CN114715854B - Method for recycling elemental sulfur from high-sulfur slag by zinc-oxygen pressure leaching - Google Patents
Method for recycling elemental sulfur from high-sulfur slag by zinc-oxygen pressure leaching Download PDFInfo
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Abstract
The invention discloses a method for recycling elemental sulfur from zinc-oxygen pressure leaching 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 purity of recovered sulfur of higher than 98 percent.
Description
Technical Field
The invention relates to a method for recycling elemental sulfur by utilizing zinc-oxygen pressure leaching high-sulfur slag, and belongs to the field of harmless disposal and resource utilization of dangerous wastes.
Background
The zinc smelting enterprises produce 0.7 to 0.9 ton of zinc leaching slag when producing single ton of metallic zinc, and about 60 ten thousand tons of zinc oxygen pressure leaching slag are produced annually in China. The zinc oxygen pressure leaching process is a technology for realizing efficient leaching of zinc element in zinc sulfide concentrate powder by means of pressurization, oxygen introduction and surfactant (lignosulfonate) addition. The leaching slag generated by zinc leaching by utilizing 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 slag can reach more than 80%. Sulfur in the zinc-oxygen high-sulfur slag mainly exists in the forms of elemental sulfur, sulfide, sulfate (double salt) and the like. Besides being rich in sulfur, the zinc-oxygen high-sulfur slag also contains noble metal elements and various heavy metal elements. Considering the environmental hazard of zinc oxide high sulfur slag, zinc oxide high sulfur slag is listed in the national hazardous waste list (code: 321-006-48), and the hazardous property is toxicity. Therefore, compared with the zinc oxygen high sulfur slag piled up in a large amount in the current zinc smelting enterprises, the high-efficiency harmless and recycling technology must be developed for coping and disposing. If not, a great amount of piled zinc-oxygen high-sulfur slag can not only cause great threat to the environment, but also inevitably cause irreversible influence on the health, order and long-term development of the production activities of zinc smelting enterprises in the future.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for efficiently recycling elemental sulfur by utilizing zinc-oxygen pressure leaching high-sulfur slag, which has the advantages of high treatment efficiency, no generation of secondary pollutants, high elemental sulfur recycling efficiency and high purity.
The technical scheme is as follows: the method for recycling elemental sulfur from high-sulfur slag by zinc oxygen pressure leaching comprises the following steps:
drying and grinding the high-sulfur slag leached by zinc oxide to obtain high-sulfur powder leached by zinc oxide;
(2) Mixing the zinc-oxygen pressure leached high-sulfur powder with carbon powder, and stirring to obtain carbon-doped high-sulfur powder;
(3) Incinerating the carbon-doped high sulfur powder, and introducing gas generated in the incineration process into the capture agent solution to obtain a sulfur-loaded capture agent solution;
(4) Carrying out low-temperature plasma irradiation treatment on the sulfur-carrying capturing agent solution twice continuously to obtain sulfur suspension slurry;
(5) And filtering the sulfur suspension slurry, drying and grinding the obtained solid to obtain elemental sulfur.
In the step (2), the mass ratio of the carbon powder to the high-sulfur powder leached by the zinc oxide is 0.5-1.5:1.
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.
Wherein in the step (3), the concentration of the capturing agent solution is 1-10M.
In the step (4), when the first low-temperature plasma irradiation treatment of the low-temperature plasma irradiation treatments is performed twice in succession, the voltage is 5-75 kV, and the atmosphere is air.
In the step (4), when the second low-temperature plasma irradiation treatment of the low-temperature plasma irradiation treatments is performed twice in succession, the voltage is 5-75 kV, and the atmosphere is a mixed gas of hydrogen gas and carbon dioxide gas.
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.
Reaction mechanism: the high sulfur slag leached by zinc oxygen is dried and ground into powder, and then is mixed with carbon powder, so that the effective contact surface between the carbon powder and the high sulfur powder leached by zinc oxygen can be improved, and the uniformity of mixing is improved. The carbon-doped high-sulfur powder is blown into a combustion furnace for full burning, the high-sulfur powder is further ignited after the carbon powder is ignited in the burning process, the carbon powder is fully burnt to release carbon dioxide, and the high-sulfur powder is fully burnt to release sulfur dioxide gas. Carbon dioxide and sulfur dioxide gas are absorbed by the scavenger solution to produce carbonate and sulfite. In the primary low-temperature plasma irradiation process, oxygen and water vapor in the air are ionized and dissociated in the discharge channel to generate oxygen free radicals and hydroxyl free 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 radical and elemental sulfur. The sodium hydroxide can strengthen the solid-water separation process of elemental sulfur. In the secondary low-temperature plasma irradiation process, hydrogen generates hydrogen free radicals in the discharge channel, the hydrogen free radicals can react with sulfite to generate elemental sulfur and water, and the elemental sulfur generation process can be further enhanced. Excess carbon dioxide introduced during the secondary low temperature plasma irradiation process can react with sodium in the solution to produce soluble sodium bicarbonate.
The beneficial effects are 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 efficient 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, does not generate secondary pollutants, has the highest recovery efficiency of 78.15 percent, and has the purity of the recovered sulfur 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 described below with reference to the accompanying drawings.
The zinc oxygen pressure leaching high sulfur slag is obtained from inner Mongolia zinc smelting company and contains 52.61% of S, 32.78% of O, 6.94% of Zn, 3.52% of Fe, 2.53% of Si, 1.24% of Pb and 0.38% of other impurities.
Example 1 influence of carbon powder and Zinc oxygen pressure leaching high Sulfur powder Mass ratio on Sulfur recovery efficiency and recovery Sulfur purity
And drying the high-sulfur slag subjected to zinc oxygen pressure leaching, and grinding the high-sulfur slag into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. Carbon powder and zinc oxide pressure leaching high-sulfur powder are respectively weighed 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, and are uniformly mixed, so that nine groups of carbon-doped high-sulfur powder are obtained. And (3) respectively blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and respectively introducing gas generated in the combustion process into the trapping agent solutions to obtain nine groups of sulfur-loaded trapping agent solutions, wherein the trapping agent solutions are sodium formate solutions with the concentration of 1M. Carrying out continuous low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution twice, wherein when the sulfur-carried trapping agent solution is subjected to the first low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 5kV, and the action atmosphere of the low-temperature plasma is air; and when the sulfur-carrying trapping agent solution is subjected to the second low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 5kV, the action atmosphere of the low-temperature plasma 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 (3) filtering the nine groups of sulfur suspension slurries respectively, drying the obtained solid part for 24 hours at the temperature of 50 ℃, and grinding to obtain nine groups of elemental sulfur.
Sulfur recovery efficiency calculation: the sulfur recovery efficiency was calculated according to the following formula (1), wherein α% is the sulfur recovery efficiency, m s For recovering the amount (g) of sulfur obtained, m t The amount (g) of high sulfur slag is pressure leached for disposal of zinc oxygen.
α％＝m s /(0.5261×m t )×100％ (1)
Determination of purity of recovered sulfur: purity of recovered sulfur according to industrial sulfur part 1: the solid product (GB/T2449.1-2014) was assayed.
The results of the above experiments are shown in Table 1.
TABLE 1 influence of carbon powder and Zinc oxygen pressure leaching high Sulfur powder mass ratio on sulfur recovery efficiency and recovery Sulfur purity
As can be seen from Table 1, the purity of the recovered sulfur is higher than 98% under the condition that the mass ratio of the carbon powder to the zinc-oxygen pressure leached high-sulfur powder is changed. When the mass ratio of the carbon powder to the zinc oxide pressure leaching high-sulfur powder is smaller than 0.5:1, the carbon powder doping amount is small, 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 oxide pressure leaching high-sulfur powder. When the mass ratio of the carbon powder to the zinc oxide is equal to 0.5-1.5:1, the carbon-doped high-sulfur powder is blown into a combustion furnace for full burning, the high-sulfur powder is further ignited after the carbon powder is ignited in the burning process, the carbon powder is fully burned to release carbon dioxide, and the high-sulfur powder is fully burned to release sulfur dioxide gas. Finally, the sulfur recovery efficiency is higher than 62%. And when the mass ratio of the carbon powder to the zinc oxide pressure leaching high-sulfur powder is more than 1.5:1, the sulfur recovery efficiency is not obvious along with the further increase of the mass ratio of the carbon powder to the zinc oxide pressure leaching high-sulfur powder. Therefore, when the mass ratio of the carbon powder to the zinc oxide pressure leaching high sulfur powder is equal to 0.5-1.5:1, the method is most beneficial to improving the sulfur recovery efficiency and the purity of the recovered sulfur.
Example 2 Effect of Capture agent solution concentration on Sulfur recovery efficiency and recovery Sulfur purity
And drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. The carbon-doped high-sulfur powder is blown into a combustion furnace for full incineration, and gas generated in the combustion process is introduced into a trapping agent solution, wherein the concentration of the trapping agent solution is respectively 0.5M, 0.7M, 0.9M, 1M, 5.5M, 10M, 10.5M, 11.5M and 12.5M sodium formate solution, so that nine groups of sulfur-loaded trapping agent solutions are obtained. Carrying out continuous low-temperature plasma irradiation treatment on nine groups of sulfur-carrying capture agent solutions twice, wherein when the sulfur-carrying capture agent solutions are subjected to the first low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 40kV, and the action atmosphere of the low-temperature plasma is air; and when the sulfur-carrying trapping agent solution is subjected to the second low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 40kV, the action atmosphere of the low-temperature plasma is 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 (3) filtering the nine groups of sulfur suspension slurry respectively 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 nine groups of solid parts 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 recovery Sulfur purity
As can be seen from Table 2, the recovered sulfur was more than 99% pure under varying conditions of the concentration of the scavenger solution. And when the concentration of the scavenger solution is less than 1M, the amount of carbon dioxide and sulfur dioxide gas 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 trapping agent solution is equal to 1-10M, carbon dioxide and sulfur dioxide gas are absorbed by the trapping agent solution to generate carbonate and sulfite. In the primary low-temperature plasma irradiation process, oxygen and water vapor in the air are ionized and dissociated in the discharge channel to generate oxygen free radicals and hydroxyl free 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 radical and elemental sulfur. The sodium hydroxide can strengthen the solid-water separation process of elemental sulfur. In the secondary low-temperature plasma irradiation process, hydrogen generates hydrogen free radicals in the discharge channel, the hydrogen free radicals can react with sulfite to generate elemental sulfur and water, and the elemental sulfur generation process can be further enhanced. Finally, the sulfur recovery efficiency was higher than 67%. When the concentration of the scavenger solution is more than 10M, the sulfur recovery efficiency does not significantly change with further increase of the concentration of the scavenger solution. Thus, combining benefits with costs, the most advantageous is to increase the efficiency of sulfur recovery and purity of the recovered sulfur when the concentration of the scavenger solution is equal to 1-10M.
EXAMPLE 3 Effect of Hydrogen and carbon dioxide gas molar ratios on Sulfur recovery efficiency and purity of recovered sulfur
And drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. And (3) blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a trapping agent solution to obtain a sulfur-loaded trapping agent solution, wherein the trapping agent solution is a sodium formate solution with the concentration of 10M. Carrying out continuous low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution twice, wherein when the sulfur-carried trapping agent solution is subjected to the first low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, and the action atmosphere of the low-temperature plasma is air; when the sulfur-carrying capturing agent solution is subjected to the second low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is mixed gas of hydrogen and carbon dioxide, and the molar ratio of the hydrogen to the carbon dioxide is 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 respectively, so that nine groups of sulfur suspension slurries are obtained. And (3) filtering the nine groups of sulfur suspension slurries respectively to obtain nine groups of solid parts, drying the nine groups of solid parts at 150 ℃ for 6 hours, and grinding the nine groups of solid parts 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 the molar ratio of Hydrogen to carbon dioxide gas on the recovery efficiency of Sulfur and the purity of the recovered sulfur
As can be seen from Table 3, the purity of the recovered sulfur was higher than 99% under the conditions of varying 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 less than 1:10, the hydrogen gas has smaller inlet amount, and hydrogen radicals generated by the hydrogen gas in the discharge channel are reduced, so that the sulfur recovery efficiency is obviously reduced along with the reduction of the molar ratio of the hydrogen gas to the carbon dioxide gas. When the mole ratio of the hydrogen to the carbon dioxide is equal to 1-4:10, hydrogen generates hydrogen free radicals in the discharge channel in the secondary low-temperature plasma irradiation process, the hydrogen free radicals can react with sulfite to generate elemental sulfur and water, and the elemental sulfur generation process can be further enhanced. Finally, the sulfur recovery efficiency is higher than 72%. When the molar ratio of hydrogen gas to carbon dioxide gas is greater than 4:10, the sulfur recovery efficiency does not significantly change as the molar ratio of hydrogen gas to carbon dioxide gas is further increased. Thus, combining benefits with costs, when the molar ratio of hydrogen to carbon dioxide is equal to 1-4:10, it is most advantageous to increase the sulfur recovery efficiency and purity of the recovered sulfur.
Example 4 Effect of the species of Capture agent solution on Sulfur recovery efficiency and recovery Sulfur purity
And drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. And (3) blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a trapping agent solution, wherein the trapping agent solution is respectively a sodium formate solution, a sodium lactate solution or a sodium oxalate solution with the concentration of 10M, so as to obtain three groups of sulfur-loaded trapping agent solutions. Performing continuous low-temperature plasma irradiation treatment on three groups of sulfur-loaded trapping agent solutions twice, wherein when the sulfur-loaded trapping agent solutions are subjected to the first low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, and the action atmosphere of the low-temperature plasma is air; when the sulfur-carrying capturing agent solution is subjected to secondary low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is 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 slurries are obtained. And respectively filtering the three groups of sulfur suspension slurries to obtain three groups of solid parts, drying the three groups of solid parts for 6 hours at the temperature of 150 ℃, and grinding the three groups of solid parts 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 Effect of Capture reagent solution species on Sulfur recovery efficiency and recovery Sulfur purity
As can be seen from Table 4, when the scavenger solution is selected from sodium formate, sodium lactate or sodium oxalate solution, the sulfur recovery efficiency is greater than 76% and the purity of the recovered sulfur is greater than 99%.
Comparative example 1 Effect of different comparative processes on sulfur recovery efficiency and recovered sulfur purity
The process comprises the following steps: and adopting the condition that the capturing agent solution in the embodiment 4 is sodium formate, namely drying the zinc oxygen pressure leaching high-sulfur slag, and grinding the dried zinc oxygen pressure leaching high-sulfur slag into powder to obtain the zinc oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. And (3) blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a capturing agent solution to obtain sulfur-loaded capturing agent solutions, wherein the capturing agent solutions are respectively sodium formate solutions with the concentration of 10M. Carrying out continuous twice low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution, wherein when the first low-temperature plasma irradiation treatment is carried out on the sulfur-carried trapping agent solution, the action voltage of the low-temperature plasma is 75kV, and the action atmosphere of the low-temperature plasma is air; when the sulfur-carrying trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is 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.
Comparison Process 1: and under the condition of not adding carbon powder, drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And (3) blowing zinc oxygen pressure leaching high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a trapping agent solution to obtain sulfur-carrying trapping agent solutions, wherein the trapping agent solutions are respectively sodium formate solutions with the concentration of 10M. Carrying out continuous low-temperature plasma irradiation treatment on the sulfur-carried trapping agent solution twice, wherein when the sulfur-carried trapping agent solution is subjected to the first low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, and the action atmosphere of the low-temperature plasma is air; when the sulfur-carrying trapping agent solution is subjected to secondary low-temperature plasma irradiation treatment, the action voltage of the low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is 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.
Comparison process 2: and (3) only carrying out low-temperature plasma irradiation for the first time, drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. And (3) blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a capturing agent solution to obtain sulfur-loaded capturing agent solutions, wherein the capturing agent solutions are respectively sodium formate solutions with the concentration of 10M. And performing one-time low-temperature plasma irradiation treatment on the sulfur-carrying trapping agent solution, wherein when the first-time low-temperature plasma irradiation treatment is performed on the sulfur-carrying trapping agent solution, the low-temperature plasma action voltage is 75kV, and the low-temperature plasma action atmosphere is air, 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.
Contrast process 3: and only carrying out the second low-temperature plasma irradiation, drying the zinc-oxygen pressure leaching high-sulfur slag, and grinding the dried zinc-oxygen pressure leaching high-sulfur slag into powder to obtain the zinc-oxygen pressure leaching high-sulfur powder. And respectively weighing carbon powder and zinc oxide pressure leaching high-sulfur powder according to the mass ratio of 1.5:1, mixing and stirring uniformly to obtain the carbon-doped high-sulfur powder. And (3) blowing the carbon-doped high-sulfur powder into a combustion furnace for full incineration, and introducing gas generated in the combustion process into a capturing agent solution to obtain sulfur-loaded capturing agent solutions, wherein the capturing agent solutions are respectively sodium formate solutions with the concentration of 10M. And carrying out one-time low-temperature plasma irradiation treatment on the sulfur-carrying trapping agent solution, wherein when the first-time low-temperature plasma irradiation treatment is carried out on the sulfur-carrying trapping agent solution, the action voltage of the low-temperature plasma is 75kV, the action atmosphere of the low-temperature plasma is 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.
Comparison process 4: in the prior art, the process for recovering elemental sulfur by utilizing the zinc-oxygen pressure leaching high-sulfur slag comprises the steps of drying the zinc-oxygen pressure leaching high-sulfur slag, and then ball milling the dried zinc-oxygen pressure leaching high-sulfur slag for 2 hours, wherein the rotating speed of a ball mill is 240rpm, and the ball-solid ratio is 0.45. Mixing the zinc-oxygen pressure leached high-sulfur slag after ball milling with water with equal mass, stirring uniformly, and sieving with a 100-mesh sieve. Vacuum filtering the sieved emulsion, and drying for 6 hours at the temperature of 150 ℃ to obtain elemental sulfur.
The calculation of the sulfur recovery efficiency and the measurement of the purity of the recovered sulfur in the inventive process and comparative processes 1 to 4 were the same as in example 1, and the results are shown in Table 5.
TABLE 5 influence of different comparative processes on the recovery efficiency of sulfur and the purity of recovered sulfur
| 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 efficiency of each of comparative process 1, comparative process 2, comparative process 3, and comparative process 4 was significantly lower than that of the present invention, and the sum of the sulfur recovery efficiencies of comparative process 1, comparative process 2, and comparative process 3 was lower than that of the present invention. The purity of the recovered sulfur in the comparison process 1, the comparison process 2, the comparison process 3 and the comparison process 4 is lower than that in the process of the invention, and the sum of the purity of the recovered sulfur in the comparison process 2 and the purity of the recovered sulfur in the comparison process 3 is lower than that in the process of the invention.
Claims (5)
1. The method for recycling elemental sulfur by utilizing zinc-oxygen pressure leaching high-sulfur slag is characterized by comprising the following steps of:
(1) Drying and grinding the high-sulfur slag leached by zinc oxide pressure to obtain high-sulfur powder leached by zinc oxide pressure;
(2) Mixing the zinc-oxygen pressure leached high-sulfur powder with carbon powder, and stirring to obtain carbon-doped high-sulfur powder;
(3) Incinerating the carbon-doped high sulfur powder, and introducing gas generated in the incineration process into a capture agent solution to obtain a sulfur-loaded capture agent solution, wherein the capture agent solution is any one of a sodium formate solution, a sodium lactate solution and a sodium oxalate solution;
(4) Continuously performing low-temperature plasma irradiation treatment on the sulfur-carrying capturing agent solution twice to obtain sulfur suspension slurry, wherein the voltage is 5-75 kV when the sulfur-carrying capturing agent solution is continuously subjected to the first low-temperature plasma irradiation treatment in the low-temperature plasma irradiation treatment twice, the atmosphere is air, the voltage is 5-75 kV when the sulfur-carrying capturing agent solution is continuously subjected to the second low-temperature plasma irradiation treatment in the low-temperature plasma irradiation treatment twice, and the atmosphere is a mixed gas of hydrogen and carbon dioxide gas;
(5) And filtering the sulfur suspension slurry, drying and grinding the obtained solid to obtain elemental sulfur.
2. The method for recycling elemental sulfur from high sulfur slag by zinc oxygen pressure leaching according to claim 1, wherein in the step (2), the mass ratio of carbon powder to high sulfur powder by zinc oxygen pressure leaching is 0.5-1.5:1.
3. The method for recycling elemental sulfur from high-sulfur slag by utilizing zinc oxygen pressure leaching according to claim 1, wherein in the step (3), the concentration of the capturing agent solution is 1-10M.
4. The method for recycling elemental sulfur by utilizing zinc oxygen pressure leaching high-sulfur slag according to claim 1, wherein the molar ratio of hydrogen gas to carbon dioxide gas is 1-4:10.
5. The method for recycling elemental sulfur by utilizing 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 hours.
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| CN110314649B (en) * | 2019-07-05 | 2022-05-17 | 清华大学深圳研究生院 | Carbon-based heavy metal capture agent and preparation method thereof |
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