于铜精矿冶炼，1吨再生黄铜制品可减少二氧化碳排放约5.5万吨；回收1吨黄铜可节约4.5吨铜精矿。开发利用二次资源，不仅能够最大限度的实现资源再利用，给企业带来可观的经济效益，也成为实现可持续发展的重要途径。但是再生黄铜原料来源广泛、种类多样、形态各异，夹杂物、附着物等污染物多。这些原料直接熔炼后，导致熔体中杂质元素种类繁多、含量高等特点，不同程度地影响着铜材的加工性能和物理力学性能。因此，为了提高再生黄铜合金的质量，在再生黄铜合金熔炼时去除熔体中的杂质元素是非常重要的，这有助于最大程度地发挥黄铜合金的再生潜力，并且提高合金材料的纯净度和综合性能。
现有技术中提及了一种利用废杂铜料生产铜粉的电解槽，包括：槽体和位于槽体内的圆环阳极夹套和阴极铜柱；圆环阳极夹套套在阴极铜柱外；槽体内填充有电解液；圆环阳极夹套用于放置待电解铜料。该电解槽能够将较低品位的废杂铜料电解成符合国标的电解铜粉产品。但是对设备要求较高，电解铜液需要定期更换，操作繁琐，且直流电场能耗较高，生产成本高，不契合当前工业绿色发展规划的要求。
现有技术中还提及了一种从铜基固废中综合回收有价金属的方法，包括以下步骤：将铜基固废、煤与熔剂均匀混合配料后进行还原熔炼，产出粗铜、还原渣、烟尘；产出的粗铜进行阳极精炼，燃料率为5-15％，造渣率为3-30％，得到铜阳极板、精炼渣、烟尘；产出的精炼渣采用酸浸，得到电铜、浸出渣。该方法既能使铜基固废中的铜高效分离，又能处理废杂铜、次氧化锌烟尘、锡渣等重金属固废，实现全流程铜锌铅锡的梯级综合高效回收的目的。但是再生流程长，参数变量复杂，实现不了短流程合金熔体净化除杂的效果。
现有技术中关于废杂铜除铁的方法，其主要工艺包括原料预处理—磁选—熔炼—浇铸。废杂铜原料首先经过预处理，拆解容易分离的铁制品，利用金属剪切机破碎后磁选，进一 步物理分离铁制品，然后在感应炉内完全熔化后加入铜箔包裹的精炼剂氯化铜或者氯化亚铜，熔炼温度为950℃-1500℃；搅拌保温15-60min，浇铸成锭。铸锭铜合金中铁元素含量下降至0.1％以下，处理后的铜合金中铁含量大大降低，实现了再生铜熔体净化的目的。但精炼剂造渣降杂的引入不免会引入新的杂质元素，影响后续合金加工性能。精炼剂造渣降杂过程也将发生一定程度黄铜本体金属Cu、Zn的氧化、还原介质的损耗，造成净化体系的损失。
针对上述再生黄铜合金现有工艺和技术的不足，亟待开发一种短流程、低成本、低能耗、低碳排放量的用于实际工业生产制备低杂再生黄铜合金的方法及装置来应对现有技术的不足，以解决或减轻上述问题。
发明内容
本发明要解决的技术问题是提供一种利用电极分步插入制备低杂再生黄铜合金的装置及方法，一方面可解决避免精炼剂造渣除杂引入新的杂质的问题，另一方面，若直接插入底部由于大体积熔体尺寸效应，利用电迁移效应除杂不明显(元素水平方向迁移)，而由于杂质元素与基体的密度差异，在电流密度梯度驱动下，熔体内杂质元素发生垂直方向上的迁移；因此，利用所述分步插入电极的装置及生产方法改变脉冲电流施加过程中电极在熔体中的位置，可以在熔体中形成更高的电流密度梯度，促进杂质元素在垂直方向上的迁移，实现再生黄铜大体积熔体的净化效果；将电场辅助熔体净化技术与再生黄铜合金生产系统有机结合，制备出低杂黄铜合金。
该装置包括熔体加热装置、电极位移装置和脉冲电流发生装置，其中，熔体加热装置包括加热源、金属熔体和熔池；电极位移装置包括石墨电极板、连接器、连接杆、固定旋钮、伸缩杆、液压装置、电机、滑动板、平行金属滑动板底座、固定底座和固定螺母，用于控制电极位置，实现电极分步式插入熔体中；脉冲电流发生装置和金属导线用于提供脉冲电流。
石墨电极板一端插入金属熔体内，另一端与连接器连接，连接器通过固定螺母与连接杆连接，连接杆穿过伸缩杆后通过固定旋钮用于调节控制石墨电极板前后方向移动，伸缩杆通过液压装置和电机用于控制石墨电极板上下方向移动；液压装置和电机安装在滑动板上，滑动板连接平行金属滑动板底座，滑动板与平行金属滑动板底座控制石墨电极板左右方向移动，平行金属滑动板底座安装在固定底座上，金属导线连接连接器和脉冲电流发生装置。
其中，伸缩杆和液压装置组合成电极自动升降装置。
滑动板内部设有强磁装置用于滑动板与平行金属滑动板底座的固定。
该装置的应用方法，包括步骤如下：
S1：将高杂再生黄铜原料放置于熔池内，启动熔体加热装置，使原料熔化，并对其搅拌和保温；
S2：将石墨电极板通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将石墨电极板插入到金属熔体内，启动脉冲电流电流发生装置，对金属熔体进行固定时间的脉冲电流处理；
S3：控制电极自动升降装置降低石墨电极板在熔体中的插入深度，下降距离与S2中石墨电极板离金属熔体表面的距离保持一致，进行脉冲电流处理且处理时间与S2相同；
S4：循环S3对金属熔体进行脉冲电流处理，直至石墨电极板插入深度接近熔池底部；由于杂质元素与基体的密度差异，在电流密度梯度驱动下，熔体内杂质元素发生垂直方向上的迁移；因此，利用所述分步插入电极的装置及生产方法改变脉冲电流施加过程中电极在熔体中的位置，可以在熔体中形成更高的电流密度梯度，促进杂质元素在垂直方向上的迁移，实现再生黄铜大体积熔体的净化效果，生产出低杂质再生黄铜合金；
S5：在保温阶段完成脉冲电流处理后，取样检测，调控熔体温度，出炉得到低杂再生黄铜合金。
其中，S1中熔体加热温度为1000～1200℃，搅拌时间为1～60min，熔体保温温度为900～1200℃，保温时间为1～500min。
S2中脉冲电流的电流为1～5000A，电脉冲频率为1Hz～120kHz，脉宽为1μs～1000ms，电压为1～36V，电极每次插入熔体深度占熔体总高度的20％～25％，每段脉冲电流的施加时间为1-60min，最终，电极底部距熔池底部距离为2-30cm。
S5中调控熔体温度为850℃～1100℃，出炉。
上述高杂再生黄铜原料中多元杂质元素包括以下成分中的一种或多种：Pb0.001-7.0wt.％、Bi 0.001-6.0wt.％、Fe 0.1-2.5wt.％、Al 0.01-2.45wt.％、Si 0.01-2.5wt.％、Sn0.1-2.0wt.％。
上述低杂再生黄铜合金中的多元杂质元素的去除率效率范围为Pb 60～90％、Bi 50～90％、Fe 55～85％、Al 50～82％、Si 50～80％、Sn 50～70％。
一般的，熔体加热装置中加热源包括但不限于工频感应炉。
本发明的上述技术方案的有益效果如下：
上述方案中，再生黄铜加热熔炼装置、电极位移装置和脉冲电流发生装置结合可实现对再生黄铜降杂和合金化制备的一体化生产，成功将电场辅助净化熔体技术与再生黄铜合 金制备有机结合，且具备大规模连续生产的能力。该装置及生产方法制备低杂再生黄铜合金生产流程短、操作简易化、设备能耗低、除杂效率高，符合当前工业绿色发展规划的要求，且适用于各种有色金属合金再生和大规模连续生产。本发明可通过电极位移装置实现大体积多元杂质元素再生黄铜熔体降杂的效果，将电场辅助熔体净化技术与再生黄铜合金生产系统有机结合，制备出低杂黄铜合金。一方面解决了避免精炼剂造渣除杂引入新的杂质的问题，另一方面通过电极位移装置可对大体积黄铜熔体实现降杂效果。
附图说明
图1为本发明的利用电极分步插入制备低杂再生黄铜合金的装置结构示意图；
图2为本发明实施例中有无脉冲电流处理黄铜凝固后电极间Bi元素的对比，其中，(a)为未施加脉冲电流，(b)为施加脉冲电流。
其中：1-加热源；2-金属熔体；3-熔池；4-石墨电极板；5-固定螺母；6-连接器；7-连接杆；8-固定旋钮；9-伸缩杆；10-液压装置；11-电机；12-滑动板；13-平行金属滑动板底座；14-固定底座；15-金属导线；16-脉冲电流发生装置。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述。
本发明提供一种利用电极分步插入制备低杂再生黄铜合金的装置及方法。
如图1所示，该装置包括熔体加热装置、电极位移装置和脉冲电流发生装置16，其中，熔体加热装置包括加热源1、金属熔体2和熔池3；电极位移装置包括石墨电极板4、连接器5、连接杆7、固定旋钮8、伸缩杆9、液压装置10、电机11、滑动板12、平行金属滑动板底座13、固定底座14和固定螺母5；
石墨电极板4一端插入金属熔体2内，另一端与连接器6连接，连接器6通过固定螺母5与连接杆7连接，连接杆7穿过伸缩杆9后通过固定旋钮8用于调节控制石墨电极板4前后方向移动，伸缩杆9通过液压装置10和电机11用于控制石墨电极板4上下方向移动；液压装置10和电机11安装在滑动板12上，滑动板12连接平行金属滑动板底座13，滑动板12与平行金属滑动板底座13控制石墨电极板4左右方向移动，平行金属滑动板底座13安装在固定底座14上，金属导线15连接连接器6和脉冲电流发生装置16。
其中，伸缩杆9和液压装置10组合成电极自动升降装置。
滑动板12内部设有强磁装置用于滑动板12与平行金属滑动板底座13的固定。
一般的，该装置具体工艺参数为：处理高杂黄铜熔体质量为100-5000kg，石墨电极：矩形电极(长5～200cm、宽1～20cm、高80～300cm)。
该装置的应用方法，包括步骤如下：
S1：将高杂再生黄铜原料放置于熔池内，启动熔体加热装置，使原料熔化，并对其搅拌和保温；
S2：将石墨电极板通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将石墨电极板插入到金属熔体内，启动脉冲电流电流发生装置，对金属熔体进行固定时间的脉冲电流处理；
S3：控制电极自动升降装置降低石墨电极板在熔体中的插入深度，下降距离与S2中石墨电极板离金属熔体表面的距离保持一致，进行脉冲电流处理且处理时间与S2相同；
S4：循环S3对金属熔体进行脉冲电流处理，直至石墨电极板插入深度接近熔池底部(一般的，最终，电极底部距熔池底部距离为2-30cm)；
S5：在保温阶段完成脉冲电流处理后，取样检测，调控熔体温度(一般出炉温度为850℃～1100℃)，出炉得到低杂再生黄铜合金。
本发明通过分步插入电极的方式对高杂黄铜熔体施加脉冲电流，电极自动升降装置控制电极在熔体中的深度随时间从顶部逐渐下降到熔体底部，多次改变电极位置导致熔体内电流线分布更加密集，具有更强的电驱动力，促使熔体内杂质元素发生定向迁移。其机理为：杂质元素相对基体密度(Cu 8.96g/cm-3、Zn 7.14g/cm-3)的不同，利用此装置分段式改变电极位置营造更强大的电流密度梯度，促使熔体内杂质元素发生垂直方向的迁移。例如杂质元素Pb、Bi(Pb 11.343g/cm-3、Bi 9.8g/cm-3)，在分步电极的作用下，更强的电驱动力迫使密度大的杂质最终在熔池底部聚集，定期停炉打炉壁阶段将其去除；而像杂质元素Si、Fe(Si 2.33g/cm-3、Fe 7.86g/cm-3)密度低于黄铜基体元素，由熔体内部移动并聚集到熔体表面，进行扒渣处理后，将其去除。最终可降低熔体内部多元杂质元素的含量，提高再生黄铜合金的洁净度，生产出低杂再生黄铜合金。
下面结合具体实施例予以说明。
实施例1
一种利用电极分步插入制备低杂再生黄铜合金的装置及生产方法，该装置包括熔体加热装置、电极位移装置、脉冲电流发生装置。其中加热装置包括加热源1、金属熔体2、熔池3，用于加热熔体；电极位移装置包括：石墨电极板4、固定螺母5、连接器6、连接杆7、固定旋钮8、伸缩杆9、液压装置10、电机11、滑动板12、平行金属滑动板底座13、固定底座14，用于控制电极位置，实现电极分步式插入熔体中；金属导线15和脉冲电流发生装 置16用于提供脉冲电流。
本实施例原料采用高杂Bi黄铜原料(Bi 5.983wt.％)，具体步骤如下：
第一步：将高杂Bi黄铜原料重约100kg的块状废杂铜放置到熔池中。利用加热源使熔体加热至1100℃，搅拌1min，保温温度1000℃，保温时间10min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将柱状石墨电极板(长×宽×高5cm×1cm×100cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度2cm，启动脉冲电流电流发生装置，脉冲电流处理10min；脉冲电流发生装置具体参数为：电压17V，脉冲电流150A，频率2000Hz，脉宽500μs。
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Bi平均质量浓度为0.633wt.％、对应的去除率达到了89.42％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量，结果对比图如图2所示。
实施例2
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 6.83wt.％、Bi 3.482wt.％、Fe 2.51wt.％、Al 1.56wt.％、Si 0.1wt.％、Sn 0.2wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约500kg的块状废杂铜放置到熔池中。利用加热源使熔体加热至1100℃，搅拌5min，保温温度900℃，保温时间20min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形石墨电极(长×宽×高10cm×5cm×100cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度10cm，启动脉冲电流电流发生装置，脉冲电流处理15min；脉冲电流发生装置具体参数为：电压24V，脉冲电流1500A，频率10000Hz，脉宽100μs。
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电 流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在2.675wt.％、0.514wt.％、0.612wt.％、0.2652wt.％、0.0196wt.％、0.0585wt.％，其对应的去除率分别达到60.84％、85.24％、75.6％、83％、80.45％、70.74％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
实施例3
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 5.3wt.％、Bi 3.269wt.％、Fe1.0wt.％、Al 0.01wt.％、Si 0.374wt.％、Sn 1.2wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约500kg的块状废杂铜放置到熔池中。利用加热源使熔体加热至1050℃，搅拌5min，保温温度900℃，保温时间15min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形石墨电极(长×宽×高10cm×5cm×100cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度1cm，启动脉冲电流电流发生装置，脉冲电流处理5min；脉冲电流发生装置具体参数为：电压12V，脉冲电流1500A，频率1Hz，脉宽1000ms。
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在2.125wt.％、1.308wt.％、0.45wt.％、0.005wt.％、0.187wt.％、0.6wt.％，其对应的去除率分别达到59.89％、60％、55％、52.3％、50％、50％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
实施例4
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 3.93wt.％、Bi 0.001wt.％、Fe 0.1wt.％、Al 2.45wt.％、Si 2.578wt.％、Sn 0.3wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约1000kg的块状废杂铜装入到工频感应炉熔池内。启动加热装置，将工频感应炉加热至1100℃，搅拌10min，保温温度980℃，保温时间20min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形状石墨电极(长×宽×高70cm×15cm×200cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度10cm，启动脉冲电流电流发生装置，脉冲电流处理20min；脉冲电流发生装置具体参数为：电压36V,脉冲电流2000A，频率10000Hz，脉宽100μs。
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在0.573wt.％、0.00013wt.％、0.0146wt.％、0.473wt.％、0.516wt.％、0.0861wt.％，其对应的去除率分别达到85.43％、86.82％、85.4％、80.71％、80％、71.3％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
实施例5
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 0.001wt.％、Bi 5.471wt.％、Fe 1.5wt.％、Al 0.3wt.％、Si 2.478wt.％、Sn 0.14wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约2000kg的块状废杂铜装入到工频感应炉熔池内。启动加热装置，将工频感应炉加热至1100℃，搅拌15min，保温温度1000℃，保温时间30min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形状石墨电极(长×宽×高70cm×20cm×250cm)通过金属导线与脉冲电 流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度10cm，启动脉冲电流电流发生装置，脉冲电流处理10min；脉冲电流发生装置具体参数为：电压36V，脉冲电流2500A，频率20000Hz，脉宽50μs。
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在0.00013wt.％、2.210wt.％、0.366wt.％、0.063wt.％、0.6442wt.％、0.0308wt.％，其对应的去除率分别达到87％、59.6％、75.6％、79％、74％、78％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
实施例6
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 4.587wt.％、Bi 3.412wt.％、Fe 0.745wt.％、Al0.01wt.％、Si 0.01wt.％、Sn 2.00wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约2500kg的块状废杂铜装入到工频感应炉熔池内。启动加热装置，将工频感应炉加热至1100℃，搅拌20min，保温温度1000℃，保温时间40min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形状石墨电极(长×宽×高200cm×10cm×300cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度20cm，启动脉冲电流电流发生装置，脉冲电流处理20min；脉冲电流发生装置具体参数为：电压36V，脉冲电流3000A，频率100000Hz，脉宽1μs；
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的 杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在1.335wt.％、0.839wt.％、0.193wt.％、0.002wt.％、0.002wt.％、0.896wt.％，其对应的去除率分别达到70.89％、75.41％、74.1％、80.71％、80％、55.2％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
实施例7
本发明适用于多元杂质元素黄铜合金熔体净化制备低杂再生黄铜合金，本实施案例以一种多元杂质元素再生黄铜合金为原材料。
本实施例原料采用高杂黄铜原料(Pb 7.0wt.％、Bi 5.947wt.％、Fe 0.15wt.％、Al 2.41wt.％、Si 0.374wt.％、Sn 0.1wt.％)，具体步骤如下：
第一步：将高杂黄铜原料重约5000kg的块状废杂铜装入到工频感应炉熔池内。启动加热装置，将工频感应炉加热至1200℃，搅拌20min，保温温度1000℃，保温时间60min，使熔体彻底熔化并得到成分均匀的再生黄铜熔体；
第二步：将矩形状石墨电极(长×宽×高200cm×20cm×300cm)通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将电极插入到熔体内，电极插入熔体深度10cm，启动脉冲电流电流发生装置，脉冲电流处理10min；脉冲电流发生装置具体参数为：电压36V，脉冲电流4500A，频率120000Hz，脉宽500ms；
第三步：控制电极升降装置使电极插入熔体的下降距离与脉冲电流处理时间、脉冲电流发生装置参数与第二步相同；
第四步：循环操作第三步的步骤对熔体进行脉冲电流处理，直至电极插入深度接近坩埚底部。
第五步：脉冲电流处理结束后，保温，除渣，出炉铸锭得到低杂再生黄铜合金。对脉冲处理后电极之间的铜合金采用X射线荧光分析仪(XRF)进行成分分析，测得脉冲处理后的杂质元素Pb、Bi、Fe、Al、Si、Sn质量浓度分别在2.625wt.％、2.289wt.％、0.0225wt.％、1.205wt.％、0.097wt.％、0.03wt.％，其对应的去除率分别达到62.5％、61.5％、85％、50％、74％、70％。可发现采用分步插入电极的方式脉冲电流处理后可有效大面积的降低废杂铜中的多元杂质元素含量。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (9)

  1. 一种利用电极分步插入制备低杂再生黄铜合金的装置，其特征在于，包括熔体加热装置、电极位移装置和脉冲电流发生装置，其中，熔体加热装置包括加热源、金属熔体和熔池；电极位移装置包括石墨电极板、连接器、连接杆、固定旋钮、伸缩杆、液压装置、电机、滑动板、平行金属滑动板底座、固定底座和固定螺母；
    石墨电极板一端插入金属熔体内，另一端与连接器连接，连接器通过固定螺母与连接杆连接，连接杆穿过伸缩杆后通过固定旋钮用于调节控制石墨电极板前后方向移动，伸缩杆通过液压装置和电机用于控制石墨电极板上下方向移动；液压装置和电机安装在滑动板上，滑动板连接平行金属滑动板底座，滑动板与平行金属滑动板底座控制石墨电极板左右方向移动，平行金属滑动板底座安装在固定底座上，金属导线连接连接器和脉冲电流发生装置。
  2. 根据权利要求1所述的利用电极分步插入制备低杂再生黄铜合金的装置，其特征在于，所述伸缩杆和液压装置组合成电极自动升降装置。
  3. 根据权利要求1所述的利用电极分步插入制备低杂再生黄铜合金的装置，其特征在于，所述滑动板内部设有强磁装置用于滑动板与平行金属滑动板底座的固定。
  4. 根据权利要求1所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，包括步骤如下：
    S1：将高杂再生黄铜原料放置于熔池内，启动熔体加热装置，使原料熔化，并对其搅拌和保温；
    S2：将石墨电极板通过金属导线与脉冲电流发生装置连接，启动电极自动升降装置，将石墨电极板插入到金属熔体内，启动脉冲电流电流发生装置，对金属熔体进行固定时间的脉冲电流处理；
    S3：控制电极自动升降装置降低石墨电极板在熔体中的插入深度，下降距离与S2中石墨电极板离金属熔体表面的距离保持一致，进行脉冲电流处理且处理时间与S2相同；
    S4：循环S3对金属熔体进行脉冲电流处理，直至石墨电极板插入深度接近熔池底部；
    S5：在保温阶段完成脉冲电流处理后，取样检测，调控熔体温度，出炉得到低杂再生黄铜合金。
  5. 根据权利要求4所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，所述S1中熔体加热温度为1000～1200℃，搅拌时间为1～60min，熔体保温温度为900～1200℃，保温时间为1～500min。
  6. 根据权利要求4所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，所述S2中脉冲电流的电流为1～5000A，电脉冲频率为1Hz～120kHz，脉宽为 1μs～1000ms，电压为1～36V，电极每次插入熔体深度占熔体总高度的2％～50％，每段脉冲电流的施加时间为1-60min，最终，电极底部距熔池底部距离为2-30cm。
  7. 根据权利要求4所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，所述S5中调控熔体温度为850℃～1100℃，出炉。
  8. 根据权利要求4所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，所述高杂再生黄铜原料中多元杂质元素包括以下成分中的一种或多种：Pb 0.001-7.0wt.％、Bi 0.001-6.0wt.％、Fe 0.1-2.5wt.％、Al 0.01-2.45 wt.％、Si 0.01-2.5wt.％、Sn 0.1-2.0wt.％。
  9. 根据权利要求4所述的利用电极分步插入制备低杂再生黄铜合金的装置的应用方法，其特征在于，所述低杂再生黄铜合金中的多元杂质元素的去除率效率范围为Pb 60～90％、Bi 50～90％、Fe 55～85％、Al 50～82％、Si 50～80％、Sn 50～70％。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104161A (zh) * 1985-05-31 1987-03-04 曼内斯曼股份公司 直流电弧加热装置
DE102012001907A1 (de) * 2012-02-02 2013-08-08 Badische Stahl-Engineering Gmbh Kombiniertes Hub- und Schwenkwerk
CN108326266A (zh) * 2018-04-25 2018-07-27 大同新成新材料股份有限公司 一种石墨电极升降装置
CN113753900A (zh) * 2021-10-09 2021-12-07 北京科技大学 一种利用脉冲电流分离多晶硅中杂质元素的方法及多晶硅
CN113755892A (zh) * 2021-08-05 2021-12-07 北京科技大学 一种利用脉冲电流去除废杂铜中多元杂质元素的方法
CN114959327A (zh) * 2022-05-10 2022-08-30 北京科技大学 利用电极分步插入制备低杂再生黄铜合金的装置及方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4204757C2 (de) * 1992-02-18 2001-02-15 Ald Vacuum Techn Ag Umschmelzofen
JP2008123724A (ja) * 2006-11-08 2008-05-29 Sanyo Special Steel Co Ltd ロードセルにより制御する電気炉の消耗した電極の伸ばし装置及び電極の伸ばし方法
CN109911902B (zh) * 2019-05-05 2022-06-24 上海大学 一种硅的提纯装置及方法
CN111549237B (zh) * 2020-05-20 2021-08-06 北京科技大学 一种再生铝熔体中脉冲电流分离铁元素杂质的方法
CN113718121A (zh) * 2021-08-05 2021-11-30 北京科技大学 一种快速实现稀土镁合金超洁净化冶炼的方法
CN113755891B (zh) * 2021-08-05 2023-03-21 北京科技大学 利用脉冲电流密度梯度实现金属熔体净化的方法及装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104161A (zh) * 1985-05-31 1987-03-04 曼内斯曼股份公司 直流电弧加热装置
DE102012001907A1 (de) * 2012-02-02 2013-08-08 Badische Stahl-Engineering Gmbh Kombiniertes Hub- und Schwenkwerk
CN108326266A (zh) * 2018-04-25 2018-07-27 大同新成新材料股份有限公司 一种石墨电极升降装置
CN113755892A (zh) * 2021-08-05 2021-12-07 北京科技大学 一种利用脉冲电流去除废杂铜中多元杂质元素的方法
CN113753900A (zh) * 2021-10-09 2021-12-07 北京科技大学 一种利用脉冲电流分离多晶硅中杂质元素的方法及多晶硅
CN114959327A (zh) * 2022-05-10 2022-08-30 北京科技大学 利用电极分步插入制备低杂再生黄铜合金的装置及方法

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