CN116174469A - Application of double-effect restoration agent taking electrolytic manganese slag as base material in restoration of heavy metal contaminated soil - Google Patents
Application of double-effect restoration agent taking electrolytic manganese slag as base material in restoration of heavy metal contaminated soil Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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Abstract
The invention relates to the technical field of environmental heavy metal soil remediation, in particular to application of a remediation agent taking electrolytic manganese slag as a base material in heavy metal contaminated soil remediation. According to the invention, electrolytic manganese slag is taken as a base material, the electrolytic manganese slag is mixed with iron-containing materials and ball-milled for modification, and the silicate components and the iron-manganese elements in the electrolytic manganese slag are utilized to passivate heavy metal ions in soil, so that the passivation of heavy metals in the soil can be promoted, the contents of the medium elements such as calcium, magnesium, sulfur, silicon and manganese in the soil can be increased, the fertilizer efficiency of the soil can be enhanced, and only the electrolytic manganese slag-based repairing agent is mixed into the heavy metal polluted soil without other operations, so that the method has important environmental benefits and social values, and provides a certain technical guide for recycling and harmlessness of the electrolytic manganese slag.
Description
Technical Field
The invention relates to the technical field of environmental heavy metal soil remediation, in particular to application of a double-effect remediation agent taking electrolytic manganese slag as a base material in heavy metal contaminated soil remediation.
Background
In the increasingly developing process of industrial and mining activities, a large amount of waste residues are generated, and are piled up around mines or factories, so that soil around the mines or factories is polluted by air sedimentation, rain water leaching, dust diffusion and the like, and heavy metal pollution is caused to the periphery of the soil, so that the life production activities of human beings are influenced.
The electrolytic manganese slag is acid leaching slag generated after mineral powder is subjected to sulfuric acid leaching in the electrolytic manganese production process. The electrolytic manganese industry is a high pollution industry, and a large amount of solid waste residues are generated in the process of producing electrolytic manganese, so that environmental pollution is caused.
At present, farmland soil is mainly restored by using mineral (class) materials, but the farmland soil is faced with implementation pain points of high cost, complex construction, low long-acting performance and the like. Therefore, the development of a long-acting, economical and safe soil heavy metal restoration agent is urgent.
At present, the existing research on the treatment of the heavy metal contaminated land at home and abroad mainly comprises the step of compounding pure substances such as ferrous sulfate and the like into passivating agents to repair and stabilize heavy metals in the soil, but most of the passivating agents are used for single heavy metal contaminated soil or similar heavy metal contaminated soil, and the research on more heavy metal contaminated soil is less because most of the chemical toxicity of the compounding agents consisting of the pure chemical agents is easy to pollute the soil once the chemical toxicity is improper.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention firstly aims to provide the application of the double-effect repairing agent taking electrolytic manganese slag as a base material in repairing heavy metal contaminated soil.
The substances in the electrolytic manganese slag can be changed into substances containing muscovite and the like and other similar silicate substances through activation, so that the electrolytic manganese slag has wide prospect of removing heavy metal ions in the passivated soil. The electrolytic manganese slag is used as a base material to prepare a repairing agent for repairing heavy metal contaminated soil, so that the original waste material can be recycled, and the heavy metal contamination in the soil can be effectively relieved.
In order to achieve the above purpose, the present invention proposes the following technical solutions:
the invention provides an application of a double-effect repairing agent taking electrolytic manganese slag as a base material in repairing heavy metal polluted soil, wherein the repairing agent is a mixture of electrolytic manganese slag and iron-containing materials, and the iron-containing materials are selected from pyrite and FeSO 4 And reduced iron powder. Further, the heavy metal in the heavy metal contaminated soil at least comprises cadmium, chromium, lead and arsenicIs a kind of the above-mentioned materials.
Further, the mass ratio of the electrolytic manganese slag to the iron-containing material is (0.5-3): 1; the preferred mass ratio is (1 to 1.5): 1.
Further, the specific operation of the application is as follows: and (3) mixing the repairing agent into the heavy metal polluted soil according to the mass ratio of 0.2% -5%.
When the double-effect repairing agent using the electrolytic manganese slag as the base material is applied to heavy metal polluted soil, the passivation of the heavy metal in the soil can be promoted, the content of nutrient elements such as calcium, magnesium, sulfur and the like in the soil can be increased, and the fertilizer efficiency of the soil can be enhanced. Meanwhile, the application process of the repairing agent is convenient to implement, has no complicated objective conditions, can be suitable for various heavy metal polluted soil environments, and is low in implementation cost. The material can increase the content of the medium elements such as calcium, magnesium, sulfur, silicon, manganese and the like in the soil, enhance the fertilizer efficiency of the soil and passivate heavy metals in the soil.
The invention also provides a preparation method of the double-effect repairing agent with electrolytic manganese slag as a base material, which sequentially comprises the following steps:
s1 mixing
Mixing electrolytic manganese slag and iron-containing materials according to a certain proportion to obtain a mixture;
s2 ball milling
And (3) putting the mixture obtained in the step (S1) into a ball mill, ball milling, taking out the ball-milled solid, and grinding and screening to obtain the double-effect repairing agent.
Preferably, the ball milling time is 1-5h, and the ball milling rotating speed is 200-600r/min.
Most preferably, the iron-containing material is reduced iron powder, the mass ratio of the electrolytic manganese slag to the reduced iron powder is 1:1, the ball milling speed is 500r/min, the ball milling time is 1h, and the ball-material ratio is 10:1.
The mechanism of the electrolytic manganese slag-based restoration agent for adsorbing soil heavy metals is as follows:
the electrolytic manganese slag contains high content of silicon dioxide and manganese dioxide, and is mixed with iron substances in the ore, ball-milled and activated to enable the iron substances to be activated into silicate substances, the content of ferrous ions and sulfur is increased, then active groups in the activated electrolytic manganese slag react with positive divalent ions such as lead, cadmium and copper in the heavy metal contaminated soil firstly after the activated electrolytic manganese slag contacts with the heavy metal contaminated soil, and then the activated calcium ions and the activated iron ions are slowly released to be combined with arsenic in the soil, so that arsenic in the soil is fixed through the electrolytic manganese slag and iron-manganese elements in the iron-containing material, the mobility of the arsenic is reduced, the arsenic is fixed and stabilized, and the leaching toxicity of the arsenic is reduced. On the other hand, the method can also increase the medium-nutrient elements such as calcium, magnesium, sulfur and the like of the soil.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the double-effect repairing agent using the electrolytic manganese slag as the base material has the characteristics of simple preparation method, convenient operation, no secondary pollution, good adsorption effect and passivation effect, low cost, excellent adsorption performance on toxic heavy metal ions at normal temperature, and provides a new idea for recycling the electrolytic manganese slag, and has important environmental benefit and good application prospect.
The invention is a material using electrolytic manganese slag as base material, the electrolytic manganese slag and the iron ore are mixed together, and the electrolytic manganese slag and the iron ore are modified, and the components in the electrolytic manganese slag are used for passivating heavy metal ions in soil, so that the electrolytic manganese slag has important environmental benefit and social value.
Drawings
FIG. 1 is an XRD pattern obtained for electrolytic manganese slag (EMR) used in the examples, and the numbers in the patterns are respectively: 1-calcium carbonate, 2-dolomite, 3-wollastonite, 4-quartz, 5-gypsum, 6-white wollastonite, 7-rosepside;
FIG. 2 is an XRD pattern of the restorative obtained in example 1, with the numbers shown in the figures: 1-FeOOH,2-CaCO 3 ,3-Ca(OH) 2 ,4-Ca 2 SiO 4 ,5-FeS 2 ,6-SiO 2 ,7-MnSiO 3 ,8-MnO 2 ,9-CaSO 4 ·0.5H 2 O。
As can be seen from fig. 1 and 2, the crystalline phases of electrolytic manganese slag are mainly quartz, gypsum, wollastonite, white wollastonite, and rosepside; then ball milling activation is carried out after iron ore is added, the crystal phase is changed into an amorphous crystal phase, and the iron element in the electrolytic manganese slag is changed into ferrihydrite (FeOOH) along with the ferrihydrite, manganese dioxide and a calcium-containing compound to form a calcium-manganese-iron compound, so that passivation and repair of arsenic element in soil are facilitated.
2FeS 2 +2H 2 O+7O 2 →2Fe 2+ +4SO 4 2- +4H + (3)
4Fe 2+ +O 2 +8OH - →4FeOOH+2H 2 O (4)
4Fe 2+ +O 2 +4H + →4Fe 3+ +2H 2 O (5)
2MnO+O 2 →2MnO 2 (6)
MnSO 4 +2OH - →Mn(OH) 2 +SO 4 2- (7)
AsO 4 3- +FeOOH→FeAsO 4 +H 2 O (8)
2AsO 4 3- +3Ca 2+ →Ca 3 (AsO 4 ) 2 (9)
Detailed Description
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
The following examples are given for illustration of the invention only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present invention based on the specific embodiments of the present invention.
In the following examples, the starting materials used: electrolytic manganese slag (EMR) from Zhongxin Daganese mining Co., ltd, having a particle size of 149 μm; the electrolytic manganese slag was analyzed for its composition by weight percent by XRF (X-ray fluorescence spectroscopy: zetium, netherlands, panalytics b.v.), as shown in the following table:
TABLE 1
Sample | MgO | Al 2 O 3 | SiO 2 | CaO | Fe 2 O 3 | Na 2 O | P 2 O 5 | CO 2 | SO 3 | K 2 O | MnO |
EMR/% | 1.73 | 1.85 | 17.59 | 13.20 | 7.05 | 0.11 | 0.27 | 19.95 | 31.80 | 0.81 | 5.33 |
Example 1 an electrolytic manganese slag-based restoration agent was prepared as follows:
s1 mixing
6g of electrolytic manganese slag and 4g of pyrite (components: 55.88% Fe,35.55% S,2.28% Si) were mixed to obtain a mixture;
s2 ball milling
Putting the mixture obtained in the step S1 into a ball mill, ball milling for 2 hours at the ball material ratio of 10:1 at 500r/min, taking out the obtained solid, grinding, and sieving with a 100-mesh sieve to obtain the repairing agent for later use.
0.02g of the repairing agent is respectively added into 0.02L of arsenic acid with the initial concentration of arsenic element of 50mg/L and As 2 O 3 In the solution, after turning and oscillating for 1h at normal temperature, filtering, measuring the content of the residual arsenic by an atomic spectrophotometer, and calculating: the adsorption capacity of the repairing agent for As (V) is 35.10mg/g, and the adsorption capacity for As (III) is 29.11mg/g.
The prepared repairing agent is applied to heavy metal polluted soil to detect the soil repairing performance.
Specifically, a heavy metal-severely contaminated soil (the moisture content of which is 60%) in a mining area in Hubei province was taken, and the heavy metal content in the soil is shown in Table 2.
TABLE 2 soil heavy metal content
Mixing 100g of the soil with 3g of the repairing agent uniformly, culturing for 10d-30d at room temperature, stirring the soil irregularly during the culturing process, supplementing water in time to maintain the water content of the soil to be the water content of the original soil all the time, extracting heavy metals by adopting a TCLP leaching method, and analyzing and detecting, wherein the result is shown in the table 3.
TABLE 3 extraction of heavy Metal concentration by TCLP Leaching method (TCLP, μg/L)
Cr | As | Cd | Pb | Ni | Cu | |
Before repair | 370.65 | 62.81 | 131.65 | 612.28 | 192.47 | 729.29 |
10d | 25.92 | 7.87 | 71 | 32.08 | 171.13 | 323.02 |
20d | 15.63 | 7.2 | 61.05 | 69.94 | 111.25 | 384.25 |
30d | 19.29 | 8.82 | 73.73 | 21.91 | 169.93 | 412.16 |
10d, 20d, 30d in the table represent the soil cultivated 10d, 20d and 30d at room temperature in the above experiment, respectively.
As can be seen from the data in the table, the repairing agent prepared in the embodiment has passivation effect on various heavy metals in the soil, so that leaching toxicity of Cr, as, cd, pb, ni, cu and the like in the polluted soil is remarkably reduced, and meanwhile, the result of monitoring the leaching amount of manganese in the soil shows that the leaching manganese content in the soil is not increased along with the increase of the incubation time.
Example 2 an electrolytic manganese slag-based restoration agent was prepared as follows:
s1 mixing
Mixing 5g of electrolytic manganese slag and 5g of reduced iron powder to obtain a mixture;
s2 ball milling
Putting the mixture obtained in the step S1 into a ball mill, ball milling for 1h at a ball material ratio of 10:1 at 500r/min, taking out the obtained solid, grinding, and sieving with a 100-mesh sieve to obtain the repairing agent for later use.
0.02g of the repairing agent is respectively added into 0.02L of arsenic acid and As with initial concentration of arsenic element of 50mg/L 2 O 3 In the solution, after turning and oscillating for 1h at normal temperature, filtering, measuring the content of the residual arsenic by an atomic spectrophotometer, and calculating: the adsorption capacity of the repairing agent for As (V) is 35.10mg/g, and the adsorption capacity for As (III) is 39.11mg/g.
The prepared repairing agent is applied to heavy metal polluted soil to detect the soil repairing performance. Specifically, heavy metal-contaminated soil was taken, and the same soil as that sampled together in example 1 was taken.
After 10g of the soil and 0.3g of the repairing agent are uniformly mixed, the soil is cultivated for 1d at room temperature, the soil is stirred irregularly during the cultivation process, meanwhile, water is timely supplied to maintain the water content of the soil to be 60% all the time, and then, a TCLP leaching method (the same as in example 1) is adopted to extract heavy metals and analyze and detect, and the results are shown in Table 4.
TABLE 4 extraction of heavy Metal concentration by TCLP Leaching method (TCLP, μg/L)
Cr | As | Cd | Pb | Ni | Cu | |
Before repair | 370.65 | 62.81 | 131.65 | 612.28 | 192.47 | 729.29 |
1d | 40.46 | 0.89 | 29.33 | 52.09 | 138.63 | 223.02 |
As can be seen from the data in the table, the repairing agent prepared in the embodiment has passivation effect on various heavy metals in the soil, so that leaching toxicity of Cr, as, cd, pb, ni, cu and the like in the polluted soil is remarkably reduced, and meanwhile, the result of monitoring the leaching amount of manganese in the soil shows that the leaching manganese content in the soil is not increased along with the increase of the incubation time.
Example 3 an electrolytic manganese slag-based restoration agent was prepared as follows:
s1 mixing
Taking 5g of electrolytic manganese slag and 5g of FeSO 4 Mixing to obtain a mixture;
s2 ball milling
Putting the mixture obtained in the step S1 into a ball mill, ball milling for 1h at a ball material ratio of 10:1 at 500r/min, taking out the obtained solid, grinding, and sieving with a 100-mesh sieve to obtain the repairing agent for later use.
0.02g of the repairing agent is respectively added into 0.02L of arsenic element with initial concentration of all50mg/L arsenic acid and As 2 O 3 In the solution, after turning and oscillating for 1h at normal temperature, filtering, measuring the content of the residual arsenic by an atomic spectrophotometer, and calculating: the adsorption capacity of the repairing agent for As (V) is 26.55mg/g, and the adsorption capacity for As (III) is 30.11mg/g.
The prepared repairing agent is applied to heavy metal polluted soil to detect the soil repairing performance. Specifically, heavy metal-contaminated soil was taken, and the same soil as that sampled together in example 1 was taken.
After 10g of the soil and 0.3g of the repairing agent are uniformly mixed, the soil is cultivated for 1d at room temperature, the soil is stirred irregularly during the cultivation process, meanwhile, water is timely supplied to maintain the water content of the soil to be 60% all the time, and then, a TCLP leaching method (the same as in example 1) is adopted to extract heavy metals and analyze and detect, and the results are shown in Table 5.
TABLE 5 extraction of heavy Metal concentration by TCLP Leaching method (TCLP, μg/L)
Cr | As | Cd | Pb | Ni | Cu | |
Before repair | 370.65 | 62.81 | 131.65 | 612.28 | 192.47 | 729.29 |
1d | 53.49 | 5.57 | 56.86 | 45.60 | 138.09 | 223.02 |
As can be seen from the data in the table, the repairing agent prepared in the embodiment has passivation effect on various heavy metals in the soil, so that leaching toxicity of Cr, as, cd, pb, ni, cu and the like in the polluted soil is remarkably reduced, and meanwhile, the result of monitoring the leaching amount of manganese in the soil shows that the leaching manganese content in the soil is not increased along with the increase of the incubation time.
Comparative example 1
Ball milling the electrolytic manganese slag at 400r/min for 2h, taking out the obtained solid, grinding, and sieving with a 100-mesh sieve to obtain the ball-milled electrolytic manganese slag for later use.
Respectively putting 0.02g of ball-milled electrolytic manganese slag into 0.02L of arsenic acid with initial concentration of arsenic element of 50mg/L and As 2 O 3 In the solution, after turning and oscillating for 1h at normal temperature, filtering, measuring the content of the residual arsenic by an atomic spectrophotometer, and calculating: the adsorption capacity of the electrolytic manganese slag after ball milling for As (V) is 5mg/g, and the adsorption capacity for As (III) is 6mg/g.
And applying the prepared ball-milled electrolytic manganese slag to heavy metal polluted soil, and detecting the soil restoration performance. Specifically, the soil seriously contaminated by heavy metals is taken and the same soil is sampled together with the soil in the embodiment 1, 100g of the soil and 3g of the ball-milled electrolytic manganese slag are evenly mixed, then the mixture is cultivated for 10d at room temperature, the soil is stirred irregularly in the cultivation process, meanwhile, water is timely supplied to maintain the moisture content of the soil to be the moisture content of the original soil all the time, and then the TCLP leaching method (same as the embodiment 1) is adopted to extract heavy metals and analyze and detect the heavy metals, so that the results are shown in the table 6.
TABLE 6 influence of electrolytic manganese slag after ball milling on heavy metal concentration in contaminated soil (TCLP, μg/L)
Conclusion: the leaching toxicity of heavy metals in the soil treated by ball milling electrolytic manganese slag is reduced, but the leaching toxicity is not reduced much after mixing, which indicates that the electrolytic manganese slag after ball milling has passivation effect on the heavy metals in the soil, but weaker than the mixed passivation effect.
Comparative example 2
0.02g of electrolytic manganese slag is respectively put into 0.02L of arsenic acid with the initial concentration of arsenic element of 50mg/L and As 2 O 3 In the solution, after turning and oscillating for 1h at normal temperature, filtering, measuring the content of the residual arsenic by an atomic spectrophotometer, and calculating: the adsorption capacity of the electrolytic manganese slag for As (V) is 0.90mg/g, and the adsorption capacity for As (III) is 4.29mg/g.
And applying the electrolytic manganese slag to the soil polluted by the heavy metal, and detecting the soil restoration performance. Specifically, the soil seriously contaminated by heavy metals is taken and the same soil is sampled together with the soil in the embodiment 1, 100g of the soil and 3g of electrolytic manganese slag are uniformly mixed, then the soil is cultivated for 10 days at room temperature, the soil is not regularly stirred in the cultivation process, meanwhile, water is timely added to maintain the moisture content in the soil to be 60% all the time, and then the TCLP leaching method (same as the embodiment 1) is adopted to extract the heavy metals and analyze and detect the heavy metals, and the result is shown in the table 7.
TABLE 7 influence of electrolytic manganese slag on heavy metal concentration in contaminated soil (TCLP, μg/L)
Conclusion: the leaching toxicity of heavy metals in the soil treated by the original electrolytic manganese slag is reduced, but the leaching toxicity is reduced more after the electrolytic manganese slag is not mixed, which indicates that the electrolytic manganese slag after ball milling has passivation effect on the heavy metals in the soil, but the passivation effect is weaker than that of the mixed electrolytic manganese slag.
According to the invention, the electrolytic manganese slag is combined with the iron-containing material, and the electrolytic manganese slag and the iron-containing material are subjected to mechanical ball milling to prepare the soil restoration agent, so that on one hand, the cost can be saved, the secondary pollution of the electrolytic manganese slag can be avoided, and the soil restoration agent can be used for restoring heavy metal pollution of soil. On the other hand, nitrogen element in the repairing agent can be slowly released into soil with the passage of time, and a great amount of nutrients can be provided for the growth of plants in the soil, so that the soil environment polluted by heavy metals is further improved.
Claims (5)
1. Application of double-effect restoration agent taking electrolytic manganese slag as base material in restoration of heavy metal polluted soil, wherein the double-effect restoration agent is a mixture of electrolytic manganese slag and iron-containing materials, and the iron-containing materials are selected from pyrite and FeSO 4 And reduced iron powder.
2. The use according to claim 1, wherein the heavy metal in the heavy metal contaminated soil comprises at least one of cadmium, chromium, lead and arsenic.
3. The application according to claim 1, characterized in that the specific operation of the application is: and mixing the double-effect restoration agent into the heavy metal polluted soil according to the mass ratio of 0.2% -5%.
4. The use according to claim 1, wherein the double-effect restoration agent based on electrolytic manganese slag is prepared by the following method:
s1 mixing
Mixing electrolytic manganese slag and iron-containing materials according to a certain proportion to obtain a mixture;
s2 ball milling
And (3) putting the mixture obtained in the step (S1) into a ball mill for ball milling, and then taking out the solid after ball milling, grinding and screening to obtain the double-effect repairing agent.
5. The use according to claim 4, wherein the mass ratio of the electrolytic manganese slag to the iron-containing material in S1 is (0.5-3): 1.
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CN116731719A (en) * | 2023-07-14 | 2023-09-12 | 北京建工环境修复股份有限公司 | Circulating magnetic manganese-based mercury contaminated soil restoration agent and preparation method and application thereof |
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CN116731719A (en) * | 2023-07-14 | 2023-09-12 | 北京建工环境修复股份有限公司 | Circulating magnetic manganese-based mercury contaminated soil restoration agent and preparation method and application thereof |
CN116731719B (en) * | 2023-07-14 | 2024-01-16 | 北京建工环境修复股份有限公司 | Circulating magnetic manganese-based mercury contaminated soil restoration agent and preparation method and application thereof |
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