CN111172563A - Method and device for electrolyzing antimony sulfide-containing material by using molten salt - Google Patents
Method and device for electrolyzing antimony sulfide-containing material by using molten salt Download PDFInfo
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Abstract
The invention discloses a method and a device for electrolyzing molten salt containing antimony sulfide materials. Mixing antimony sulfide-containing materials and inert molten salt, placing the mixture in an electrolysis device, heating for electrolysis and smelting, blowing inert gas into the electrolysis device to stir a molten pool in the smelting process, gradually enriching the lower layer in the device along with the low-temperature molten salt electrolysis to obtain a liquid antimony melt layer, and gradually enriching the liquid antimony melt layer in a flue gas collection device to obtain elemental sulfur. The invention strengthens the mass transfer of molten salt ions, produces high-grade antimony and elemental sulfur in one step and avoids the low-concentration SO in the traditional pyrometallurgical antimony smelting2The pollution to the environment. Has the advantages of low energy consumption, high antimony direct recovery rate, cleanness and environmental protection. The device of the invention is simple and practical, and good antimony can be obtained by processing antimony sulfide concentrate,The metallurgical effect of sulfur extraction.
Description
Technical Field
The invention relates to a clean metallurgy method and a device for obtaining refined antimony and elemental sulfur by molten salt electrolysis of antimony sulfide-containing materials, belonging to the field of nonferrous metallurgy.
Background
Antimony (Sb) is a silver-white brittle metal, and is an acid-resistant substance at normal temperature. It is a metal with wide application, and is praised as "fire-extinguishing and fire-proofing assistant and assistant", "strategic metal", "metal hardening agent", "fluorescent tube and electronic tube protective agent".
The existing production methods of metal antimony can be divided into two major categories, namely a pyrogenic method and a wet method. The technological process includes the first pelletizing or pelletizing antimony sulfide concentrate or antimony containing material, the subsequent adding the pelletized antimony sulfide concentrate or antimony containing material together with coke and flux into blast furnace, and volatilizing and smelting in the operation system of "low material column, thin material layer, high coke rate and hot furnace top" to volatilize and oxidize antimony sulfide and separate it from gangue and other impurities, and the produced antimony oxide and fume are collected in a condensing and dust collecting system and reduced in a reverberatory furnace to produce coarse antimony. The process has strong adaptability to raw materials and large processing capacity, but generally has the defects of high coke rate, large energy consumption, huge dust collecting system, complex operation and the like. Especially low concentration SO generated in the blast furnace volatilization smelting process2The smoke and heavy metal dust seriously pollute the ecological environment, and are an unsolved technical problem up to now.
In recent years, many researchers have tried to apply oxygen-rich bath smelting techniques (such as bottom blowing, top blowing, side blowing, etc.) that have been successful in the copper, lead, tin, etc. smelting industry to the smelting of antimony sulfide concentrates to solve the problem of low SO concentration in antimony smelting process2Pollution and the like. However, from theoretical analysis and a great deal of research results, the oxygen-enriched intensified smelting technology is difficult to be applied to antimony smelting at present. For antimony smelting, oxygen-enriched intensified smelting and SO2The acid preparation has a contradiction, and the core of the contradiction is that the antimony sulfide is easily decomposed at high temperature. This is an inherent property of antimony sulfide itself. Meanwhile, the outermost 5S due to Sb electron configuration2p3The structure ensures that Sb has multiple valence states under different oxygen potentials of strengthening smelting, so that Sb is easily formed at the oxygen direct injection port2O4、SbXOYAnd other easily nodulizing phases, and in severe cases, the furnace chamber, the flue and the like are blocked. So that the oxygen-enriched melting pool or flash smelting technology is difficult to be applied to antimony smelting. In addition, because the production scale is relatively small, the treatment capacity is difficult to expand and the like, the traditional antimony smelting method is adopted in most of China at presentThe production process comprises the steps of blast furnace volatilization and reverberatory furnace high-temperature reduction smelting. The concentration of sulfur dioxide generated in the smelting process can not meet the acid making requirement, most of sulfur dioxide is directly emptied after simple adsorption and desulfurization, the surrounding environment is polluted, and the sulfur in the antimony sulfide concentrate can not be recycled. In summary, the existing smelting process of antimony sulfide concentrate in China still has the defects of low efficiency, high energy consumption and low concentration of SO2Serious pollution and the like. The development of the antimony sulfide-containing material, particularly the low-carbon clean smelting of antimony sulfide concentrate, has great technical significance from the viewpoints of sufficient recovery and utilization of antimony and sulfur resources and environmental protection.
At the early stage, the inventor invented "a low-temperature molten salt electrolysis clean metallurgical method and device (201710775124.0) for antimony", but three major defects were found in the subsequent scale-up application practice: firstly, the molten salt is in a static state during electrolysis, and the mass transfer capacity of molten salt ions is not strong. After the electrolysis of the molten salt is finished, except that the decomposition rate of the antimony-containing material in the anode region is higher, the decomposition rate of the antimony material in the molten salt far away from the anode region is not high, and the farther away from the anode, the lower the decomposition rate is; and secondly, antimony obtained by decomposition is mixed in the molten salt in a fine antimony bead form and is difficult to separate and collect. In actual operation, a large amount of molten salt needs to be discharged through an antimony discharging port, the molten salt is cooled, finely ground and sieved to recover antimony beads, and operation is very troublesome, so that the molten salt is lost and is difficult to recycle; third, when processing antimony sulfide concentrate, Sb2S3The form of the sulfur element is difficult to control and is easy to oxidize to produce SO2After the electrolysis of the molten salt is finished, sulfur elements exist in polymorphic and multi-phase forms, are mainly mixed on the surface layer of the molten salt and are difficult to separate, the high-efficiency recovery of sulfur in antimony sulfide concentrate cannot be realized, and a certain degree of SO also exists2And (4) pollution problem.
Disclosure of Invention
In view of the problems, the primary object of the present invention is to provide a method for clean smelting of antimony sulfide-containing materials, especially antimony sulfide concentrate, and simultaneously obtaining metallic antimony and elemental sulfur.
The invention inserts a spray pipe from the bottom of the fused salt electrolytic bath, and the spray pipe is used for fused salt electrolysisInert gas with certain pressure is added to stir the molten pool, so that the mass transfer of molten salt ions is enhanced, and the electrolysis efficiency is improved; promoting the condensation and sedimentation of fine antimony beads in the molten salt to obtain a large antimony layer, which is beneficial to the separation and recovery of antimony; meanwhile, elemental sulfur produced by anode molten salt electrolysis is timely conducted into a smoke dust collecting bag through airflow for enrichment. Through improvement, the invention can solve the problems of high energy consumption, complex equipment and the like in the existing pyrometallurgical antimony smelting process, and avoid low-concentration SO2The pollution, high-grade refined antimony is refined in one step, the direct yield of antimony is improved, and the associated sulfur resource in the antimony concentrate is efficiently recovered. The invention can also solve the problem of the patent 201710775124.0 in the practice of scale-up application.
The technical scheme of the invention is as follows:
a molten salt electrolysis method for antimony sulfide-containing materials comprises the steps of mixing antimony sulfide-containing materials and inert molten salt, placing the mixture in an electrolysis device, heating, carrying out electrolysis smelting, blowing inert gas into the device to stir a molten pool in the smelting process, gradually enriching the lower layer in the device along with the low-temperature molten salt electrolysis to obtain a liquid antimony melt layer, and gradually enriching the liquid antimony melt layer in a flue gas collection device to obtain elemental sulfur.
In the above method, the inert gas may be blown from any part of the electrolyzer, but it is preferable to blow the inert gas from the bottom of the molten bath.
The invention firstly blows inert gas into the molten salt electrolysis process combined with the antimony-containing material, and obtains good effect.
Further, the inert gas is preferably nitrogen or argon. Further, it is preferable to preheat before blowing the inert gas. The preheating is to prevent the low-temperature inert gas from influencing the reaction speed, and the preheating can shorten the reaction time.
Further, it is preferable that the temperature of the preheated gas is 800 to 1000 ℃.
According to the method, the cell voltage is within the range of 2.0-2.5V during electrolytic smelting, the cathode-anode distance is 2-15 cm, and the optimal distance is 3-8 cm.
In the electrolytic smelting, the invention can treat materials with weight of any scale, but the treatment of materials with weight of large scale has more practical significance, so the invention preferably treats the antimony sulfide-containing materials with the amount of more than 0.5kg, and further preferably not less than 1 kg.
In the method, the pressure of the blown gas is 0.1-0.5 Mpa. The pressure of the blown gas is too small to play a role of stirring, and the pressure is too large to cause the materials to fly, thereby also influencing the effect of electrolytic smelting.
In practice, the pressure of the gas blown in can be adjusted according to the weight of the treated material and the volume and shape of the electrolytic cell. During specific implementation, the sizes of the hearths are different, the melt heights of materials with the same weight in hearths with different capacities are different, and the melt depth of the material layer exceeds the cathode-anode distance.
In the method, the electrolytic smelting reaction time is at least 30min, preferably 60-120 min.
The method can improve the large reaction efficiency of electrolytic smelting and obviously shorten the reaction time.
Further, in the method
The inert molten salt comprises a mixture of sodium chloride and potassium chloride and a combined molten salt of sodium sulfide or potassium sulfide.
In the mixture of sodium chloride and potassium chloride, the ratio of the amount of sodium chloride to the amount of potassium chloride is 0.5-2: 1.
The mass percentage of the sodium sulfide or the potassium sulfide in the combined molten salt is 1 wt.% to 30 wt.%.
The mass ratio of the antimony sulfide-containing material to the inert molten salt is 0.1-1: 1.
The electrolysis temperature is 800-1000 ℃.
The method, the antimony sulfide containing material comprises antimony sulfide concentrate, and the Sb content in the antimony sulfide concentrate is higher than 30 wt%
The invention also aims to provide a device which is matched with the molten salt electrolysis method of the antimony sulfide-containing material, is simple and practical and can comprehensively obtain the separation and recovery effects of antimony and sulfur.
A molten salt electrolysis device for antimony sulfide-containing materials comprises a closed electrolytic bath, a cathode guide rod, an anode guide rod, a graphite anode and a direct current power supply; the electrolysis trough bottom be equipped with gaseous spray tube and be used for putting antimony mouth of the ejection of compact, the top is equipped with feed inlet and exhanst gas outlet, the electrolysis trough bottom use graphite as the inside lining, the one end of negative pole guide arm links to each other with the graphite inside lining of electrolysis trough bottom, the other end passes through the wire and links to each other with DC power supply negative pole, the one end of positive pole guide arm stretches into from the furnace top, links to each other with the inside graphite positive pole of electrolysis trough, the other end passes through the wire and links to each other with DC power supply.
Further, in the above-mentioned case,
the device is characterized in that a resistance heating layer is arranged outside the electrolytic cell.
The device, the gas spray pipe, the cathode guide rod and the anode guide rod are made of stainless steel or refined copper.
In the device, the flue gas outlet receives a dust cloth bag.
In conclusion, compared with the prior proposal patent 201710775124.0,
1. through the design of a specific bottom blowing molten salt electrolysis system, molten salt in an electrolytic cell forms a molten pool with violent convection in the range of 800-1000 ℃, the mass transfer of molten salt ions is greatly enhanced, the molten salt electrolysis efficiency is greatly improved, fine antimony beads in the molten salt are promoted to be condensed and settled, a massive antimony layer is obtained, and the separation and recovery of antimony are facilitated. Patent 201710775124.0 actually has the problem that antimony beads cannot be agglutinated in both the pilot plant and the scale treatment. In order to collect antimony obtained by electrolysis, molten salt can only be discharged and cooled, and then the antimony is collected by fine grinding and sieving, so that the problem is more prominent particularly in large-scale treatment, the treatment difficulty is greatly increased, and the molten salt is lost.
2. According to the invention, the inert gas is blown into the bottom, so that the mass transfer of molten salt ions is enhanced, the separated elemental sulfur can be protected from being oxidized, the gas-phase elemental sulfur separated from the molten salt can be taken as a load gas, and the gas-phase elemental sulfur can be carried away from the molten salt and is timely conducted to the smoke dust collecting bag along the airflow direction for enrichment, 201710775124.0 molten salt is static, and the sulfur separated from the molten salt is difficult to separate from the molten salt and is enriched in the smoke dust collecting bag.
3. The invention has short reaction time, obviously improves the reaction efficiency, needs only 30 to 60 minutes at the shortest time, does not exceed 120 minutes in scale treatment, and needs at least 210 minutes in patent 201710775124.0.
4. The invention does not need to have a specific cloth mode like 201710775124.0, only needs simple mixing and is convenient to operate.
Compared with the existing antimony smelting blast furnace volatilization-reverberatory furnace high-temperature fire reduction smelting process, the invention can greatly reduce the fire smelting temperature of antimony concentrate, produce high-grade antimony in one step and recover elemental sulfur, has the advantages of short flow, low energy consumption and high direct yield of antimony and sulfur, and has great significance for promoting the technical progress of antimony smelting in China and saving energy and reducing emission.
Drawings
FIG. 1 is a schematic view of a bottom-blown molten salt electrolyzer of the present invention.
In the figure, 1-a molten salt electrolytic cell, 2-an anode guide rod, 3-a direct current power supply, 4-a flue gas outlet, 5-an antimony discharging port, 6-a gas spray pipe, 7-anode graphite, 8-a graphite inner layer, 9-a cathode guide rod, 10-a resistance heating layer and 11-a feeding port.
Detailed Description
The following examples are intended to further illustrate the invention without forming a limitation thereon.
The invention relates to a bottom blowing molten salt electrolysis device, which comprises a closed electrolysis bath [1], an anode guide rod [2], a cathode guide rod [9], a graphite anode [7] and a direct current power supply [3 ]; the bottom of the electrolytic tank is provided with an antimony discharging port [5] and a gas spray pipe [6] which are used for discharging materials, a resistance heating layer [10] is arranged outside the electrolytic tank, the top of the electrolytic tank is provided with a feed inlet [11] and a flue gas outlet [4] of a one-way valve, the bottom of the electrolytic tank takes graphite as a lining, one end of a cathode guide rod [9] is connected with a graphite lining [8] at the bottom of the electrolytic tank [1], the other end of the cathode guide rod is connected with the negative electrode of a direct current power supply [3] through a lead, one end of an anode guide rod [2] extends into the electrolytic tank [1] from the top and is connected with a graphite anode [7], the other end of the anode guide rod is connected with the positive electrode of the direct.
The following examples all employ the above-described apparatus.
Example 1
The chemical composition of antimony sulfide concentrate A (%)：Sb 51.5、Fe 2.3、S 16.6、As 0.39、Pb 0.42、SiO212.1. Respectively weighing 600g of the antimony sulfide concentrate and 120g of Na2S, 474.6g NaCl and 605.4g KCl. After being uniformly mixed, the mixture is tiled at the bottom of the bottom blowing molten salt electrolysis device. And adjusting the height of the anode guide rod to insert the graphite anode into the mixed material, and enabling the cathode-anode polar distance to be 4 cm. And starting an external resistance heating layer power supply, and heating to 880 ℃. Blowing nitrogen with preheating temperature of 880 ℃ and pressure of 0.2MPa into a gas nozzle at the bottom of the electrolytic cell to stir molten salt, switching on a direct current electrolytic power supply, setting the cell voltage to be stable 2.2V, and finishing the reaction after reacting for 60 min. Cooling after discharging antimony from an antimony discharging port, directly collecting 306g of whole antimony, wherein the antimony grade is 98.5%, the antimony direct yield is 97.5%, and collecting 88.8g of simple substance S with the purity of 92.2% in a smoke collecting cloth bag.
Example 2
The chemical composition of the antimony sulfide concentrate B is (%): sb 32.1, Fe 16.4, S30.2, As 1.5, SiO213.5 and Pb1.2. 1200g of the antimony sulfide concentrate B, 600g K were weighed2S, 1054.8g NaCl and 1345.2g KCl, and mixing uniformly. And then the mixed material is flatly paved at the bottom of the bottom blowing molten salt electrolysis device. And adjusting the height of the anode guide rod to insert the graphite anode into the upper mixed material, and enabling the cathode-anode polar distance to be 10 cm. And starting an external resistance heating layer power supply, and heating to 920 ℃. Argon gas with the preheating temperature of 920 ℃ and the pressure of 0.3MPa is blown into a gas nozzle at the bottom of the electrolytic cell to stir the molten salt, a direct-current electrolytic power supply is switched on, the cell voltage is set to be stable 2.3V, and the reaction is finished after 90min of reaction. Cooling after discharging antimony from an antimony discharging port, directly collecting 384g of whole antimony, wherein the antimony grade is 98.3%, the antimony direct yield is 98%, and collecting a simple substance S318g with the purity of 92.5% in a smoke collecting cloth bag.
Example 3
Carrying out low-temperature molten salt electrolysis on antimony concentrate by using the same raw materials and test parameters in the example 1, enlarging the experimental scale by 10 times, and respectively weighing 6000g of the antimony sulfide concentrate and 1200g of Na2S, 4746g NaCl and 6054g KCl. However, the temperature, pressure, voltage and other parameters were unchanged, and the reaction was terminated after 120min of reaction. Cooling the antimony after discharging the antimony from the antimony discharging port, and directly collecting 3042g of whole antimony, namely an antimony product98.1 percent, the direct yield of antimony is 96.6 percent, and the simple substance S906g with the purity of 90.5 percent is collected in a smoke collection bag.
Comparative example 1 (non bottom blowing pulse current molten salt electrolysis scheme)
Molten salt electrolysis was carried out using the same raw materials as in example 1, in accordance with the protocol of example 1 described in "a method and apparatus for clean metallurgy by molten salt electrolysis of antimony (201710775124.0)" with the exception that the scale of the experiment was enlarged by 10 times. After the experiment is finished, large antimony blocks which are coagulated together are not discharged from the antimony discharging port, and a plurality of small antimony beads which are mixed with the molten salt are discharged intermittently. In order to collect the antimony obtained by electrolysis, the molten salt can be discharged completely and then cooled, then 892g of antimony with the antimony grade of 49.4% is collected after fine grinding and sieving (which is inconvenient to operate and also loses part of lava), and only 158g of elemental sulfur with the grade of 56.4% is collected in a smoke collection bag.
Comparative example 2 (No bottom blowing DC current molten salt electrolysis scheme)
The same raw materials and the same parameters as those in example 1 were used. The only difference is that the bath is not agitated by blowing gas from the bottom. After the reaction was carried out for 60min, the reaction was terminated. When the antimony valve is opened, no liquid antimony flows out, and no obvious antimony beads are seen. After all the molten salt is discharged, sampling analysis and detection show that the decomposition rate of the antimony sulfide is less than 30%.
Comparative example 3 (bottom blowing pulse current molten salt electrolysis scheme)
The same raw materials and the same parameters as those in example 1 were used. The only difference is the use of the pulsed current regime and parameters in 201710775124.0. After the experiment is finished, an antimony discharging valve is opened, 151g of antimony in the whole block is directly collected, the antimony grade is 90.5%, the antimony direct yield is only 47.6%, 41.2g of elemental S with the purity of 88.2% is collected in a smoke collecting bag, and the yield of elemental sulfur is only 36.5%.
Claims (10)
1. A molten salt electrolysis method for antimony sulfide-containing materials is characterized in that the antimony sulfide-containing materials and inert molten salt are mixed and placed in an electrolysis device to be heated for electrolytic smelting, inert gas is blown in during smelting to stir a molten pool, a liquid antimony melt layer is obtained by gradually enriching the lower layer in the device along with the low-temperature molten salt electrolysis, and elemental sulfur is obtained by gradually enriching in a flue gas collection device.
2. The method according to claim 1, characterized in that an inert gas, preferably nitrogen or argon, is blown from the bottom of the bath, preferably preheated before the gas is blown, more preferably the preheated gas temperature is 800 ℃ to 1000 ℃.
3. The method according to claim 1, wherein the cell voltage during electrolytic smelting is in the range of 2.0 to 2.5V, and the cathode-anode distance is 2 to 15cm, preferably 3 to 8 cm.
4. A method according to any one of claims 1-3, characterized in that the antimony sulphide containing material is added in an amount of more than 0.5kg, preferably not less than 1 kg.
5. The method according to any one of claims 1 to 4, wherein the pressure of the gas to be blown in is 0.1 to 0.5 MPa.
6. The method according to any one of claims 1 to 5, characterized in that the electrolytic smelting reaction time is at least 30min, preferably 60-120 min.
7. The method according to claim 1, wherein the inert molten salt comprises a mixture of sodium chloride and potassium chloride and a combined molten salt of sodium sulfide or potassium sulfide, the amount ratio of sodium chloride to potassium chloride in the mixture of sodium chloride and potassium chloride is 0.5-2: 1, the mass percentage of sodium sulfide or potassium sulfide in the combined molten salt is 1-30 wt.%, and the mass ratio of antimony sulfide-containing material to inert molten salt is 0.1-1: 1; the temperature of molten salt electrolysis is 800-1000 ℃.
8. The method of claim 1, wherein the antimony sulfide bearing material comprises an antimony sulfide concentrate having an Sb content greater than 30 wt.%.
9. A molten salt electrolysis device for antimony sulfide-containing materials is characterized by comprising a closed electrolytic cell, a cathode guide rod, an anode guide rod, a graphite anode and a direct current power supply; the electrolysis trough bottom be equipped with gaseous spray tube and be used for putting antimony mouth of the ejection of compact, the top is equipped with feed inlet and exhanst gas outlet, the electrolysis trough bottom use graphite as the inside lining, the one end of negative pole guide arm links to each other with the graphite inside lining of electrolysis trough bottom, the other end passes through the wire and links to each other with DC power supply negative pole, the one end of positive pole guide arm stretches into from the furnace top, links to each other with the inside graphite positive pole of electrolysis trough, the other end passes through the wire and links to each other with DC power supply.
10. The apparatus of claim 9, wherein the electrolytic cell is externally provided with a resistance heating layer.
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| CN115012003A (en) * | 2022-06-20 | 2022-09-06 | 中南大学 | Method and device for molten salt electrolysis continuous production of antimony sulfide ore |
| WO2023246367A1 (en) * | 2022-06-20 | 2023-12-28 | 中南大学 | Antimony-sulfide-containing ore-based molten salt electrolysis continuous production method and apparatus |
| CN115012003B (en) * | 2022-06-20 | 2024-02-06 | 中南大学 | Method and device for continuously producing antimony sulfide ore through molten salt electrolysis |
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