CN110860548A - Control method for high-sulfur high-iron gangue pollutant release and passivation material thereof - Google Patents
Control method for high-sulfur high-iron gangue pollutant release and passivation material thereof Download PDFInfo
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- 238000002161 passivation Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 239000011593 sulfur Substances 0.000 title claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 45
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- 231100000719 pollutant Toxicity 0.000 title claims abstract description 39
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000006028 limestone Substances 0.000 claims description 21
- 235000019738 Limestone Nutrition 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 230000000087 stabilizing effect Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
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- 239000002351 wastewater Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
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- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
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- 239000002910 solid waste Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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Abstract
The invention discloses a method for controlling release of high-sulfur and high-iron gangue pollutants, which effectively controls the release of pollutants in gangue by adding a passivation material A and a passivation material B into the gangue. The invention can effectively inhibit the release and acid production capability of various pollutants of the waste rock, and reduce the concentration of various pollutants in the waste rock leachate, thereby protecting the surrounding environment of the waste rock storage yard and laying a good foundation for ecological restoration of the waste rock storage yard in the later period. The material used in the invention is mainly natural mineral, and the material is easy to obtain and process, low in price, simple in construction process, remarkable in effect and strong in operability.
Description
Technical Field
The invention relates to a method for controlling pollutant release, in particular to a method for controlling the release of high-sulfur high-iron gangue pollutants.
Background
Various gangue rich in sulfur and iron is easy to oxidize to produce acid after being stacked in the open air, thereby seriously polluting the surrounding environment and threatening the health of human bodies. Wherein, the coal gangue is larger in quantity, wider in distribution and most prominent in pollution. Coal gangue is solid waste generated in the coal mining and washing processes, the accumulation amount of the coal gangue is nearly 50 hundred million t in China at present, more than 1600 coal gangue hills with large scale occupy about 1.5 kilohm of land2. Under the comprehensive action of air oxidation, rainwater leaching, acid-producing microorganisms and the like in a natural environment, acid mine wastewater (AMD) which has a low pH value, high contents of iron, manganese and sulfate radicals and contains various harmful heavy metal ions is easily weathered, and the environment such as surrounding water, soil and the like is seriously polluted, so that the degradation of terrestrial and aquatic ecosystems is caused. The weathering process, pollution release and possible environmental ecological risks, pollution prevention and ecological restoration of the sulfur-containing tailings of the coal gangue have attracted extensive attention.
The pollution control of the traditional high-sulfur high-iron gangue is mostly the terminal treatment of pollutants, such as the treatment of acid mine wastewater. Because the release of acid and accompanying pollutants generated by the weathered oxidation of the gangue is a slow and continuous process, the treatment of the acid mine wastewater by using the traditional terminal treatment technology is a long-lasting process with long treatment period, high comprehensive investment and large consumption of manpower and material resources. The technology for treating the acid mine wastewater at the tail end is not easy to popularize and apply in economic poor and ecologically fragile karst coal mine areas. Therefore, how to reduce the release of pollutants in the high-sulfur high-iron gangue is very effective for fundamentally solving the AMD pollution problem.
The existing common methods for treating waste rock pollution in situ include tailing treatment methods such as a reclamation method, a tailing pond, a filling method and a consolidation method, but the method is not suitable for treating the high-sulfur and high-iron waste rock, so that the treatment cost is huge, and the ecological environment cannot be improved. In addition, water system covering (CN107080916A) is utilized to reduce the oxidation of sulfur-containing minerals in tailings and the generation of AMD, but the whole process is complicated for a gangue storage yard which is stored for years. And antibacterial measures (CN103357641A) are also adopted to inhibit the microbial oxidation in the gangue so as to achieve the effect of in-situ control of gangue pollutants, but the adoption of the antibacterial agent is very easy to threaten the ecology of a gangue storage yard and is not beneficial to the ecological reconstruction of the gangue storage yard in the later period. .
Disclosure of Invention
The invention aims to provide a control method for releasing high-sulfur high-iron gangue pollutants. The invention can effectively inhibit the release and acid production capability of various pollutants of the waste rock, and reduce the concentration of various pollutants in the waste rock leachate, thereby protecting the surrounding environment of the waste rock storage yard and laying a good foundation for ecological restoration of the waste rock storage yard in the later period. The material used in the invention is mainly natural mineral, and the material is easy to obtain and process, low in price, simple in construction process, remarkable in effect and strong in operability.
The technical scheme of the invention is as follows: a control method for releasing high-sulfur and high-iron gangue pollutants is characterized in that a passivation material A and a passivation material B are added into gangue to effectively control the release of pollutants in the gangue; the passivation material is obtained by the following method:
and (3) passivation material A: crushing limestone, and adding NaOH to modify the limestone to enable the pH value of the limestone to reach 9-11;
and (3) passivation material B: adding NaOH into crushed silica for modification, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, uniformly mixing to ensure that the pH value is stabilized to 10-11, drying the stabilized modified silica until the water content is 15-20%, and then adding CaO into the dried modified silica2，CaO2The addition amount of the modified silica is 5 to 12 percent of the mass of the dried modified silica.
In the control method for releasing the high-sulfur and high-iron gangue pollutants, the specific control method comprises the following steps:
(1) turning over the coal gangue, adding a passivation material A, uniformly mixing, and reacting until the pH value is stabilized to 5-6;
(2) and adding the passivation material B into the gangue reacted by the passivation material A, and uniformly mixing.
In the control method for releasing the high-sulfur and high-iron gangue pollutants, the adding amount of the passivation material B is 3% -12% of the dry weight of the gangue.
In the method for controlling the release of the high-sulfur and high-iron gangue pollutants, CaCO in the limestone3The content is 82-90%.
In the control method for releasing the high-sulfur and high-iron gangue pollutants, in the preparation process of the passivation material, the limestone and the silica are respectively crushed to be less than 50 meshes.
The passivation material prepared by the method for controlling the release of the high-sulfur high-iron gangue pollutants is provided.
The invention has the beneficial effects that: compared with the prior art, the invention provides a control method for the release of high-sulfur and high-iron gangue pollutants, the material used in the method is a composite passivation material, and the passivation material comprises modified limestone, modified silica and calcium peroxide; in the components, the modified limestone can improve the pH in the gangue and reduce the gangue acid-producing capacity, so that the pH of gangue leachate is reduced, the pH in the gangue can be improved again by adding the modified silica, exchangeable Fe, Mn and other heavy metals in the gangue can be adsorbed and fixed by utilizing the high specific surface activity (large specific surface area) of the modified silica, and the Fe in the gangue can be rapidly reduced by adding the calcium peroxide2+The content of the sulfur-oxidizing bacteria and the biological activity of the sulfur-oxidizing bacteria, so that the chemical oxidation and the biological oxidation of the gangue are inhibited to the maximum extent, the reasonable matching of the components can fully play various roles, and finally the release of pollutants in the gangue is effectively controlled.
Drawings
FIG. 1 is a graph showing the effect of passivating agent addition on pH of high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 2 is a graph showing the effect of passivator addition on the high-sulfur high-iron gangue (coal gangue) leachate Eh;
FIG. 3 is a graph showing the effect of passivator addition on Fe content in high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 4 is a graph showing the effect of passivator addition on Mn content of high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 5 is a graph showing the effect of passivant addition on Cd content in high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 6 is a graph showing the effect of passivating agent addition on Cr content in high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 7 is a graph showing the effect of passivator addition on Zn content in high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 8 is a graph showing the effect of passivating agent addition on Cu content of high-sulfur high-iron gangue (coal gangue) leachate;
FIG. 9 shows the leaching liquor SO of high-sulfur and high-iron gangue (coal gangue) added with passivating agent4 2-Influence graph of content;
FIG. 10 is a graph showing the effect of passivating agent addition on leaching output of high-sulfur and high-iron gangue (coal gangue) leachate.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1 of the invention: a control method for releasing high-sulfur high-iron coal gangue pollutants specifically comprises the following steps:
(1) the used coal gangue waste residue is collected from a high-sulfur high-iron coal gangue storage yard, weathered coal gangue is collected and taken back to a laboratory, the weathered coal gangue is paved on kraft paper and naturally dried indoors, and the dried coal gangue is sieved by a 2mm sieve and fully and uniformly mixed.
(2) Adding 5% of passivation material A by weight of the coal gangue, reacting for 1 month, and stabilizing the pH to 5-6;
(3) and (3) adding 5% of passivation material B into the coal gangue component (2) according to the weight of the coal gangue, and stabilizing for 1 month to stabilize the pH value in a coal gangue system to about 6.
The passivation material A and the passivation material B are obtained by the following method:
(1) and (3) passivation material A: selecting CaCO3And crushing the limestone with the content of 82% -90% to be less than 50 meshes, and then adding NaOH to modify the limestone to enable the pH value to reach 9-11.
(2) And (3) passivation material B: silicon is mixedCrushing the silica into powder with a particle size of less than 50 meshes, adding NaOH, uniformly mixing the powder and the NaOH for modification, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, stabilizing the pH value of the silica-NaOH system to 10-11, drying the stabilized modified silica until the water content is 15-20%, and adding CaO into the dried silica2Mixing, sealing and storing. Added CaO2The amount of the modified silica is 10% of the modified silica mass which is dried until the water content is 15% -20%.
Example 2 of the invention: a control method for releasing high-sulfur high-iron coal gangue pollutants specifically comprises the following steps:
(1) the used coal gangue waste residue is collected from a high-sulfur high-iron coal gangue storage yard, weathered coal gangue is collected and taken back to a laboratory, the weathered coal gangue is paved on kraft paper and naturally dried indoors, and the dried coal gangue is sieved by a 2mm sieve and fully and uniformly mixed.
(2) Adding 10% of passivation material A by weight of the coal gangue, reacting for 1 month, and stabilizing the pH to 5-6;
(3) adding 12% of passivation material B into the coal gangue component (2) according to the weight of the coal gangue, and stabilizing for 1 month to stabilize the pH value in a coal gangue system to about 6.
The passivation material A and the passivation material B are obtained by the following method:
(1) and (3) passivation material A: selecting CaCO3And crushing the limestone with the content of 82% -90% to be less than 50 meshes, and then adding NaOH to modify the limestone to enable the pH value to reach 9-11.
(2) And (3) passivation material B: crushing silica to less than 50 meshes, adding NaOH, uniformly mixing, modifying, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, stabilizing the pH value to 10-11, drying the stabilized modified silica to ensure that the water content is 15-20%, and adding CaO into the dried silica2Mixing, sealing and storing. Added CaO2The amount of the modified silica is 12% of the modified silica mass which is dried until the water content is 15% -20%.
Example 3 of the invention: a control method for releasing high-sulfur high-iron coal gangue pollutants specifically comprises the following steps:
(1) the used coal gangue waste residue is collected from a high-sulfur high-iron coal gangue storage yard, weathered coal gangue is collected and taken back to a laboratory, the weathered coal gangue is paved on kraft paper and naturally dried indoors, and the dried coal gangue is sieved by a 2mm sieve and fully and uniformly mixed.
(2) Adding 2% of a passivation material A according to the weight of the coal gangue, reacting for 1 month, and stabilizing the pH value to 5-6;
(3) adding 3% of passivation material B into the coal gangue component (2) according to the weight of the coal gangue, and stabilizing for 1 month to stabilize the pH value in the coal gangue system to about 6.
The passivation material A and the passivation material B are obtained by the following method:
(1) and (3) passivation material A: selecting CaCO3And crushing the limestone with the content of 82% -90% to be less than 50 meshes, and then adding NaOH to modify the limestone to enable the pH value to reach 9-11.
(2) And (3) passivation material B: crushing silica to less than 50 meshes, adding NaOH, uniformly mixing, modifying, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, stabilizing the pH value to 10-11, drying the stabilized modified silica to ensure that the water content is 15-20%, and adding CaO into the dried silica2Mixing, sealing and storing. Added CaO2The amount of the modified silica is 5% of the modified silica mass which is dried until the water content is 15% -20%.
Example 4 of the invention: a control method for releasing high-sulfur high-iron coal gangue pollutants specifically comprises the following steps:
(1) the used coal gangue waste residue is collected from a high-sulfur high-iron coal gangue storage yard, weathered coal gangue is collected and taken back to a laboratory, the weathered coal gangue is paved on kraft paper and naturally dried indoors, and the dried coal gangue is sieved by a 2mm sieve and fully and uniformly mixed.
(2) Adding 7% of passivation material A by weight of the coal gangue, reacting for 1 month, and stabilizing the pH to 5-6;
(3) adding 7% of passivation material B into the coal gangue component (2) according to the weight of the coal gangue, and stabilizing for 1 month to stabilize the pH value in a coal gangue system to about 6.
The passivation material A and the passivation material B are obtained by the following method:
(1) and (3) passivation material A: selecting CaCO382 to 90 percent of limestone is prepared fromCrushing the limestone until the particle size is smaller than 50 meshes, and then adding NaOH to modify the limestone until the pH value reaches 9-11.
(2) And (3) passivation material B: crushing silica to less than 50 meshes, adding NaOH, uniformly mixing, modifying, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, stabilizing the pH value to 10-11, drying the stabilized modified silica to ensure that the water content is 15-20%, and adding CaO into the dried silica2Mixing, sealing and storing. Added CaO2The amount of the modified silica is 7% by mass of the modified silica which is dried until the water content is 15-20%.
To demonstrate that the control method is applied to the most main metal ions and SO in gangue (coal gangue)4 2-Impact of release, i performed a relevant test. The coal gangue after the passivation treatment of the 4 embodiments is respectively taken for testing. The test process comprises the following steps:
(1) the coal gangue added with the passivation material and the coal gangue not added with the passivation material are respectively filled in a leaching column with the length of 50cm and the diameter of 110mm, the local rainfall of one year is taken, leaching is carried out on the coal gangue added with the passivation material and the coal gangue not added with the passivation material in five times by adopting a leaching mode, and the coal gangue not added with the passivation material is used as a Control (CK).
(2) After each leaching test is finished, analyzing the pH, Eh, Fe, Mn, main heavy metals and SO of the coal gangue leachate4 2-And the like.
In the above tests, the tests of the coal gangue without the passivation material and with the passivation material are repeated for 3 times, so as to reduce the test error.
Wherein the test data for example 1 is shown in table 1 and figures 1-10.
TABLE 1 passivator addition to the most predominant metal ions and SO in high sulfur high iron gangue4 2-Effect of Release
As shown in the drawing and the attached table, the results show that the additionThe passivation material can reduce main metal ions and SO in the coal gangue4 2-The leaching amount of leaching solution, Eh, Fe, Mn, Cu, Zn, Cd, Cr and SO are reduced4 2-Increasing the pH value of the leachate to make the leachate alkaline or slightly alkaline. The test results show that the passivation material and the method successfully realize effective control of pollutant release in the coal gangue leachate, the improvement effect is obvious, and the control effect on the coal gangue treatment is as follows:
(1) pH in the leachate: the improvement range is 293.00% -397.63%;
(2) eh in the filtrate: the reduction amplitude is 60.02 to 91.27 percent;
(3) and (3) Fe release amount in the coal gangue: the reduction amplitude is 99.83 to 99.97 percent;
(4) the release amount of Mn in the coal gangue is as follows: the reduction amplitude is 85.31-97.54%;
(5) the release amount of Cu in the coal gangue is as follows: the reduction amplitude is 56.65-84.17%;
(6) the release amount of Zn in the coal gangue is as follows: the reduction amplitude is 95.20 to 100 percent;
(7) the release amount of Cd in the coal gangue is as follows: the reduction amplitude is 89.36 to 96.31 percent;
(8) the release amount of Cr in the coal gangue is as follows: the reduction amplitude is 56.49-68.60%;
(9) SO in coal gangue4 2-The release amount is as follows: the reduction amplitude is 69.30-80.56%.
The test results of other embodiments are similar to the test structure of embodiment 1, and the results show that the method for controlling the release of the high-sulfur high-iron gangue pollutants provided by the invention can effectively control the release of various pollutants in the coal gangue.
Another core of the present invention is to provide a passivation material for controlling the release of high-sulfur high-iron gangue pollutants, which is composed of passivation material a and passivation material B in the above embodiments, and the specific preparation method thereof has been described in the above embodiments and will not be described herein again.
Claims (6)
1. A control method for releasing high-sulfur high-iron gangue pollutants is characterized by comprising the following steps: the release of pollutants in the gangue is effectively controlled by adding the passivation material A and the passivation material B into the gangue; the passivation material is obtained by the following method:
and (3) passivation material A: crushing limestone, and adding NaOH to modify the limestone to enable the pH value of the limestone to reach 9-11;
and (3) passivation material B: adding NaOH into crushed silica, uniformly mixing, modifying, adding a proper amount of water to ensure that the water content in a silica-NaOH system is 40-50%, stabilizing the pH value to 10-11, drying the stabilized modified silica until the water content is 15-20%, and adding CaO into the dried modified silica2，CaO2The addition amount of the modified silica is 5 to 12 percent of the mass of the dried modified silica.
2. The method for controlling the release of high-sulfur high-iron gangue pollutants as claimed in claim 1, wherein the method comprises the following steps: the specific control method comprises the following steps:
(1) turning up waste rocks, adding a passivation material A, uniformly mixing, and reacting until the pH value is stabilized to 5-6;
(2) and adding the passivation material B into the gangue reacted by the passivation material A, and uniformly mixing.
3. The method for controlling the release of high-sulfur high-iron gangue pollutants as claimed in claim 2, wherein the method comprises the following steps: the addition amount of the passivation material B is 3-12% of the dry weight of the gangue.
4. The method for controlling the release of high-sulfur high-iron gangue pollutants as claimed in claim 1, wherein the method comprises the following steps: CaCO in the limestone3The content is 82-90%.
5. The method for controlling the release of high-sulfur high-iron gangue pollutants as claimed in claim 1, wherein the method comprises the following steps: in the preparation process of the passivation material, limestone and silica are respectively crushed to below 50 meshes.
6. The passivation material prepared by the method for controlling the release of the high-sulfur high-iron gangue pollutants according to any one of claims 1 to 5.
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| CN114588579A (en) * | 2022-03-17 | 2022-06-07 | 西安科技大学 | Method for passivating metals in heavy metal abnormal coal gangue by using solid passivator |
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