CN111705337B - Method for preparing lead-calcium master alloy by molten salt galvanic cell method - Google Patents
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Abstract
The invention discloses a method for preparing a lead-calcium master alloy by a molten salt primary battery method, belongs to the technical field of lead storage batteries, and solves the problems that the lead-calcium master alloy prepared by the prior art is very uneven in combination or generates harmful gas in the preparation process and the like. The method comprises the following steps: step 1, placing a crucible in a lead melting furnace, and melting lead into lead liquid at 350-400 ℃; step 2, adding halide salt into a crucible, and melting to obtain molten salt; step 3, placing a certain mass of metal calcium in a stainless steel basket and placing the metal calcium in molten salt; forming a primary battery by using metal calcium, molten salt and lead liquid, wherein the lead liquid is a positive electrode of the primary battery, the molten salt is an electrolyte, and the metal calcium is a negative electrode; constant current discharge is carried out between the positive electrode and the negative electrode, calcium ions are generated by dissolving metal calcium and enter molten salt, and the calcium ions are alloyed at the positive electrode of the lead liquid to generate lead-calcium master alloy; and 4, after the metal calcium is completely consumed, reducing the temperature to 350-500 ℃, solidifying molten salt, and discharging the liquid lead-calcium master alloy from the bottom. The method is suitable for preparing the lead-calcium master alloy.
Description
Technical Field
The invention belongs to the technical field of lead storage batteries, and particularly relates to a method for preparing a lead-calcium master alloy by a molten salt primary battery method.
Background
Since the advent of lead storage batteries, a great deal of research has been conducted on a wide variety of lead alloy-based grid materials. At present, the most widely used materials for the storage battery are lead-antimony-based alloy and lead-calcium alloy. In 1881, lead-antimony alloy replaces pure lead to make electrode grid, greatly improving the manufacturing process of lead storage battery and batteryThe performance becomes an important improvement in the development process of lead storage batteries, and has occupied an important position for more than 100 years later, but a plurality of problems appear in the use process: 1. the resistance of the lead-antimony alloy is large; 2. the existence of antimony can reduce the decomposition voltage of water, the water is easy to decompose during charging, the hydrogen evolution amount of the storage battery during overcharge and storage can be accelerated, and the self-discharge of the battery is increased during storage, so that the storage battery using the lead-antimony alloy grid cannot be made into a sealed type, and water needs to be added into the battery frequently; 3. SbH gas evolved during overcharge3Is toxic; 4. poor casting performance of lead-antimony alloy, etc. The lead-calcium alloy has the greatest advantage of being maintenance-free, and as a lead storage battery grid material which can be maintenance-free, the lead-calcium alloy has a series of advantages, but the lead-calcium alloy also has some defects in the use process, such as easy burning loss of calcium in the melting process. Based on this, people add the working alloy in the form of master alloy, and reduce burning loss.
At present, the preparation process of the lead-calcium master alloy mainly comprises a pair-doped smelting method and a molten salt electrolysis method. The opposite-doping smelting method is a direct alloying process and is carried out in a vacuum induction furnace. The method comprises the following steps of melting lead in a lead melting furnace, fishing slag after the lead is completely melted, removing surface impurities, adding calcium into the furnace, heating to 750 ℃ under an inert atmosphere, stirring for a period of time, and cooling to obtain the lead-calcium master alloy. And cutting off part of the master alloy for later use, continuously melting metal lead, adding the previously prepared master alloy into a lead melting furnace after complete melting, stirring, dredging slag, and finally preparing the required lead alloy through a pouring device or a die. The nature of the doping and melting method is physical mixing, and problems of uneven mixing, serious alloy segregation and the like can be caused. The lead-calcium master alloy prepared by the molten salt electrolysis method is prepared by taking graphite as an anode, taking lead liquid as a cathode and halide salt as electrolyte, and carrying out constant current electrolysis at 600 ℃ to obtain metal calcium at the cathode and generate gas at the anode, wherein the halide salt is required to be continuously supplemented in the production process. Although the molten salt electrolysis is an ion deposition process, the alloying effect is better than that of direct smelting, toxic gas is generated in the process, and halide salt needs to be continuously supplemented into the electrolyte.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for preparing a lead-calcium master alloy by a molten salt galvanic cell method, so as to solve the problems of uneven mixing of the lead-calcium master alloy prepared by the prior art or harmful gas generation in the preparation process.
The purpose of the invention is mainly realized by the following technical scheme:
a method for preparing a lead-calcium master alloy by a molten salt galvanic cell method comprises the following steps:
step 1, placing a crucible in a lead melting furnace, and melting lead into lead liquid at 350-400 ℃;
step 2, adding the halide salt into a crucible, and melting the halide salt in the crucible at 600-700 ℃ to obtain molten salt;
step 3, placing a certain mass of metal calcium in a stainless steel basket and placing the metal calcium in molten salt;
the metal calcium, the molten salt and the lead liquid form a primary battery, the lead liquid is a positive electrode of the primary battery, the molten salt is an electrolyte, and the metal calcium is a negative electrode; constant current discharge is carried out between the positive electrode and the negative electrode, calcium ions are generated by dissolving metal calcium and enter molten salt, and the calcium ions are alloyed at the positive electrode of the lead liquid to generate lead-calcium master alloy;
and 4, after the metal calcium is completely consumed, reducing the temperature to 350-500 ℃, solidifying molten salt, and discharging the liquid lead-calcium master alloy from the bottom.
And further, the method comprises the step 5 of raising the temperature to 600-700 ℃, adding new calcium metal negative electrodes and new lead positive electrodes, and continuing to prepare the alloy.
Further, in step 1, a stirring device is used for stirring the lead.
Further, after the lead is melted in the step 1, slag is fished, and surface impurities are removed.
Further, the crucible is a graphite crucible or a stainless steel crucible.
Further, the halide salt is one or more of sodium chloride, magnesium chloride, potassium chloride and calcium chloride.
Further, the halide salt comprises sodium chloride, and the mole fraction of the sodium chloride is more than or equal to 40%.
Further, the halide salt is a mixed salt of NaCl and KCl, and the molar ratio of the NaCl to the KCl is (0.45-0.55): (0.45-0.55).
Further, the halide salt in the step 2 is dried before being added into the crucible.
Further, the halide salt is added into the crucible within 1 to 30 minutes.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) the invention utilizes the difference of electrode potentials of metal calcium and liquid metal lead in electrolyte halide salt to generate potential difference, the metal calcium can be spontaneously dissolved to generate release electrons, and the release electrons are transferred to calcium ions losing electrons at the positive electrode through an external circuit, so that the electrons obtained by the calcium ions on the positive electrode of the liquid metal lead are reduced into metal and are alloyed with the liquid lead. The whole process is a spontaneous reaction, does not need the outside to provide energy, and converts the chemical energy of the process into the electric energy, thereby achieving the effect of saving energy consumption.
2) The method does not generate toxic gas in the whole process, the electrolyte can be repeatedly used, the electrolyte does not need to be supplemented all the time, and only the anode lead and the cathode calcium need to be continuously replaced. And the high-temperature molten salt has high ion conduction rate, so that the discharge can be completed quickly, and the reaction speed is high.
3) The method can avoid the danger caused by the release of a large amount of heat due to the high-temperature contact of lead and calcium. The method of the invention uses the liquid molten salt to isolate air, has extremely low metal lead and calcium burning loss rate, and reduces economic loss caused by burning loss.
4) The invention adopts the stainless steel basket to contain the calcium metal, is convenient to place in the fused salt, and has the advantages of easy preparation, lower price and corrosion resistance. The basket can be set up to the cuboid or be similar to the basket shape, and the foremost has the gap, can carry out the material exchange with the lead liquid, makes calcium all contact with the electrolyte for the reaction is abundant.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
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The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a process flow chart of preparing a lead-calcium master alloy by a molten salt primary battery method.
Detailed Description
A method for preparing a lead-calcium master alloy by a molten salt galvanic cell method will be described in further detail with reference to specific examples, which are provided for comparison and explanation purposes only, and the present invention is not limited to these examples.
The invention provides a method for preparing a lead-calcium master alloy by a molten salt primary battery method. Because the electrode potentials of the metal calcium and the liquid metal lead in the halide salt electrolyte are different, and a potential difference is generated, the potential difference between the two electrodes is utilized to design a closed-loop galvanic cell. The method is characterized in that metal calcium is used as a negative electrode, liquid metal lead is used as a positive electrode, halide salt is used as electrolyte, the metal calcium is dissolved under the action of potential difference, electrons are lost to generate ions and enter molten salt, the electrons reach the liquid metal lead on the positive electrode through an external circuit, and at the moment, according to the Nernst equation, the method can be known as follows:
Eeqis a metal ion An+Equilibrium electrode potential during deposition in liquid metal B;
Eθ A n+ /Ais an electricity pair An+A standard electrode potential of/a;
r is a gas constant; t is the molten salt temperature; f is a Faraday constant; n is the charge transfer number; alpha is alphaA(inPb)Is the activity value, alpha, of substance A in substance PbAn + is the activity value of the substance A in a molten salt system, and the electrolyte is continuously dissolved with the metal calcium on the negative electrodeCalcium ion concentration in the calcium salt is higher and higher, namely alphaAThe n + value is higher and higher, and the activity value of metal calcium in liquid metal lead is very low, namely alphaA(inPb)The value is small, and the two factors are that metal calcium cations in the electrolyte are preferentially precipitated on liquid metal lead by electron deposition and undergo alloying reaction to form the lead-calcium alloy. The essence is that the molten salt is used for separating calcium and lead to realize indirect alloy reaction, and the reaction speed is controlled by the mass transfer speed of metal calcium ions in the molten salt. The molten salt alloy reaction can control the dissolution and deposition rate of calcium, avoid the direct reaction of calcium 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.
A method for preparing a lead-calcium master alloy by a molten salt galvanic cell method is shown in figure 1 and comprises the following steps:
step 1, placing a crucible in a lead melting furnace, and melting lead into lead liquid at 350-400 ℃;
step 2, adding the halide salt into a crucible, and melting the halide salt in the crucible at 600-700 ℃ to obtain molten salt;
step 3, placing a certain mass of metal calcium in a stainless steel basket and placing the metal calcium in molten salt;
the metal calcium, the fused salt and the lead liquid form a primary battery (a stainless steel basket filled with the calcium is used as a battery cathode, a crucible filled with the lead liquid is used as a battery anode, and the stainless steel basket and the crucible are connected by a guide rod to form an external circuit), the lead liquid is the primary battery anode, the fused salt is electrolyte, and the metal calcium is the cathode; constant current discharge is carried out between a positive electrode and a negative electrode (the electrode potential of calcium and lead in electrolyte is certain, so the current passing during the reaction is also approximately stable), metal calcium is melted to generate calcium ions which enter molten salt, and the calcium ions are reduced and alloyed at the positive electrode of lead liquid to generate a lead-calcium master alloy;
and 4, after the metal calcium is completely consumed, reducing the temperature to 350-500 ℃, solidifying molten salt, and discharging the liquid lead-calcium master alloy from the bottom.
And further, the method comprises the step 5 of raising the temperature to 600-700 ℃, adding new calcium metal negative electrodes and new lead positive electrodes, and continuing to prepare the alloy. Preferably, the lead is added first and the calcium is added after the halide salt is melted.
Preferably, in step 1, the lead is stirred by a stirring device, so that the lead is heated uniformly and melting of the lead is accelerated. And (4) fishing slag after the lead is melted, and removing surface impurities.
Illustratively, the crucible is a graphite crucible or a stainless steel crucible.
The quality of the lead and calcium depends on the demand of the lead-calcium master alloy, and the halide, after melting, as an electrolyte, needs to be highly covered with calcium, and the quality of the halide is also related to the diameter of the crucible. Illustratively, the mass of the added lead is 1t, the mass of the halide salt is 10-50 kg, and the mass of the metal calcium is 0.6-1.8 kg.
And (3) drying the halide salt in the step (2) before adding the halide salt into the crucible, wherein the halide salt is added into the crucible within 1-30 minutes.
The halide salt is one or more of sodium chloride, magnesium chloride, potassium chloride, and calcium chloride. The effect on the reaction rate is the potential difference of calcium and lead at different electrolytes.
Preferably, the halide salt is a mixed salt of two or three salts including sodium chloride, the mole fraction of the sodium chloride being above 40%. Illustratively, the halide salt is a mixed salt of NaCl and KCl, and the molar ratio is (0.45-0.55): (0.45-0.55). Illustratively, the halide salt is a mixed salt of sodium chloride, calcium chloride and magnesium chloride, and the molar ratio of the sodium chloride, the calcium chloride and the magnesium chloride is 0.4: 0.33: 0.27. illustratively, the halide salt is a mixed salt of sodium chloride, calcium chloride and potassium chloride, the molar ratio of sodium chloride, calcium chloride and potassium chloride being 0.43: 0.31: 0.26.
the stainless steel basket is easy to prepare, has lower price and is more corrosion-resistant. The basket can be arranged into a cuboid or a shape similar to the basket, and is mainly provided with a gap which can exchange substances with lead liquid. The calcium is brought into full contact with the electrolyte, allowing for full reaction.
Example 1
Putting a dry and clean graphite crucible into a lead melting furnace, adding 1t of lead into the crucible, and putting the crucible into a stirring device; raising the temperature to 350-400 ℃, starting the stirrer, stirring for 3-5 minutes, and then fishing out the slag to remove surface impurities.
Adding 10-50 kg of halide salt which is dried for later use into a crucible within 1-30 minutes, wherein the halide salt is a mixed salt of NaCl and KCl, and the molar ratio of the NaCl to the KCl is 0.55: 0.45, covering the cover, and raising the temperature to 600-700 ℃. When the temperature is stable, the salt in the crucible is melted and used as the electrolyte. 0.6-1.8 kg of metal calcium is placed in a stainless steel basket and placed in molten salt to serve as a primary battery cathode, and lead liquid serves as a cathode.
Constant current discharge is carried out between the anode and the cathode, ions generated by dissolving the metal calcium cathode enter molten salt, and the ions generate calcium at the cathode (the lead anode) and further generate lead-calcium master alloy through alloying.
When the consumption of metal calcium on the negative electrode is finished, the temperature is reduced to 350-500 ℃, molten salt is solidified, and liquid lead-calcium master alloy is discharged from the bottom to obtain a lead-calcium alloy with the mass ratio of 1000: (0.6-1.8) a lead-calcium master alloy; and raising the temperature to 600-700 ℃, adding a new calcium metal cathode and a new lead cathode, and continuing to prepare the alloy.
Example 2
A method for preparing a lead-calcium master alloy by a molten salt primary battery method. Firstly, placing a dry and clean graphite crucible in a lead melting furnace, adding 1t of lead into the crucible, and placing the crucible into a stirring device; raising the temperature to 350 ℃ for lead melting, starting a stirrer, stirring for 5 minutes, then fishing out slag, and removing surface impurities; then 20kg of halide salt which is dried for later use is added into the crucible within 20 minutes, wherein the halide salt is a mixed salt of sodium chloride, calcium chloride and magnesium chloride, and the molar ratio of the sodium chloride to the calcium chloride to the magnesium chloride is 0.4: 0.33: 0.27. the lid was closed and the salt melting treatment was carried out by raising the temperature to 600 ℃. When the temperature is stable, the salt in the crucible is melted, 1kg of metal calcium is placed in a stainless steel basket and placed in the molten salt to be used as a cathode of the primary battery, and the lead liquid is used as an anode; constant current discharge is carried out between the cathode and the anode, the discharge temperature is 600 ℃ of the melting treatment temperature of the molten salt, the metal calcium cathode is dissolved to generate ions which enter the molten salt, and the ions are alloyed with the lead anode at the cathode to generate lead-calcium alloy; when the calcium on the negative electrode is completely consumed, the temperature is reduced to 500 ℃, the molten salt is solidified, and the liquid lead-calcium alloy is discharged from the bottom to obtain a lead-calcium alloy with the mass ratio of 1000: 1, lead-calcium master alloy; raising the temperature to 600 ℃, adding new calcium cathode and lead cathode, and continuing to prepare the alloy.
Example 3
A method for preparing lead-calcium alloy by a molten salt primary battery method. Putting a dry and clean graphite crucible into a lead melting furnace, adding 1t of lead into the crucible, and putting the crucible into a stirring device; the temperature is raised to 400 ℃, the stirrer is started and stirred for 4 minutes, and then slag is fished to remove surface impurities.
Adding 10kg of dried electrolyte for later use into a crucible within 10 minutes, wherein the halide salt is a mixed salt of sodium chloride, calcium chloride and potassium chloride, and the molar ratio of the sodium chloride to the calcium chloride to the potassium chloride is 0.43: 0.31: 0.26. the lid was closed and the temperature was raised to 700 ℃. When the temperature is stable, the salt in the crucible is melted and used as the electrolyte. 1.5kg of metal calcium is placed in a stainless steel basket and placed in molten salt to be used as a primary battery cathode, and lead liquid is used as a cathode.
Constant current discharge is carried out between the anode and the cathode, ions generated by dissolving the metal calcium cathode enter molten salt, and the ions generate calcium at the cathode (the lead anode) and further generate lead-calcium master alloy through alloying.
When the consumption of metal calcium on the negative electrode is finished, the temperature is reduced to 400 ℃, molten salt is solidified, and liquid lead-calcium master alloy is discharged from the bottom to obtain a lead-calcium alloy with the mass ratio of 1000: 1.5 of a lead-calcium master alloy; raising the temperature to 700 ℃, adding new calcium metal cathode and lead cathode, and continuing to prepare the alloy.
Example 4
A method for preparing lead-calcium alloy by a molten salt primary battery method. A method for preparing a lead-calcium master alloy by a molten salt primary battery method. Firstly, placing a dry and clean graphite crucible in a lead melting furnace, adding 1t of lead into the crucible, and placing the crucible into a stirring device; raising the temperature to 350 ℃ for lead melting, starting a stirrer, stirring for 5 minutes, then fishing out slag, and removing surface impurities; 20kg of halide salt dried for use are then added to the crucible over a period of 5 minutes. The lid was closed and the salt melting treatment was carried out by raising the temperature to 650 ℃. When the temperature is stable, the salt in the crucible is melted, 0.8kg of metal calcium is placed in a stainless steel basket and placed in the molten salt to be used as a primary battery cathode, and the lead liquid is used as a positive electrode; constant current discharge is carried out between the cathode and the anode, the discharge temperature is 650 ℃, the metal calcium cathode is dissolved to generate ions which enter the molten salt, and the ions are alloyed with the lead anode at the cathode to generate lead-calcium alloy; when the calcium on the negative electrode is completely consumed, the temperature is reduced to 500 ℃, molten salt is solidified, and liquid lead-calcium alloy is discharged from the bottom; and raising the temperature to 650 ℃, melting the molten salt, adding a new calcium cathode and a new lead anode, and continuing to prepare the alloy.
Example 5
A method for preparing lead-calcium alloy by a molten salt primary battery method. The difference from example 1 is that: the temperature is raised to 650 ℃ for salt melting treatment, the discharge temperature is 650 ℃, and the temperature is raised to 650 ℃ after the liquid lead-calcium alloy is discharged from the bottom, and the rest is the same.
Example 6
A method for preparing lead-calcium alloy by a molten salt primary battery method. The difference from example 1 is that: the halide salt is a mixed salt of NaCl and KCl, and the molar ratio of the NaCl to the KCl is 0.51: 0.49, the melting point of the molar ratio is 657 ℃, the temperature is raised to 700 ℃ for salt melting treatment, the discharge temperature is also 700 ℃, and after the liquid lead-calcium alloy is discharged from the bottom, the temperature is raised to 700 ℃, and the rest is the same.
Example 7
A method for preparing lead-calcium alloy by a molten salt primary battery method. The difference from example 2 is that: the halide salt is a mixed salt of sodium chloride, calcium chloride and magnesium chloride, and the molar ratio of the sodium chloride to the calcium chloride to the magnesium chloride is 0.5: 0.3: and (3) raising the temperature to 700 ℃ for salt melting treatment at 0.2, wherein the discharge temperature is 700 ℃, and after the liquid lead-calcium alloy is discharged from the bottom, the raising temperature is also 700 ℃, and the rest are the same.
The invention is characterized in that the difference of electrode potentials of metal calcium and liquid metal lead in electrolyte halide salt is utilized to generate potential difference, the metal calcium can be dissolved spontaneously to generate release electrons, and the release electrons are transferred to calcium ions losing electrons at the positive electrode through an external circuit, so that the electrons obtained by the calcium ions on the positive electrode of the liquid metal lead are reduced into metal and are alloyed with the liquid lead. The whole process is a spontaneous reaction, does not need the outside to provide energy, and converts the chemical energy of the process into the electric energy, thereby achieving the advantage of saving energy consumption. In addition, no toxic gas is generated in the whole process, no electrolyte is required to be added, and only the anode lead and the cathode calcium are required to be continuously replaced. Secondly, the high-temperature molten salt has high ion conduction rate, so that the discharge can be completed quickly, and the reaction speed is high. Thirdly, the method can avoid the danger caused by the release of a large amount of heat due to the high-temperature contact of lead and calcium. Finally, the method of the invention uses the liquid molten salt to isolate the air, the burning loss rate of the metal lead and calcium is extremely low, and the economic loss caused by burning loss is reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (3)
1. A method for preparing a lead-calcium master alloy by a molten salt galvanic cell method is characterized by comprising the following steps:
step 1, placing a crucible in a lead melting furnace, and melting lead into lead liquid at 350-400 ℃;
step 2, adding the halide salt into a crucible, and melting the halide salt in the crucible at 600-700 ℃ to obtain molten salt; the halide salt is a mixed salt of NaCl and KCl, and the molar ratio of the NaCl to the KCl is (0.45-0.55): (0.45-0.55);
step 3, placing a certain mass of metal calcium in a stainless steel basket and placing the metal calcium in molten salt;
separating calcium and lead by molten salt; realizing indirect alloy reaction;
forming a primary battery by using metal calcium, molten salt and lead liquid, wherein the lead liquid is a positive electrode of the primary battery, the molten salt is an electrolyte, and the metal calcium is a negative electrode; constant current discharge is carried out between the positive electrode and the negative electrode, calcium ions are generated by dissolving metal calcium and enter molten salt, and the calcium ions are alloyed at the positive electrode of the lead liquid to generate lead-calcium master alloy;
step 4, after the metal calcium is completely consumed, reducing the temperature to 350-500 ℃, solidifying molten salt, and discharging the liquid lead-calcium master alloy from the bottom;
step 5, raising the temperature to 600-700 ℃, adding new calcium metal negative electrodes and new lead positive electrodes, and continuing to prepare the alloy;
connecting a stainless steel basket filled with calcium as a battery cathode and a crucible filled with lead liquid as a battery anode by a guide rod to form an external circuit; the stainless steel basket is provided with a gap and can exchange substances with lead liquid, so that calcium is completely contacted with electrolyte;
the electrode potentials of the metal calcium and the liquid metal lead in the electrolyte halide salt are different to generate a potential difference, the metal calcium, the molten salt and the lead liquid form a primary battery, the metal calcium is spontaneously dissolved to generate released electrons, the released electrons are transmitted to calcium ions losing electrons at the positive electrode through an external circuit, and the electrons obtained by the calcium ions on the positive electrode of the liquid metal lead are reduced into metal and are alloyed with the liquid lead to generate a lead-calcium master alloy.
2. The method for preparing the lead-calcium master alloy by the molten salt galvanic cell method according to claim 1, wherein the crucible is a graphite crucible or a stainless steel crucible.
3. The method for preparing the lead-calcium master alloy by the molten salt primary battery method according to claim 1 or 2, wherein the halide salt is added into the crucible within 1-30 minutes.
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