CN112872003A - Method for leaching and repairing copper in mine polluted soil - Google Patents
Method for leaching and repairing copper in mine polluted soil Download PDFInfo
- Publication number
- CN112872003A CN112872003A CN202110404418.9A CN202110404418A CN112872003A CN 112872003 A CN112872003 A CN 112872003A CN 202110404418 A CN202110404418 A CN 202110404418A CN 112872003 A CN112872003 A CN 112872003A
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- copper
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- leaching
- mine
- eluting
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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
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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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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- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of remediation of heavy metal contaminated soil, in particular to a method for remediating copper in mine contaminated soil by leaching. The method comprises the following steps of (1) removing soil copper by using a polycarboxylic acid compound as an eluent, wherein the polycarboxylic acid compound is any one of acrylic acid-hydroxypropyl acrylate or phosphine polycarboxylic acid, and the concrete operation method comprises the following steps: preparing the eluent into the eluent with the pH value of 3-9, mixing the eluent with the polluted soil, shaking and leaching, and then carrying out centrifugal separation, wherein the clear liquid of the polycarboxylic acid compound at the upper layer contains copper leached from the soil, and the content of the copper in the soil leached at the lower layer meets the national soil environment standard. The method is convenient and simple, has obvious leaching effect on the copper-polluted soil, ensures that the copper content in the leached soil meets the national soil environment standard, and the leaching agent in the leaching solution is nontoxic and biodegradable, and cannot cause secondary pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of remediation of heavy metal contaminated soil in the environment, and particularly relates to a method for remediating copper in mine contaminated soil by leaching.
Background
In recent years, heavy metal pollution of soil caused by the increase of human activities such as mining, smelting and chemical industry has become one of the serious environmental problems facing the world. China has a large amount of mineral resources, wherein the southwest area is particularly rich, and the mining scale is large, so that the heavy metal pollution of the surrounding soil is serious. Among the heavy metals, copper is a trace element necessary for animals and plants to maintain normal life activities, can affect functions of plant oxidation, photosynthesis, protein and carbohydrate metabolism, nitrogen fixation and the like, and has important significance for maintaining normal growth and development of organisms and breeding offspring. However, excessive copper interferes with all processes of organism life metabolism, causes reduction of soil microbial activity, soil fertility and crop yield, induces diseases of brain, heart and skin of human body through food chain enrichment, and is harmful to human health. Therefore, the remediation of copper-contaminated soil is one of the problems to be solved urgently.
At present, the common soil heavy metal remediation methods mainly comprise three main types, namely physical, chemical and biological remediation, including thermal desorption, immobilization and stabilization, electric remediation, phytoremediation, leaching methods and the like. The leaching technology has an action mechanism that pollutants fixed or adsorbed on soil colloid are removed by combining leacheate with pollutants in the soil through the actions of chelating, desorbing or dissolving, and the like, so that the purpose of repairing the polluted soil is achieved. Therefore, the leaching method is more suitable for repairing the soil with high pollution concentration and concentration, has the advantages of simple operation, short period, rapidness, high efficiency and durability, can thoroughly remove heavy metals, and avoids the environmental risk caused by the reactivation of the heavy metals in the soil. The key to the implementation of this repair technique is the choice of eluent. The currently used eluting agents mainly comprise inorganic eluting agents, chelating agents, surfactants and the like. Wherein, hydrochloric acid and FeCl3The inorganic eluting agents can effectively remove heavy metals such as lead, zinc, cadmium, copper, nickel and the like in soil, but the use conditions of the inorganic eluting agents have higher requirements on the corrosion resistance of equipment, and the physicochemical properties of the soil are easy to destroy, so that a large amount of soil nutrients are eluted, the soil is hardened and salinized; the artificial chelating agents such as EDTA, EDDS and the like have good effect of removing heavy metals in soil, but have long residual time in soil and poor biodegradability, are easy to cause secondary environmental pollution and are not beneficial to subsequent soilRestoring and reusing ecological functions; and the surfactant such as tween 80, sodium dodecyl sulfate and the like has high cost and limited sources, and has poor repairing effect on heavy metal pollution. Therefore, screening of the novel efficient, environment-friendly and low-cost eluting agent has certain practical significance for strengthening removal of copper in the polluted soil of the mining area.
Disclosure of Invention
The invention aims to solve the technical problems and provides a leaching agent which is convenient, simple and easy, has an obvious leaching effect on copper-polluted soil, ensures that the content of copper in the leached soil meets the national soil environment standard, is nontoxic and biodegradable, and does not cause secondary pollution to the environment.
The technical scheme adopted by the invention is as follows:
a method for leaching and repairing copper in mine polluted soil adopts a polycarboxylic acid compound as a leaching agent.
Further, the polycarboxylic acid compound is any one of acrylic acid-hydroxypropyl acrylate or a phosphonopolycarboxylic acid.
Further, the phosphinopolycarboxylic acid is phosphinopolyamic acid.
Further, the method for leaching and repairing copper in the mine polluted soil specifically comprises the following steps:
step 1: preparation of leacheate:
preparing the eluent from distilled water, adjusting pH, and storing in dark.
Step 2: and (3) leaching the polluted soil:
adding the leacheate obtained in the step 1 into copper-polluted soil, and eluting copper in the soil by oscillation to obtain a mixed liquid;
and step 3: and (3) soil-liquid separation:
and (3) carrying out centrifugal separation on the mixed liquid oscillated in the step (2) to obtain the washed soil.
Further, the concentration of the leacheate in the step 1 is 1% -15%.
Further, in the step 1, dilute nitric acid and sodium hydroxide solution are adopted to adjust the pH value of the leacheate to 3-9.
Further, the oscillation rate in the step 2 is 200r/min, and the oscillation time is 1-8 h.
Further, the ratio of the copper-contaminated soil to the leacheate in the step 2 is 1:10-1:20(g: mL).
Further, the copper-contaminated soil crushed in the step 2 is sieved by a 2mm sieve and then mixed with an eluent for oscillation.
Further, the rotating speed of the centrifuge in the centrifugal separation process in the step 3 is 3000-.
The invention has the beneficial effects that:
1. the invention adopts acrylic acid-hydroxypropyl acrylate and phosphino polymaleic acid as the eluent, which has wide source, biodegradability, low cost and no secondary pollution to soil.
2. The method adopts an ectopic leaching mode, the leaching process is convenient and simple to operate, the leaching effect on the copper-polluted soil is obvious, the risk that the leaching solution infiltrates and pollutes the underground water caused by in-situ leaching is avoided, meanwhile, a better effect can be achieved in a shorter time, and the time cost can be saved.
3. Compared with distilled water, the removal capacity of acrylic acid-hydroxypropyl acrylate and phosphino-polymaleic acid to copper in the polluted soil is greatly improved (the leaching rates of distilled water to copper in the soil are respectively 0.25%), wherein the leaching effect of phosphino-polymaleic acid is most obvious, and after one-time leaching, the leaching rates of 1%, 5% and 15% phosphino-polymaleic acid leachates to copper in the soil are respectively 28.35%, 44.77% and 52.34%. Meanwhile, compared with common organic phosphonic acid, the phosphorus content of the phosphino polymaleic acid is lower, and the risk of eutrophication of surface water after soil washing is reduced.
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Detailed Description
The invention is further described in the following examples without limiting the scope of the invention, it being understood that modifications and variations may be resorted to based on the description set forth above, those skilled in the art readily departing from the scope of the invention as set forth in the appended claims.
The method is implemented by taking phosphino polymaleic acid or acrylic acid-hydroxypropyl acrylate for leaching and repairing polluted soil in certain copper ore area in Panzhihua county.
Example 1:
1# experimental group:
a method for leaching and repairing copper in mine polluted soil (phosphine based polymaleic acid is adopted as a leaching agent):
step 1: preparing an eluent:
phosphinopolyamic acid (solid content 50%) was diluted to 1%, 5% and 15% with distilled water, respectively, and the leacheate was adjusted to 3.0 ± 0.5 with dilute nitric acid and sodium hydroxide.
Step 2: mixing the leacheate with the polluted soil, and then shaking and leaching:
and (3) taking 20mL of each of the leacheate in the step (1) with different concentrations, adding 2.00g of copper-polluted soil according to the solid-to-liquid ratio of 1:10(g: mL), and oscillating at the rotating speed of 200r/min for 2h to obtain a mixed liquid.
And step 3: separation of soil and liquid
Pouring the mixed solution oscillated in the step 2 into a centrifuge tube, centrifuging for 5min at the speed of 3500r/min to obtain the washed soil, taking the supernatant, filtering, and measuring the copper content in the filtrate by using a flame Atomic Absorption Spectrometer (AAS) (table 1).
2# Experimental group
A method for leaching and repairing copper in mine polluted soil (acrylic acid-hydroxypropyl acrylate is used as a leaching agent):
step 1: preparing an eluent:
acrylic acid-hydroxypropyl acrylate (solid content 30%) was diluted with distilled water to 1%, 5% and 15%, respectively, and the leacheate was adjusted to 3.0 ± 0.5 with dilute nitric acid and sodium hydroxide.
Step 2 and step 3 were the same as in example 1, and the copper content in the filtrate was measured by flame Atomic Absorption Spectroscopy (AAS) (table 1).
3# Experimental group
A method for leaching and repairing copper in mine polluted soil (distilled water is used as a leaching agent):
step 1:20 mL of distilled water is taken and is adjusted to be 3.0 +/-0.5 by dilute nitric acid and sodium hydroxide.
Step 2: mixing the leacheate with the polluted soil, and then shaking and leaching:
20mL of distilled water is added into 2.00g of copper contaminated soil according to the solid-to-liquid ratio of 1:10(g: mL), and the mixture is oscillated for 2 hours at the rotating speed of 200r/min to obtain a mixed liquid.
Step 3 the same as in example 1, the supernatant was filtered and the copper content of the filtrate was measured by flame Atomic Absorption Spectroscopy (AAS) (table 1).
TABLE 1 efficiency of three reagents for leaching copper from contaminated soil in mining area
Note: each treatment was repeated 3 times and the data in the table are the average of 3 replicates of a wash.
According to analysis, the leaching removal rate of the added leaching agent on the copper-polluted soil generally tends to increase along with the increase of the concentration of the added leaching agent, and particularly at the concentrations of 1%, 5% and 15%, the removal rate of the phosphino polymaleic acid leaching agent on the copper-polluted soil is respectively 28.35%, 44.77% and 52.34% under the conditions of the embodiment; the leaching rates of acrylic acid-hydroxypropyl acrylate on copper in soil are 16.13%, 29.60% and 34.12% respectively. The total leaching effect is obviously higher than the leaching rate of distilled water on copper in soil.
In conclusion, the phosphino polymaleic acid and the acrylic acid-hydroxypropyl acrylate have outstanding effects on repairing copper-polluted soil as leaching materials.
Example 2: copper leaching efficiency under different leaching time
The preparation method of the eluting agent and the eluting step of the eluting agent on the polluted soil are consistent with the conditions in the example 1, the dilution concentration of the phosphino-polymaleic acid in the No. 1 is 5%, the concentration of the acrylic acid-hydroxypropyl acrylate in the No. 2 is 5% consistent with that of the No. 1, the No. 2 and the No. 3 experimental groups only change the eluting oscillation time in the step 2, and the experimental groups only change the eluting rate under different oscillating times, and specific data refer to the table 2.
TABLE 2 efficiency of two reagents for removing copper from contaminated soil in a mining area at different leaching times
Note: each treatment was repeated 3 times and the data in the table are the average of 3 replicates of a wash.
As can be seen from table 2, under the same conditions, the leaching time of the leaching agent prepared from phosphino-polymaleic acid and hydroxypropyl acrylate respectively affects the leaching efficiency of copper in soil under the same leaching agent concentration condition, but different reagents are affected by different time degrees. Overall, when the leaching time is 8h, the leaching effect is the best.
Example 3: copper leaching efficiency at different pH
The preparation method of the eluting agent and the eluting step of the eluting agent on the polluted soil are consistent with the conditions in the example 1, the dilution concentration of the phosphino polymaleic acid in the No. 1 is 5%, the concentration of the acrylic acid-hydroxypropyl acrylate in the No. 2 is 5% consistent with that of the No. 1, the No. 2 and the No. 3 experimental groups only change the pH value in the step 1, and the experimental groups only change the eluting rate under different pH values, and the specific data refer to the table 3.
TABLE 3 efficiency of two reagents for removing copper from contaminated soil in mining area at different pH
Note: each treatment was repeated 3 times and the data in the table are the average of 3 replicates of a wash.
The copper leaching rates in acidic, neutral and alkaline states were tested separately in this study, and it can be seen from table 3 that, under the same conditions, the pH of the leaching agent has a decisive effect on the leaching efficiency of copper in soil under the same concentration of the leaching agent using the leaching agents prepared from phosphino-polymaleic acid and hydroxypropyl acrylate, respectively. In general, phosphino-polymaleic acid and hydroxypropyl acrylate have the best leaching effect on copper in soil under acidic conditions, and have poor leaching effects under neutral and alkaline conditions.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. A method for leaching and repairing copper in mine polluted soil is characterized in that a polycarboxylic acid compound is adopted as a leaching agent.
2. The method for eluting and remediating copper in mine contaminated soil as recited in claim 1, wherein the polycarboxylic acid compound is any one of hydroxypropyl acrylate or phosphino polycarboxylic acid.
3. The method for eluting and remediating copper in mine contaminated soil as recited in claim 2, wherein the phosphinopolycarboxylic acid is phosphinopolyamic acid.
4. The method for eluting and repairing copper in mine polluted soil according to any one of claims 1 to 3, wherein the method for eluting and repairing copper in mine polluted soil specifically comprises the following steps:
step 1: preparation of leacheate:
preparing the eluent from distilled water, adjusting pH, and storing in dark.
Step 2: and (3) leaching the polluted soil:
adding the leacheate obtained in the step 1 into copper-polluted soil, and eluting copper in the soil by oscillation to obtain a mixed liquid;
and step 3: and (3) soil-liquid separation:
and (3) carrying out centrifugal separation on the mixed liquid oscillated in the step (2) to obtain the washed soil.
5. The method for eluting and repairing copper in mine polluted soil according to claim 4, wherein the concentration of the eluent in the step 1 is 1% -15%.
6. The method for eluting and remediating copper in mine contaminated soil as recited in claim 4, wherein in the step 1, the pH value of the eluent is adjusted to 3-9 by using dilute nitric acid and sodium hydroxide solution.
7. The method for eluting and remediating copper in mine contaminated soil as recited in claim 4, wherein in the step 2, the oscillation rate is 200r/min, and the oscillation time is 1-8 h.
8. The method for leaching and repairing copper in mine polluted soil according to claim 4, wherein the ratio of the copper polluted soil to the leacheate in the step 2 is 1:10-1:20(g: mL).
9. The method for eluting and remediating copper in mine polluted soil as recited in claim 4, wherein the copper-polluted soil crushed in the step 2 is sieved by a 2mm sieve and then mixed with the eluent for oscillation.
10. The method for leaching and remediating copper in mine contaminated soil as recited in claim 4, wherein the centrifuge rotation speed in the centrifugal separation process of step 3 is 3000-4000r/min, and the centrifugation time is 5-10 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110404418.9A CN112872003A (en) | 2021-04-15 | 2021-04-15 | Method for leaching and repairing copper in mine polluted soil |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130665A (en) * | 2006-08-25 | 2008-02-27 | 安集微电子（上海）有限公司 | Polishing solution used for polishing low-dielectric materials |
| CN102190591A (en) * | 2010-03-12 | 2011-09-21 | 陈郁 | Metal complex, preparation method and application thereof |
| CN103482775A (en) * | 2013-09-03 | 2014-01-01 | 山东天庆科技发展有限公司 | Composite scale and corrosion inhibitor and preparation method thereof |
| CN104759265A (en) * | 2015-03-16 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Porous foam body heavy metal adsorption material preparation method |
| CN107138030A (en) * | 2017-06-08 | 2017-09-08 | 北京可林维尔化工有限公司 | Wet desulfurization system synergy scale inhibition heavy metals removal agent and preparation method thereof |
| CN109928806A (en) * | 2019-04-25 | 2019-06-25 | 四川大学 | The preparation method of complete water-soluble monoammonium phosphate containing middle microelement |
| CN109997442A (en) * | 2019-03-19 | 2019-07-12 | 湖州灵粮生态农业有限公司 | A kind of method of biology in situ rehabilitating soil |
| CN111498973A (en) * | 2020-05-14 | 2020-08-07 | 北京中科康仑环境科技研究院有限公司 | Heavy metal wastewater treatment agent and treatment method thereof |
| CN111718722A (en) * | 2019-03-18 | 2020-09-29 | 安徽中医药大学 | Modified polypropylene glycol soil remediation agent and preparation method thereof |
| CN112521950A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Soil washing composition containing phosphono carboxylic acid, application thereof and method for repairing heavy metal soil |
-
2021
- 2021-04-15 CN CN202110404418.9A patent/CN112872003A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130665A (en) * | 2006-08-25 | 2008-02-27 | 安集微电子（上海）有限公司 | Polishing solution used for polishing low-dielectric materials |
| CN102190591A (en) * | 2010-03-12 | 2011-09-21 | 陈郁 | Metal complex, preparation method and application thereof |
| CN103482775A (en) * | 2013-09-03 | 2014-01-01 | 山东天庆科技发展有限公司 | Composite scale and corrosion inhibitor and preparation method thereof |
| CN104759265A (en) * | 2015-03-16 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Porous foam body heavy metal adsorption material preparation method |
| CN107138030A (en) * | 2017-06-08 | 2017-09-08 | 北京可林维尔化工有限公司 | Wet desulfurization system synergy scale inhibition heavy metals removal agent and preparation method thereof |
| CN111718722A (en) * | 2019-03-18 | 2020-09-29 | 安徽中医药大学 | Modified polypropylene glycol soil remediation agent and preparation method thereof |
| CN109997442A (en) * | 2019-03-19 | 2019-07-12 | 湖州灵粮生态农业有限公司 | A kind of method of biology in situ rehabilitating soil |
| CN109928806A (en) * | 2019-04-25 | 2019-06-25 | 四川大学 | The preparation method of complete water-soluble monoammonium phosphate containing middle microelement |
| CN112521950A (en) * | 2019-09-17 | 2021-03-19 | 中国石油化工股份有限公司 | Soil washing composition containing phosphono carboxylic acid, application thereof and method for repairing heavy metal soil |
| CN111498973A (en) * | 2020-05-14 | 2020-08-07 | 北京中科康仑环境科技研究院有限公司 | Heavy metal wastewater treatment agent and treatment method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 夏振华等: "低分子量有机酸及其共聚物去除土壤重金属研究", 《农业环境科学学报》 * |
| 姚瑶等: "3种环保型淋洗剂对重金属污染土壤的淋洗效果", 《环境工程学报》 * |
| 曹永琳: "《江西环境应急监测技术》", 31 December 2005, 江西科学技术出版社 * |
| 王光江等: "衣康酸-丙烯酸二元共聚物的合成及其阻垢性能研究", 《工业水处理》 * |
| 钱天伟等: "《饱和－非饱和土壤污染物运移》", 28 February 2007, 中国环境科学出版社 * |
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