CN111945188A - Molten salt primary battery method lead-based master alloy preparation device and preparation method - Google Patents

Abstract

The invention provides a device for preparing a lead-based master alloy by a molten salt galvanic cell method, which comprises a resistance heating furnace, a reactor and a crucible, wherein the reactor is arranged inside the resistance heating furnace, the crucible is arranged in the reactor, the center of the bottom of the crucible is provided with a controllable lead conveying opening, the crucible is connected with an anode guide rod, active metal connected with a cathode guide rod is arranged in the crucible, and a stirring device is also arranged in the crucible. The invention also provides a molten salt primary battery method lead-based master alloy preparation method using the molten salt primary battery method lead-based master alloy preparation device. The lead-based master alloy is prepared by adopting the method, the high temperature required for melting active metal in a smelting method is not required, chlorine generated by a molten salt electrolysis method is not required, the energy is saved, the environment is protected, the formed alloy components are more uniform and stable, and the follow-up lead storage battery grid material has better performance.

Description

Molten salt primary battery method lead-based master alloy preparation device and preparation method

Technical Field

The invention relates to a preparation device and a preparation method of a lead-based master alloy, in particular to a preparation device and a preparation method of a lead-based master alloy by a molten salt galvanic cell method.

Background

In the grid material of lead storage battery, people have developed a lot of researches on lead-based alloy, wherein lead-antimony alloy and lead-calcium alloy are widely used. In recent years, researches show that the performance of the lead-based grid material can be favorably influenced by adding a small amount of active metal, so that the preparation of the lead-based active metal alloy is more and more important. At present, a doped smelting method is mostly adopted for preparing lead alloy, and a molten salt electrolysis method has certain research and application. However, when the opposite-doping smelting method is implemented, because the melting point of some doped active metals is higher, if the temperature is not enough, the content of the active metals in the molten lead alloy is less, so that the active metals are difficult to uniformly mix, and in order to avoid influencing the preparation efficiency and quality of the alloy, the temperature must be heated to a higher temperature to ensure that the metals are fully melted and mixed, so the energy consumption is higher; the molten salt electrolysis method is to obtain active metal at a cathode by electrolyzing chloride to obtain the lead-based master alloy, but chlorine generated at an anode pollutes the environment. The invention with the publication number of CN103943865A discloses a graphene lead alloy, a preparation method and application thereof in 2014, 7 and 23. The components and the weight percentage content are as follows: 0.0015 to 0.1 percent of graphene and 96.96 percent of lead; and any one, any two, any three or any four of tin, aluminum, strontium and copper thereof. The weight percentage of the tin is 0.1-1.6%, the weight percentage of the aluminum is 0.015-0.05%, the weight percentage of the strontium is 0.05-1.2%, and the weight percentage of the copper is 0.05-0.09%. The invention also protects the preparation method and the application of the alloy for the grid. The graphene lead alloy provided by the invention is used for the grid, and has the advantages of high hardness, good toughness, flowability and creep resistance, strong corrosion resistance, firm combination of the grid and an active substance, no barrier layer, less water loss of a prepared battery and long cycle life. The invention does not relate to a device for preparing the lead alloy.

Disclosure of Invention

The invention provides a molten salt primary battery method lead-based master alloy preparation device with low energy consumption and low pollution and a preparation method using the device, aiming at overcoming the defects that the conventional preparation method of the lead-based master alloy has high energy consumption and high pollution.

The technical scheme of the invention is as follows: the utility model provides a device is prepared to molten salt galvanic cell method lead-based master alloy, includes resistance heating furnace, reactor and crucible, and the inside of resistance heating furnace is located to the reactor, and the crucible is located in the reactor, and crucible bottom center is equipped with controllable defeated plumbous mouthful, even has anodal guide arm on the crucible, is equipped with the active metal of connecting the negative pole guide arm in the crucible, still is equipped with agitating unit in the crucible. The device for preparing the lead-based master alloy by the molten salt primary battery method is used for implementing the molten salt electrolysis method, massive active metal is used as a battery cathode, molten salt is used as a reaction medium and electrolyte, lead liquid is used as an anode, a crucible is used for containing lead, the molten salt and the active metal which participate in the reaction, the crucible is heated by a heating furnace to melt the molten salt and the lead, and a stirring device can stir the lead liquid to accelerate the uniform fusion of the lead liquid and the active metal ions. The active metal block is used as a battery cathode and loses electrons to generate active metal ions which enter molten salt, the active metal ions are reduced at a liquid lead cathode to generate metal to further generate lead-active metal alloy, the essential of the active metal alloy is to separate the active metal and lead by the molten salt to realize indirect alloy reaction, and the reaction speed is controlled by the mass transfer speed of the active metal ions in the molten salt. The molten salt alloy reaction can control the dissolution and deposition rate of the active metal, avoid the direct reaction of the active metal and the vertical to generate a large amount of heat, and convert the heat energy into electric energy. The whole alloy reaction process does not consume molten salt electrolyte, and the molten salt can be reused. When the molten salt primary battery method lead-based master alloy preparation device works, the hot melting of active metal is not needed, so that the energy is saved; and the process of electrolyzing chloride is not needed, harmful chlorine gas is not generated, and the method is more environment-friendly.

Preferably, the stirring device comprises a rotating shaft, a stirring nacelle and a rotating shaft driving mechanism, the rotating shaft driving mechanism is connected to the stirring nacelle, the rotating shaft is in transmission connection with the rotating shaft driving mechanism, a stirring plate is arranged on the rotating shaft, a top plate is arranged at the top of the stirring nacelle, the rotating shaft driving mechanism comprises a transmission assembly and a motor, the transmission assembly is connected between the motor and the rotating shaft, and the transmission assembly and the motor are arranged on the top plate of the stirring nacelle. The top plate of the stirring nacelle provides a mounting support for the transmission assembly and the motor, and the motor drives the rotating shaft to rotate through the transmission assembly. The rotating shaft driving mechanism can drive the rotating shaft to rotate, so that the stirring plate on the rotating shaft stirs the lead liquid, the lead liquid is stirred, the lead liquid is uniformly mixed, and the quality of the alloy is improved.

Preferably, the rotating shafts are multiple, the transmission assembly comprises chain wheels and transmission chains, the chain wheels are arranged at the middle upper ends of the rotating shafts, the transmission chains are connected between the adjacent chain wheels, and the motor is in transmission connection with one chain wheel. Through this transmission assembly, many pivots of motor synchronous drive rotate.

Alternatively, the pivot is many, transmission assembly includes the gear, and the gear is located the well upper end of each pivot and meshes in proper order, and the motor is connected with a gear drive. Through this transmission assembly, many pivots of motor synchronous drive rotate.

Preferably, the stirring basket is provided with an outer frame, the outer frame is in sliding fit with the inner wall of the crucible, and the stirring basket is connected with a lifting mechanism. Under elevating system's drive, the stirring nacelle can go up and down, and then drives the pivot and change the high position, makes to stir the board and can stir on the different degree of depth of lead liquid, promotes lead liquid and active metal ion homogeneous mixing. The stirring gondola can form nested cooperation with the crucible, helps the stirring gondola steadily go up and down along the crucible axis.

Preferably, the bottom of the mixing pod is provided with a mesh. After the lead is melted into lead liquid, impurities which are not melted may exist, and after the stirring nacelle rises to a sufficient height, the net piece can play a role of a filter screen, and scum and sediment which are not melted can be fished out.

Preferably, a valve is arranged on the controllable lead delivery port. The valve can control the outflow and the flow of the lead liquid.

Preferably, the positive electrode lead and the negative electrode lead are made of an inert metal or a transition metal. The anode guide rod and the cathode guide rod made of inert metal are not easy to react and are corrosion resistant.

A method for preparing a lead-based master alloy by a molten salt primary battery method comprises the following steps:

placing a reactor in a resistance heating furnace, and then placing a dry and clean crucible in the reactor;

closing a controllable lead conveying port, adding a lead sample into a crucible, connecting the crucible with an anode guide rod, heating to 400 ℃ to melt lead, starting the stirring device to stir for at least 5 minutes, and then fishing slag to remove surface impurities;

thirdly, slowly adding the dried and standby NaCl-KCl-BaCl2 electrolyte to the surface of the lead liquid in the crucible within 2-3 minutes; raising the temperature to 600 ℃ for salt melting treatment, and when the temperature is stable, melting the salt in the crucible; placing active metal in a stainless steel basket connected with a cathode guide rod, rapidly placing the active metal in molten salt, covering, and penetrating an anode guide rod, a cathode guide rod and an argon inlet and outlet pipe through a cover; continuously introducing argon into the reactor, and forming an argon atmosphere in the reactor;

controlling the temperature at 600 ℃, taking the active metal as the cathode of the primary battery, taking the lead liquid as the anode, performing constant current discharge between the cathode and the anode, dissolving the active metal cathode to generate ions which enter molten salt, and alloying the active metal ions with the lead anode at the cathode to generate lead-active metal alloy; after the active metal on the negative electrode is consumed, stabilizing for at least half an hour;

and step five, reducing the temperature and stabilizing at 400-500 ℃, solidifying molten salt, and discharging the liquid lead-active metal alloy from the controllable lead delivery port.

The invention utilizes the principle of a molten salt primary battery to produce the lead-based active metal master alloy, a heating furnace melts the molten salt and the lead in a non-oxidation environment formed by inert gas at 600 ℃, the active metal and the lead are separated by the molten salt, indirect alloy reaction is realized, the dissolution and deposition rate of the active metal can be controlled by the molten salt alloy reaction, a large amount of heat generated by direct reaction of the active metal and the lead is avoided, the heat energy can be converted into electric energy, the reaction temperature can be reduced, and the energy consumption and the loss of the lead at high temperature are reduced. And because the active metal enters the lead liquid in an ionic state dissolved in the molten salt, the problems of alloy segregation and segregation caused by uneven diffusion can be effectively avoided, and therefore, the alloy distribution is more uniform and stable.

The invention has the beneficial effects that:

low energy consumption, less pollution and high quality of product. The lead-based master alloy is prepared by adopting the method, the high temperature required for melting active metal in a smelting method is not required, chlorine generated by a molten salt electrolysis method is not required, the energy is saved, the environment is protected, the formed alloy components are more uniform and stable, and the follow-up lead storage battery grid material has better performance.

The implementation is convenient. The electrolyte can be recycled, the reaction speed is high, the amount of lead and active metal is changed according to the requirement of the required alloy content every time, and the preparation of the lead-based master alloy by the molten salt primary battery method can be more conveniently implemented.

Drawings

FIG. 1 is a schematic structural diagram of the present invention;

FIG. 2 is another schematic structural view of the present invention;

FIG. 3 is a schematic view showing the structure of the resistance heating furnace of the present invention;

FIG. 4 is a sectional view of the resistance heating furnace of the present invention;

FIG. 5 is a schematic view of a crucible of the present invention.

In the figure, 1-resistance heating furnace, 2-reactor, 3-crucible, 4-controllable lead conveying port, 5-positive guide rod, 6-negative guide rod, 7-stainless steel basket, 8-fused salt, 9-lead liquid, 10-rotating shaft, 11-stirring nacelle, 12-stirring plate, 13-chain wheel, 14-driving chain, 15-gear, 16-lifting motor, 17-lifting rod, 18-motor, 19-top plate, 20-mesh, 21-lifting driver, 22-lifting rod driving gear and 23-lifting motor support.

Detailed Description

The invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings.

Example 1:

as shown in fig. 1 and 3 to 5, the molten salt galvanic cell method lead-based master alloy preparation device comprises a resistance heating furnace 1, a stainless steel reactor 2 and a stainless steel crucible 3, wherein the reactor 2 is arranged in the resistance heating furnace 1, the crucible 3 is arranged in the reactor 2, and the resistance heating furnace 1, the reactor 2 and the crucible 3 are all rotating bodies. The center of the bottom of the crucible 3 is welded with a controllable lead delivery port 4, the crucible 3 is connected with an anode guide rod 5, active metal connected with a cathode guide rod 6 is arranged in the crucible 3, and the active metal is aluminum in the embodiment. Still be equipped with agitating unit in the crucible 3, agitating unit includes pivot 10, stirring nacelle 11 and pivot actuating mechanism, and pivot actuating mechanism connects on stirring nacelle 11, and pivot 10 is connected with pivot actuating mechanism transmission, is equipped with on the pivot 10 and stirs board 12. The stirring nacelle 11 is provided with an outer frame, so that the stirring nacelle 11 is integrally cage-shaped, the outer frame of the stirring nacelle 11 is in sliding fit with the inner wall of the crucible 3, a top plate 19 is arranged at the top of the stirring nacelle 11, the rotating shaft driving mechanism comprises a transmission assembly and a motor 18, the transmission assembly is connected between the motor 18 and the rotating shaft 10, and the transmission assembly and the motor 18 are arranged on the top plate 19 of the stirring nacelle 11. The rotating shafts 10 are three and arranged into a regular triangle, the transmission assembly comprises chain wheels 13 and transmission chains 14, the chain wheels 13 are arranged at the middle upper ends of the rotating shafts 10, the transmission chains 14 are connected between the adjacent chain wheels 13, and the motor 18 is overhead through a motor base and is in transmission connection with the chain wheels 13. The inner wall of the reactor 2 is radially fixed with a radial beam, the center of the radial beam is provided with a central hole of the radial beam, and a linear bearing is arranged in the central hole of the radial beam. The stirring nacelle 11 is connected with a lifting mechanism, the lifting mechanism comprises a lifting motor 16 and a lifting rod 17, a lower optical axis section and an upper thread section are arranged on the lifting rod 17, and the optical axis section is connected in a linear bearing in a central hole of the radial beam in a sliding mode in a matching mode. The fixed lifting drive support of radial roof beam centre bore top port department, the lifting drive support have with the coaxial lifter clearing hole of radial roof beam centre bore, a lifting drive 21 of lifter clearing hole internal rotation installation, lifting drive 21 is the rotator that a cross-section is the well font, lifting drive 21 is equipped with the driver centre bore along the axial, the first section inner wall of driver centre bore is equipped with the spiral channel, the screw thread section closes with this spiral channel adaptation soon. The outer peripheral surface of the middle radial projection of the lifting driver 21 is provided with a tooth. A gantry type lifting motor support 23 is fixed on the radial beam, the lifting motor 16 is fixed on the bottom surface of the lifting motor support 23, an output shaft of the lifting motor 16 is exposed out of the top surface of the lifting motor support, a lifting rod driving gear 22 is connected to an output shaft of the lifting motor 16 in a key mode, and the lifting rod driving gear 22 is meshed with the grinding teeth on the outer peripheral surface of the lifting driver 21. The top surface of the lifting motor support 23 is provided with a through hole capable of accommodating the lifting driver support, the lifting driver support is embedded in the through hole, the top of the lifting driver 21 is provided with a pressing plate, the pressing plate is fixed on the top surface of the lifting motor support through a bolt and a support column, the pressing plate is provided with a through hole capable of accommodating the top of the lifting driver 21, the top of the lifting driver 21 is connected with the joint part of the pressing plate through a bearing, and the axial position of the lifting driver 21 is limited by the pressing plate and the lifting driver support. The top plate 19 is fixed at the bottom end of the optical axis section of the lifting rod 17, three mutually isolated conducting rings are sleeved on the circumferential surface of the optical axis section near the bottom end, three cables of the motor 18 are respectively in one-to-one contact with the conducting rings through carbon brushes, the conducting rings are respectively connected with conducting wires, and the conducting wires are led to the outside through respective wiring grooves embedded in the optical axis section. When the lifting rod 17 rotates to lift, the top plate 19 also drives the rotating shafts 10 to integrally rotate, so that the lead liquid and the active metal in the crucible 3 can be promoted to be more fully and quickly mixed. The rotating shaft 10, the lifting driver 21, the lifting motor 16 and the lifting rod driving gear 22 are all made of industrial ceramics. The lifting motor 16 and the motor 18 are controlled by keys. The mixing basket 11 is provided at its bottom with a mesh 20 made of industrial ceramic. A valve is arranged on the controllable lead delivery port 4. The positive electrode lead 5 and the negative electrode lead 6 are made of refractory metal, molybdenum in this embodiment, of inert metal or transition metal.

A method for preparing a lead-based master alloy by a molten salt primary battery method comprises the following steps:

step one, placing a reactor 2 in a resistance heating furnace 1, and then placing a dry and clean crucible 3 in the reactor 2;

step two, closing the controllable lead conveying port 4, and controlling the lifting motor 16 and the motor 18 to enable the stirring nacelle 11 to descend to the bottom in the reactor 2 and the rotating shaft 10 to descend to the bottom in the crucible 3; adding 10Kg of lead into a crucible 3, connecting the crucible 3 with an anode guide rod 5, temporarily sealing without covering, heating to 400 ℃ to melt the lead, starting a motor 18 to enable a stirring device to stir the lead liquid 9 for 5 minutes, then stopping the stirring device, starting a lifting motor 16, lifting a stirring nacelle 11, filtering the lead liquid once from bottom to top by a net sheet 20 to remove impurities in the lead liquid and on the surface of the lead liquid;

step three, the stirring nacelle 11 is cleaned and then is lowered to the bottom of the reactor 2 again, and 3.2Kg of dried and standby NaCl-KCl-BaCl2 electrolyte is slowly added to the surface of the lead liquid in the crucible 3 within 2.5 minutes; raising the temperature to 600 ℃ for salt melting treatment, and when the temperature is stable, melting the NaCl-KCl-BaCl2 salt in the crucible 3, and controlling the depth of the molten salt to be about 5 cm; 100g of active metal is placed in a stainless steel basket 7 connected with a cathode guide rod 6 and is quickly placed in molten salt, a cover is covered, an anode guide rod 5, a cathode guide rod 6 and an argon inlet and outlet pipe penetrate through an opening in the cover, and gaps between the anode guide rod 5, the cathode guide rod 6, the argon inlet and outlet pipe and the opening in the cover are sealed; then continuously introducing argon into the reactor 2 through an argon inlet pipe on the reactor 2, discharging the argon from an argon outlet pipe, and forming an argon atmosphere in the reactor;

controlling the temperature at 600 ℃, taking the active metal as the cathode of the primary battery, taking the lead liquid as the anode, performing constant current discharge between the cathode and the anode, dissolving the active metal cathode to generate ions, entering the molten salt 8, and alloying the active metal ions with the lead anode at the cathode to generate lead-active metal alloy fluid; the lifting motor 16 and the motor 18 are started, the motor 18 drives the rotating shaft 10, the lead liquid 9 and the molten active metal are stirred through the stirring plate 12, the direction of the lifting motor 16 is repeatedly changed, the rotating shaft 10 is repeatedly lifted to change the height position, and the stirring plate 12 is stirred at different depths of the lead liquid 9 layer to promote the lead liquid and the active metal ions to be uniformly mixed; after the active metal on the cathode is consumed, stabilizing for at least half an hour, and simultaneously lifting the stirring nacelle 11 to be above the molten salt layer;

and step five, reducing the temperature and stabilizing the temperature at 450 ℃, solidifying molten salt, and discharging the liquid lead-active metal alloy from the controllable lead conveying port 4.

Example 2:

as shown in fig. 2, the active metal in this embodiment is zinc. The rotating shafts 10 are four and are arranged into an arc shape coaxial with the crucible 3, the transmission assembly comprises gears 15, the gears 15 are arranged at the middle upper ends of the rotating shafts 10 and are all meshed in sequence, and the motor is overhead through a motor base and is in transmission connection with the gears 15. The positive electrode guide rod 5 and the negative electrode guide rod 6 are made of platinum. Stirring for 6 minutes by using the stirring device in the second step; in the third step, dried and standby NaCl-KCl-BaCl2 electrolyte is slowly added to the surface of the lead liquid in the crucible 3 within 2 minutes; in the fifth step, the temperature is stabilized at 400 ℃. The rest is the same as example 1.

Example 3:

the positive electrode guide rod 5 and the negative electrode guide rod 6 are made of titanium. Stirring for 8 minutes by using the stirring device in the second step; in the third step, the stirring nacelle 11 is lowered to the bottom of the reactor 2 again after the mesh is removed, and dried and standby NaCl-KCl-BaCl2 electrolyte is slowly added to the surface of the lead liquid in the crucible 3 within 3 minutes; in the fifth step, the temperature is stabilized at 500 ℃. The rest is the same as example 1.

Example 4:

the rotating shaft 10 is one. The rest is the same as example 1.

Claims (9)

1. The utility model provides a device is prepared to former battery method lead-base master alloy of fused salt, characterized by includes resistance heating furnace (1), reactor (2) and crucible (3), the inside of resistance heating furnace (1) is located in reactor (2) is located in crucible (3), crucible (3) bottom center is equipped with controllable defeated plumbous mouthful (4), even there is anodal guide arm (5) on crucible (3), be equipped with the active metal of connecting negative pole guide arm (6) in crucible (3), still be equipped with agitating unit in crucible (3).

2. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 1, wherein the stirring device comprises a rotating shaft (10), a stirring nacelle (11) and a rotating shaft driving mechanism, the rotating shaft driving mechanism is connected to the stirring nacelle (11), the rotating shaft (10) is in transmission connection with the rotating shaft driving mechanism, a stirring plate (12) is arranged on the rotating shaft (10), a top plate is arranged on the top of the stirring nacelle (11), the rotating shaft driving mechanism comprises a transmission assembly and a motor, the transmission assembly is connected between the motor and the rotating shaft (10), and the transmission assembly and the motor are arranged on the top plate of the stirring nacelle (11).

3. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 2, wherein the number of the rotating shafts (10) is multiple, the transmission assembly comprises chain wheels (13) and transmission chains (14), the chain wheels (13) are arranged at the middle upper ends of the rotating shafts (10), the transmission chains (14) are connected between adjacent chain wheels (13), and the motor is in transmission connection with one chain wheel (13).

4. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 2, wherein the number of the rotating shafts (10) is multiple, the transmission assembly comprises gears (15), the gears (15) are arranged at the middle upper ends of the rotating shafts (10) and are sequentially meshed, and the motor is in transmission connection with one gear (15).

5. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 2, wherein the stirring basket (11) has an outer frame, the outer frame is in sliding fit with the inner wall of the crucible (3), and the stirring basket (11) is connected with a lifting mechanism.

6. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 5, wherein the bottom of the stirring nacelle (11) is provided with a mesh.

7. The molten salt galvanic cell method lead-based master alloy preparation device according to claim 1, wherein a valve is arranged on the controllable lead delivery port (4).

8. The molten salt galvanic cell method lead-based master alloy preparation apparatus according to any one of claims 1 to 7, wherein the positive electrode guide rod (5) and the negative electrode guide rod (6) are made of an inert metal or a transition metal.

9. A method for preparing a lead-based master alloy by a molten salt primary battery method is characterized by comprising the following steps:

step one, a reactor (2) is placed in a resistance heating furnace (1), and then a dry and clean crucible (3) is placed in the reactor (2);

closing the controllable lead conveying port (4), adding a lead sample into the crucible (3), connecting the crucible (3) with the positive guide rod (5), heating to 400 ℃ to melt lead, starting the stirring device to stir for at least 5 minutes, and then fishing slag to remove surface impurities;

thirdly, slowly adding the dried and standby NaCl-KCl-BaCl2 electrolyte to the surface of the lead liquid in the crucible (3) within 2-3 minutes; raising the temperature to 600 ℃ for salt melting treatment, and when the temperature is stable, melting the salt in the crucible (3); placing the active metal in a stainless steel basket connected with a cathode guide rod (6), quickly placing the active metal in molten salt, covering, and enabling an anode guide rod (5), the cathode guide rod (6) and an argon inlet and outlet pipe to penetrate through a cover; continuously introducing argon into the reactor (2) to form an argon atmosphere in the reactor;

controlling the temperature at 600 ℃, taking the active metal as the cathode of the primary battery, taking the lead liquid as the anode, performing constant current discharge between the cathode and the anode, dissolving the active metal cathode to generate ions which enter molten salt, and alloying the active metal ions with the lead anode at the cathode to generate lead-active metal alloy; after the active metal on the negative electrode is consumed, stabilizing for at least half an hour;

and step five, reducing the temperature and stabilizing at 400-500 ℃, solidifying molten salt, and discharging the liquid lead-active metal alloy from the controllable lead delivery port (4).

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