CN114715854A - Method for recovering elemental sulfur by leaching high-sulfur slag through zinc oxygen pressure - Google Patents
Method for recovering elemental sulfur by leaching high-sulfur slag through zinc oxygen pressure Download PDFInfo
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Abstract
The invention discloses a method for recovering elemental sulfur from zinc oxygen pressure leached high-sulfur slag, which comprises the steps of adding carbon powder into the zinc oxygen pressure leached high-sulfur slag, then carrying out incineration, gas capture and continuous twice low-temperature plasma irradiation to realize the high-efficiency recovery of sulfur in the zinc oxygen pressure leached high-sulfur slag. The method has the advantages of simple treatment process, simple and convenient process chain, high sulfur slag treatment efficiency, no generation of secondary pollutants, highest sulfur recovery efficiency of 78.15 percent and sulfur recovery purity higher than 98 percent.
Description
Technical Field
The invention relates to a method for recovering elemental sulfur from high-sulfur slag by zinc oxygen pressure leaching, belonging to the field of harmless treatment and resource utilization of hazardous wastes.
Background
0.7-0.9 ton zinc leaching slag is produced when a zinc smelting enterprise produces a single ton of metal zinc, and about 60 million tons of zinc oxygen pressure leaching slag are produced every year in China. The zinc oxygen pressure leaching process is a technology for realizing the high-efficiency leaching of zinc element in zinc sulfide concentrate powder in the modes of pressurization, oxygen introduction and surfactant (lignosulfonate) addition. The leaching residue produced by zinc leaching by using the zinc oxygen pressure leaching process contains a large amount of sulfur elements, the sulfur grade is higher than 40%, and the content of sulfur oxides in part of the leaching residue can reach more than 80%. In the zinc-oxygen-pressure high-sulfur slag, sulfur mainly exists in the forms of elemental sulfur, sulfide, sulfate (double salt) and the like. Besides being rich in sulfur, sulfur in the zinc-oxygen-pressure high-sulfur slag also contains noble metal elements and a plurality of heavy metal elements. Considering the environmental hazard of the zinc-oxygen-pressure high-sulfur slag, the zinc-oxygen-pressure high-sulfur slag is listed in national hazardous waste records (code: 321-006-48), and the hazardous property is toxicity. Therefore, compared with the zinc oxygen pressure high sulfur slag which is massively stockpiled in the current zinc smelting enterprises, the high sulfur slag needs to be dealt with and disposed by researching and developing efficient harmless and recycling technology. Otherwise, the zinc-oxygen-high-sulfur slag which is massively stacked not only can generate huge threat to the environment, but also inevitably causes irreversible influence on the health, order and long-term development of the production activities of zinc smelting enterprises within the expected time in the future.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for efficiently recovering elemental sulfur by leaching high-sulfur slag through zinc oxygen pressure, which has the advantages of high treatment efficiency, no generation of secondary pollutants, high elemental sulfur recovery efficiency and high purity.
The technical scheme is as follows: the invention discloses a method for recovering elemental sulfur by leaching high-sulfur slag through zinc oxygen pressure, which comprises the following steps of:
drying and grinding the zinc oxygen pressure leached high-sulfur slag to obtain zinc oxygen pressure leached high-sulfur powder;
(2) mixing the high-sulfur powder leached by zinc oxygen pressure with carbon powder, and stirring to obtain carbon-doped high-sulfur powder;
(3) burning carbon-doped high-sulfur powder, and introducing gas generated in the burning process into a capture agent solution to obtain a sulfur-loaded capture agent solution;
(4) continuously carrying out low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution twice to obtain sulfur suspension slurry;
(5) and filtering the sulfur suspension slurry, drying the obtained solid, and grinding to obtain the elemental sulfur.
In the step (2), the mass ratio of the carbon powder to the zinc oxygen pressure leached high-sulfur powder is 0.5-1.5: 1.
In the step (3), the trapping agent solution is any one of a sodium formate solution, a sodium lactate solution and a sodium oxalate solution.
Wherein in the step (3), the concentration of the capture agent solution is 1-10M.
In the step (4), when the first low-temperature plasma irradiation treatment in the low-temperature plasma irradiation treatment is continuously performed twice, the voltage is 5-75 kV, and the atmosphere is air.
In the step (4), when the second low-temperature plasma irradiation treatment in the low-temperature plasma irradiation treatment is continuously performed twice, the voltage is 5-75 kV, and the atmosphere is a mixed gas of hydrogen and carbon dioxide.
Wherein the molar ratio of the hydrogen gas to the carbon dioxide gas is 1-4: 10.
In the step (5), the drying temperature is 50-150 ℃, and the drying time is 6-24 hours.
The reaction mechanism is as follows: the zinc oxygen pressure leached high-sulfur slag is dried, ground into powder and then mixed with carbon powder, so that the effective contact surface of the carbon powder and the zinc oxygen pressure leached high-sulfur powder can be improved, and the mixing degree is improved. And blowing the carbon-doped high-sulfur powder into a combustion furnace for sufficient incineration, further igniting the high-sulfur powder after the carbon powder is ignited in the incineration process, fully combusting the carbon powder to release carbon dioxide, and fully combusting the high-sulfur powder to release sulfur dioxide gas. The carbon dioxide and sulfur dioxide gas are absorbed by the capture agent solution to produce carbonate and sulfite. In the process of primary low-temperature plasma irradiation, oxygen and water vapor in the air are ionized and dissociated in a discharge channel to generate oxygen radicals and hydroxyl radicals. The oxygen free radical and the hydroxyl free radical can react with sodium formate, sodium lactate and sodium oxalate to generate carbon dioxide free radical and sodium hydroxide, and the carbon dioxide free radical can react with sulfite to generate carbonate and elemental sulfur. The sodium hydroxide can strengthen the water-solid separation process of the elemental sulfur. In the secondary low-temperature plasma irradiation process, hydrogen gas generates hydrogen radicals in the discharge channel, and the hydrogen radicals can react with sulfite radicals to generate elemental sulfur and water, so that the elemental sulfur generation process can be further enhanced. The excessive carbon dioxide introduced in the secondary low-temperature plasma irradiation process can react with sodium in the solution to generate soluble sodium bicarbonate.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
the method has the advantages of simple treatment process and simple and convenient process chain, realizes the high-efficiency recovery of sulfur in the zinc-oxygen pressure leaching high-sulfur slag through incineration, gas capture and low-temperature plasma secondary irradiation, has high treatment efficiency of the high-sulfur slag, generates no secondary pollutants, has the highest sulfur recovery efficiency of 78.15 percent, and ensures that the purity of the recovered sulfur is higher than 98 percent.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Zinc oxygen pressure leach high sulphur slag was taken from certain zinc smelting company, inner mongolia, containing 52.61% S, 32.78% O, 6.94% Zn, 3.52% Fe, 2.53% Si, 1.24% Pb and 0.38% other impurities.
Example 1 influence of mass ratio of carbon powder and zinc-oxygen pressure leached high-sulfur powder on sulfur recovery efficiency and purity of recovered sulfur
And drying the zinc oxygen pressure leached high-sulfur slag, and grinding into powder to obtain the zinc oxygen pressure leached high-sulfur powder. Respectively weighing carbon powder and zinc oxygen pressure leaching high-sulfur powder according to the mass ratio of 0.25:1, 0.35:1, 0.45:1, 0.5:1, 1.0:1, 1.5:1, 1.55:1, 1.65:1 and 1.75:1, mixing and uniformly stirring to obtain nine groups of carbon-doped high-sulfur powder. And blowing the carbon-doped high-sulfur powder into a combustion furnace respectively for full combustion, and introducing gases generated in the combustion process into trapping agent solutions respectively to obtain nine groups of sulfur-carried trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 1M. Carrying out continuous two times of low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, the action voltage of low-temperature plasma is 5kV, and the action atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 5kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 1:10, so that nine groups of sulfur suspension slurries are obtained. And respectively filtering the nine groups of sulfur suspension slurries, drying the obtained solid part for 24 hours at the temperature of 50 ℃, and grinding the solid part into powder to obtain nine groups of elemental sulfur.
Calculating the sulfur recovery efficiency: the sulfur recovery efficiency was calculated according to the following formula (1), wherein α% is the sulfur recovery efficiency, msM for the amount of sulfur recovered (g)tThe amount (g) of zinc oxygen pressure leached high sulfur slag used for disposal.
α％＝ms/(0.5261×mt)×100％ (1)
And (3) determination of the purity of the recovered sulfur: the purity of the recovered sulfur was as per part 1 of industrial sulfur: solid products (GB/T2449.1-2014).
The results of the above experiments are shown in table 1.
TABLE 1 influence of mass ratio of carbon powder and zinc-oxygen pressure leached high-sulfur powder on sulfur recovery efficiency and purity of recovered sulfur
As can be seen from Table 1, the purity of the recovered sulfur is higher than 98% under the condition of changing mass ratio of the carbon powder to the zinc oxygen pressure leached high-sulfur powder. And when the mass ratio of the carbon powder to the zinc-oxygen pressure leached high-sulfur powder is less than 0.5:1, the doping amount of the carbon powder is less, the ignition efficiency of the high-sulfur powder is reduced, the combustion release amount of sulfur dioxide gas is reduced, and the sulfur recovery efficiency is obviously reduced along with the reduction of the mass ratio of the carbon powder to the zinc-oxygen pressure leached high-sulfur powder. When the mass ratio of the carbon powder to the zinc-oxygen pressure leached high-sulfur powder is 0.5-1.5: 1, blowing the carbon-doped high-sulfur powder into a combustion furnace for sufficient incineration, further igniting the high-sulfur powder after the carbon powder is ignited in the incineration process, fully combusting the carbon powder to release carbon dioxide, and fully combusting the high-sulfur powder to release sulfur dioxide gas. Finally, the sulfur recovery efficiency was higher than 62%. And when the mass ratio of the carbon powder to the zinc oxygen pressure leaching high-sulfur powder is more than 1.5:1, the sulfur recovery efficiency does not change obviously along with the further increase of the mass ratio of the carbon powder to the zinc oxygen pressure leaching high-sulfur powder. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the carbon powder to the zinc oxygen pressure leaching high-sulfur powder is equal to 0.5-1.5: 1, the sulfur recovery efficiency and the purity of the recovered sulfur are most favorably improved.
Example 2 Effect of Capture agent solution concentration on Sulfur recovery efficiency and recovered Sulfur purity
And drying the zinc oxygen pressure leaching high-sulfur slag, and grinding into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing carbon-doped high-sulfur powder into a combustion furnace for sufficient incineration, and introducing gas generated in the combustion process into a trapping agent solution, wherein the concentrations of the trapping agent solution are sodium formate solutions of 0.5M, 0.7M, 0.9M, 1M, 5.5M, 10M, 10.5M, 11.5M and 12.5M respectively, so as to obtain nine groups of sulfur-loaded trapping agent solutions. Carrying out continuous twice low-temperature plasma irradiation treatment on nine groups of sulfur-carried trapping agent solutions, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solutions, the acting voltage of low-temperature plasma is 40kV, and the acting atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 40kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 2.5:10, so that nine groups of sulfur suspension slurries are obtained. And respectively filtering the nine groups of sulfur suspension slurries to obtain nine groups of solid parts, drying the nine groups of solid parts for 15 hours at the temperature of 100 ℃, and grinding the solid parts into powder to obtain nine groups of elemental sulfur.
The calculation of the sulfur recovery efficiency and the measurement of the purity of the recovered sulfur were the same as in example 1, and the results are shown in Table 2.
TABLE 2 Effect of Capture agent solution concentration on Sulfur recovery efficiency and recovered Sulfur purity
As can be seen from Table 2, the sulfur recovery purity was higher than 99% under varying concentrations of the scavenger solution. Whereas when the concentration of the scavenger solution is less than 1M, the amount of carbon dioxide and sulfur dioxide absorbed by the scavenger solution decreases, resulting in a significant decrease in sulfur recovery efficiency as the concentration of the scavenger solution decreases. When the concentration of the capture agent solution is equal to 1-10M, carbon dioxide and sulfur dioxide gas are absorbed by the capture agent solution to generate carbonate and sulfite. In the process of primary low-temperature plasma irradiation, oxygen and water vapor in the air are ionized and dissociated in a discharge channel to generate oxygen radicals and hydroxyl radicals. The oxygen free radical and the hydroxyl free radical can react with sodium formate, sodium lactate and sodium oxalate to generate carbon dioxide free radical and sodium hydroxide, and the carbon dioxide free radical can react with sulfite to generate carbonate and elemental sulfur. The sodium hydroxide can strengthen the water-solid separation process of the elemental sulfur. In the secondary low-temperature plasma irradiation process, hydrogen gas generates hydrogen radicals in the discharge channel, and the hydrogen radicals can react with sulfite radicals to generate elemental sulfur and water, so that the elemental sulfur generation process can be further enhanced. Finally, the sulfur recovery efficiency was higher than 67%. When the concentration of the capture agent solution is greater than 10M, the sulfur recovery efficiency does not change significantly with further increase in the concentration of the capture agent solution. Therefore, in summary, combining benefits and costs, when the concentration of the capture agent solution is equal to 1-10M, the sulfur recovery efficiency and the purity of the recovered sulfur are most advantageously improved.
Example 3 influence of hydrogen and carbon dioxide gas molar ratio on sulfur recovery efficiency and recovered sulfur purity
And drying the zinc oxygen pressure leaching high-sulfur slag, and grinding into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing the carbon-doped high-sulfur powder into a combustion furnace for sufficient incineration, and introducing gas generated in the combustion process into a trapping agent solution to obtain a sulfur-carried trapping agent solution, wherein the trapping agent solution is a sodium formate solution with the concentration of 10M. Carrying out continuous twice low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, the acting voltage of low-temperature plasma is 75kV, and the acting atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 75kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratios of the hydrogen to the carbon dioxide are respectively 0.5:10, 0.7:10, 0.9:10, 1:10, 2.5:10, 4:10, 4.5:10, 5:10 and 5.5:10, so that nine groups of sulfur suspension slurries are obtained. And respectively filtering the nine groups of sulfur suspension slurries to obtain nine groups of solid parts, drying for 6 hours at the temperature of 150 ℃, and grinding to obtain nine groups of elemental sulfur.
The calculation of the sulfur recovery efficiency and the measurement of the purity of the recovered sulfur were the same as in example 1, and the results are shown in Table 3.
TABLE 3 influence of hydrogen and carbon dioxide gas molar ratio on sulfur recovery efficiency and recovered sulfur purity
It can be seen from table 3 that the sulfur recovery purity was higher than 99% under varying molar ratios of hydrogen to carbon dioxide gases. And when the molar ratio of the hydrogen gas to the carbon dioxide gas is less than 1:10, the introduction amount of the hydrogen gas is small, and hydrogen radicals generated by the hydrogen gas in the discharge channel are reduced, so that the sulfur recovery efficiency is remarkably reduced along with the reduction of the molar ratio of the hydrogen gas to the carbon dioxide gas. When the molar ratio of the hydrogen gas to the carbon dioxide gas is 1-4: 10, the hydrogen gas generates hydrogen radicals in the discharge channel in the secondary low-temperature plasma irradiation process, and the hydrogen radicals can react with sulfite to generate elemental sulfur and water, so that the elemental sulfur generation process can be further enhanced. Finally, the sulfur recovery efficiencies were all above 72%. When the hydrogen to carbon dioxide gas molar ratio is greater than 4:10, the sulfur recovery efficiency does not change significantly as the hydrogen to carbon dioxide gas molar ratio is further increased. Therefore, in summary, combining the benefits and the cost, when the molar ratio of the hydrogen gas to the carbon dioxide gas is equal to 1-4: 10, the improvement of the sulfur recovery efficiency and the purity of the recovered sulfur is most beneficial.
Example 4 influence of the type of scavenger solution on the efficiency and purity of sulfur recovery
And drying the zinc oxygen pressure leaching high-sulfur slag, and grinding the zinc oxygen pressure leaching high-sulfur slag into powder to obtain zinc oxygen pressure leaching high-sulfur powder. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing carbon-doped high-sulfur powder into a combustion furnace for full combustion, and introducing gas generated in the combustion process into trapping agent solutions, wherein the trapping agent solutions are respectively sodium formate, sodium lactate or sodium oxalate solutions with the concentration of 10M, so as to obtain three groups of sulfur-carried trapping agent solutions. Carrying out continuous twice low-temperature plasma irradiation treatment on the three groups of sulfur-carried trapping agent solutions, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solutions, the acting voltage of low-temperature plasma is 75kV, and the acting atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 75kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 4:10, so that three groups of sulfur suspension slurry are obtained. And respectively filtering the three groups of sulfur suspension slurries to obtain three groups of solid parts, drying for 6 hours at the temperature of 150 ℃, and grinding to obtain three groups of elemental sulfur.
The calculation of the sulfur recovery efficiency and the measurement of the purity of the recovered sulfur were the same as in example 1, and the results are shown in Table 4.
TABLE 4 influence of scavenger solution type on sulfur recovery efficiency and recovered sulfur purity
As shown in Table 4, when the sodium formate, sodium lactate or sodium oxalate solution is selected as the trapping agent solution, the sulfur recovery efficiency is more than 76%, and the sulfur recovery purity is more than 99%.
Comparative example 1 different comparative processes have an effect on the efficiency of sulfur recovery and on the purity of the recovered sulfur
The process of the invention comprises the following steps: the sodium formate condition is selected by adopting the trapping agent solution in the embodiment 4, namely, the zinc oxygen pressure leaching high-sulfur slag is dried and ground into powder, and the zinc oxygen pressure leaching high-sulfur powder is obtained. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing the carbon-doped high-sulfur powder into a combustion furnace for full combustion, and introducing gas generated in the combustion process into a trapping agent solution to obtain sulfur-carried trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 10M respectively. Carrying out continuous twice low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, the acting voltage of low-temperature plasma is 75kV, and the acting atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 75kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 4:10, so that the sulfur suspension slurry is obtained. And filtering the sulfur suspension slurry, drying the obtained solid part for 6 hours at the temperature of 150 ℃, and grinding to obtain elemental sulfur.
Comparative process 1: and (3) under the condition of not adding carbon powder, drying the zinc oxygen pressure leaching high-sulfur slag, and grinding the zinc oxygen pressure leaching high-sulfur slag into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Blowing the zinc oxygen pressure leached high-sulfur powder into a combustion furnace for full combustion, and introducing gas generated in the combustion process into a trapping agent solution to obtain sulfur-carried trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 10M respectively. Carrying out continuous twice low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when carrying out the first low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, the acting voltage of low-temperature plasma is 75kV, and the acting atmosphere of the low-temperature plasma is air; when the sulfur-carried trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the low-temperature plasma action voltage is 75kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 4:10, so that the sulfur suspension slurry is obtained. And filtering the sulfur suspension slurry, drying the obtained solid part for 6 hours at the temperature of 150 ℃, and grinding to obtain elemental sulfur.
Comparative process 2: and only carrying out primary low-temperature plasma irradiation, drying the zinc oxygen pressure leaching high-sulfur slag, and grinding the zinc oxygen pressure leaching high-sulfur slag into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing the carbon-doped high-sulfur powder into a combustion furnace for full combustion, and introducing gas generated in the combustion process into a trapping agent solution to obtain sulfur-carried trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 10M respectively. And carrying out primary low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when the primary low-temperature plasma irradiation treatment is carried out on the sulfur-carried trapping agent solution, the action voltage of low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is air, and the obtained sulfur suspension slurry is obtained. And filtering the sulfur suspension slurry, drying the obtained solid part for 6 hours at the temperature of 150 ℃, and grinding to obtain elemental sulfur.
Comparative process 3: and only carrying out secondary low-temperature plasma irradiation, drying the zinc oxygen pressure leaching high-sulfur slag, and grinding into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Respectively weighing carbon powder and zinc-oxygen pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and uniformly stirring to obtain the carbon-doped high-sulfur powder. Blowing the carbon-doped high-sulfur powder into a combustion furnace for full combustion, and introducing gas generated in the combustion process into a trapping agent solution to obtain sulfur-carried trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 10M respectively. And (2) carrying out primary low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when the primary low-temperature plasma irradiation treatment is carried out on the sulfur-carried trapping agent solution, the action voltage of low-temperature plasma is 75kV, the low-temperature plasma action atmosphere is a mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 4:10, so as to obtain the sulfur suspension slurry. And filtering the sulfur suspension slurry, drying the obtained solid part for 6 hours at the temperature of 150 ℃, and grinding to obtain elemental sulfur.
Comparative process 4: in the prior art, the process for recovering elemental sulfur from zinc oxygen pressure leaching high-sulfur slag comprises the steps of drying the zinc oxygen pressure leaching high-sulfur slag, and then carrying out ball milling on the dried zinc oxygen pressure leaching high-sulfur slag, wherein the ball milling time is 2 hours, the rotating speed of a ball machine is 240rpm, and the ball-solid ratio is 0.45. Mixing the ball-milled zinc oxygen pressure leaching high-sulfur slag with equal mass of water, stirring and uniformly milling, and sieving with a 100-mesh sieve. And (4) carrying out vacuum filtration on the sieved emulsion, and then drying for 6h at the temperature of 150 ℃ to obtain elemental sulfur.
The calculation of the sulfur recovery efficiency and the determination of the purity of the recovered sulfur were the same as in example 1 for the process of the present invention and the comparative processes 1 to 4, and the results are shown in Table 5.
TABLE 5 Effect of different comparative processes on Sulfur recovery efficiency and Sulfur recovery purity
| Type of process | Sulfur recovery efficiency | Relative error | Recovery of sulfur purity | Relative error |
| The process of the invention | 78.15％ | ±0.1％ | 99.58％ | ±0.1％ |
| Comparative Process 1 | 24.27％ | ±0.1％ | 89.26％ | ±0.1％ |
| Comparative Process 2 | 18.35％ | ±0.1％ | 45.12％ | ±0.1％ |
| Comparative Process 3 | 21.59％ | ±0.1％ | 51.78％ | ±0.1％ |
| Comparative Process 4 | 44.76％ | ±0.1％ | 64.59％ | ±0.1％ |
As can be seen from table 5, the sulfur recovery efficiencies of comparative process 1, comparative process 2, comparative process 3, and comparative process 4 are all significantly lower than the process of the present invention, and the sum of the sulfur recovery efficiencies of comparative process 1, comparative process 2, and comparative process 3 is lower than the process of the present invention. The purity of the recovered sulfur of the comparison process 1, the comparison process 2, the comparison process 3 and the comparison process 4 is lower than that of the process disclosed by the invention, and the sum of the purity of the recovered sulfur of the comparison process 2 and the comparison process 3 is lower than that of the recovered sulfur of the process disclosed by the invention.
Claims (8)
1. A method for recovering elemental sulfur from zinc oxygen pressure leaching high-sulfur slag is characterized by comprising the following steps:
(1) drying and grinding the zinc oxygen pressure leached high-sulfur slag to obtain zinc oxygen pressure leached high-sulfur powder;
(2) mixing the high-sulfur powder leached by zinc oxygen pressure with carbon powder, and stirring to obtain carbon-doped high-sulfur powder;
(3) burning carbon-doped high-sulfur powder, and introducing gas generated in the burning process into a capture agent solution to obtain a sulfur-loaded capture agent solution;
(4) continuously carrying out low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution twice to obtain sulfur suspension slurry;
(5) and filtering the sulfur suspension slurry, drying the obtained solid, and grinding to obtain the elemental sulfur.
2. The method for recovering elemental sulfur from zinc-oxygen pressure leaching high-sulfur slag according to claim 1, wherein in the step (2), the mass ratio of the carbon powder to the zinc-oxygen pressure leaching high-sulfur powder is 0.5-1.5: 1.
3. The method for recovering elemental sulfur from zinc-oxygen pressure leaching high-sulfur slag according to claim 1, wherein in the step (3), the capturing agent solution is any one of a sodium formate solution, a sodium lactate solution and a sodium oxalate solution.
4. The method for recovering elemental sulfur from zinc oxygen pressure leaching high sulfur slag according to claim 1, wherein in the step (3), the concentration of the capture agent solution is 1-10M.
5. The method for recovering elemental sulfur from zinc oxygen pressure leaching high sulfur slag according to claim 1, wherein in the step (4), when the first low temperature plasma irradiation treatment in the low temperature plasma irradiation treatment is continuously performed twice, the voltage is 5-75 kV, and the atmosphere is air.
6. The method for recovering elemental sulfur from zinc-oxygen pressure leaching high-sulfur slag according to claim 1, wherein in the step (4), when the second low-temperature plasma irradiation treatment is performed twice in succession, the voltage is 5 to 75kV, and the atmosphere is a mixed gas of hydrogen gas and carbon dioxide gas.
7. The method for recovering elemental sulfur from zinc oxygen pressure leaching high-sulfur slag according to claim 6, wherein the molar ratio of hydrogen gas to carbon dioxide gas is 1-4: 10.
8. The method for recovering the elemental sulfur from the zinc oxygen pressure leaching high sulfur slag according to claim 1, wherein in the step (5), the drying temperature is 50-150 ℃, and the drying time is 6-24 h.
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| CN109055749A (en) * | 2018-09-28 | 2018-12-21 | 长沙有色冶金设计研究院有限公司 | A kind of processing method of zinc oxygen leaching solution |
| CN110314649A (en) * | 2019-07-05 | 2019-10-11 | 清华大学深圳研究生院 | A kind of carbon-based heavy metal capturing agent and preparation method thereof |
| CN113233426A (en) * | 2021-03-08 | 2021-08-10 | 江苏北矿金属循环利用科技有限公司 | Method for recovering sulfur from zinc oxygen pressure leaching high-sulfur slag |
| CN113355527A (en) * | 2021-05-11 | 2021-09-07 | 江西铜业技术研究院有限公司 | Treatment method of high-sulfur smelting slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109055749A (en) * | 2018-09-28 | 2018-12-21 | 长沙有色冶金设计研究院有限公司 | A kind of processing method of zinc oxygen leaching solution |
| CN110314649A (en) * | 2019-07-05 | 2019-10-11 | 清华大学深圳研究生院 | A kind of carbon-based heavy metal capturing agent and preparation method thereof |
| CN113233426A (en) * | 2021-03-08 | 2021-08-10 | 江苏北矿金属循环利用科技有限公司 | Method for recovering sulfur from zinc oxygen pressure leaching high-sulfur slag |
| CN113355527A (en) * | 2021-05-11 | 2021-09-07 | 江西铜业技术研究院有限公司 | Treatment method of high-sulfur smelting slag |
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