CN114515750A - Eluting agent for repairing arsenic-fluorine compound contaminated soil and using method thereof - Google Patents

Eluting agent for repairing arsenic-fluorine compound contaminated soil and using method thereof Download PDF

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Publication number
CN114515750A
CN114515750A CN202111648242.8A CN202111648242A CN114515750A CN 114515750 A CN114515750 A CN 114515750A CN 202111648242 A CN202111648242 A CN 202111648242A CN 114515750 A CN114515750 A CN 114515750A
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CN
China
Prior art keywords
arsenic
contaminated soil
eluting agent
soil
fluorine
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111648242.8A
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Chinese (zh)
Inventor
周永信
朱红祥
牛婧
郑浩
赵粉红
李雄光
刘彬
韩丽杰
刘亚东
郑子健
赵振
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Guangxi Bossco Environmental Protection Technology Co Ltd
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Guangxi Bossco Environmental Protection Technology Co Ltd
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Priority to CN202111648242.8A priority Critical patent/CN114515750A/en
Publication of CN114515750A publication Critical patent/CN114515750A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/02Extraction using liquids, e.g. washing, leaching, flotation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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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)

Abstract

The invention discloses an eluent for remedying arsenic-fluorine combined contaminated soil and a using method thereof, the eluent comprises citric acid, oxalic acid, Ethylene Diamine Tetraacetic Acid (EDTA), monopotassium phosphate and water, and the proportion of citric acid, oxalic acid, EDTA and potassium dihydrogen phosphate solution is (1-2): (3-5): (1-3): (1-2); the use method of the eluting agent in the remediation of the arsenic-fluorine compound contaminated soil comprises the following steps: firstly, preparing an arsenic-fluorine compound contaminated soil eluting agent, adding the eluting agent into contaminated soil, oscillating at 15-40 ℃, finally filtering and separating the mixed solution to obtain a solid phase part, detecting the solid phase part to obtain the restored soil when the solid phase part reaches the standard, and repeating the steps if the solid phase part does not reach the standard. The method has the advantages of thorough removal of pollutants, no secondary environmental pollution and the like by leaching the arsenic and fluorine compound polluted soil, and has a good treatment effect on the pollutants such as lead, zinc, copper and the like.

Description

Eluting agent for repairing arsenic-fluorine compound contaminated soil and using method thereof
Technical Field
The invention relates to the technical field of polluted soil remediation, in particular to an eluent for remediating arsenic-fluorine composite polluted soil and a using method thereof.
Background
With the further implementation of the policies of 'two-in three-out' and 'city-in garden-out' in China, a large number of heavy industry and chemical industry enterprises are forced to be transformed, shut down or moved, a large number of polluted sites are left in cities, and great hidden dangers are brought to the health of surrounding residents and the environmental health. Wherein, the smelting plants such as steel, aluminium leave over the place and have progressively developed the improvement restoration work, and place pollutants such as heavy metal, fluoride often seriously exceed standard, and mostly compound pollution. Heavy metals are extremely hidden, durable, nondegradable and high in toxicity in soil, accumulate in plants and human bodies to generate toxicity, arsenic as a metal has similar properties, and is easy to change due to the valence state and complex in existing form, so that the arsenic is more harmful to human bodies and the environment, and the removal difficulty is higher. Fluoride enters underground water through leaching and other effects in soil, particularly water-soluble fluorine, can directly harm underground water, plants, people and livestock, and has potential adverse effects on growth and development of animals and skeleton development. Therefore, it is necessary to research the removal of arsenic, fluorine and their complex pollutants.
The conventional soil remediation method can be used for remediation of arsenic and fluorine contaminated soil, and mainly comprises a solidification/stabilization technology, a chemical leaching technology, a plant remediation technology and the like. The solidification/stabilization technology reduces the environmental risk of pollutants by changing the forms of the pollutants in the soil, but the method does not completely remove the pollutants, and the occurrence of the pollutants in the soil is difficult to ensure the safety along with the accumulation of the pollutants in time; phytoremediation utilizes plant roots to adsorb pollutants, although phytoremediation is a green and environment-friendly remediation technology, the remediation capability is limited, the phytoremediation technology only has obvious effect on pollutants on the surface layer of soil and has long remediation period, and the phytoremediation technology is difficult to be applied to polluted sites which are in urgent need of development and utilization. In conclusion, the chemical leaching effect is more prominent from the viewpoints of pollutant removal effect, repairing time, repairing cost and the like. The chemical leaching thoroughly removes the pollutants from the soil surface through the eluting agent, can directly reduce the pollutants, has short repairing time and low cost, and is widely applied to practical engineering.
One of the keys to the application of the leaching technique is the choice of the leaching agent, and common leaching agents comprise organic acid, inorganic acid, alkali, surfactant, inorganic salt and the like. In the prior art, in consideration of repair cost, only a single eluting agent is usually adopted, the eluting effect is relatively poor, but the eluting effect can be improved by adopting the compound eluting agent, but the treatment of the eluting waste liquid can cause the increase of multiple costs. Therefore, how to select the eluting agent can not only remove the pollutants accurately and efficiently, but also reduce the treatment difficulty of the eluting waste liquid and reduce the secondary environmental pollution, and is one of the hot spots and development directions of the eluting technical research.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation and application of the soil eluting agent for repairing arsenic-fluorine combined pollution.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
an eluent for remedying arsenic-fluorine combined contaminated soil comprises citric acid, oxalic acid, Ethylene Diamine Tetraacetic Acid (EDTA), monopotassium phosphate and water.
Further, the preparation method of the eluting agent comprises the following steps: dissolving citric acid, oxalic acid, EDTA and potassium dihydrogen phosphate in water to prepare aqueous solution, and mixing the aqueous solutions in proportion to obtain mixed solution, namely the arsenic-fluorine compound contaminated soil eluting agent.
Further, the concentration of the aqueous solution prepared from the raw materials is as follows: the concentration of the citric acid solution is 0.05-0.20mol/L, the concentration of the oxalic acid solution is 0.01-0.50mol/L, the concentration of the EDTA solution is 0.10-0.50mol/L, and the concentration of the potassium dihydrogen phosphate solution is 0.05-0.50 mol/L.
Further, the raw materials are prepared into an aqueous solution and then mixed according to the following mixing amount: 1-2 parts of citric acid, 3-5 parts of oxalic acid, 1-3 parts of Ethylene Diamine Tetraacetic Acid (EDTA) and 1-2 parts of monopotassium phosphate.
The application method of the eluting agent for repairing arsenic-fluorine composite polluted soil comprises the steps of firstly preparing the eluting agent for repairing arsenic-fluorine composite polluted soil, adding the eluting agent into the polluted soil to oscillate at 15-40 ℃, finally filtering and separating the mixed solution to obtain a solid phase part, detecting the solid phase part, wherein the solid phase part is detected to be up to standard, namely the repaired soil, and repeating the steps if the solid phase part is not up to standard.
The leaching agent prepared by the invention mainly aims at arsenic and fluorine compound contaminated soil, the pollutants are mainly arsenic and fluorine, and the leaching agent also comprises one or more heavy metals of lead, zinc and copper, and the leaching agent can fully contact and react with the arsenic and the fluorine in the soil by adopting a vibration and filtration method.
Further, the ratio of the quality of the polluted soil to the dosage of the eluting agent is 1 g: (5-20) ml.
Further, the leaching oscillation time is 20-120min, and the leaching frequency is 1-2 times.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the method has the advantages of thorough removal of pollutants, no secondary environmental pollution and the like by leaching the arsenic and fluorine compound polluted soil, and has a good treatment effect on the pollutants such as lead, zinc, copper and the like.
2. On the basis of removing pollutants such as arsenic, fluorine and the like by using the chelating agent alone, the organic acid and the salts are added, so that the desorption of the pollutants from soil colloid is increased, the combination and fixation of the organic acid and the chelating agent to arsenic and other heavy metals in a soil solution are more stable, and the removal efficiency of the pollutants is greatly improved by the synergistic effect of the organic acid and the chelating agent.
3. The eluent can perform various physical and chemical reactions such as desorption and complexation with pollutants in soil in the using process, can relatively comprehensively remove arsenic and fluorine in different forms in soil, and has obvious repairing effect.
4. The organic acid and the chelating agent used in the eluting agent can be biodegraded, so that the treatment difficulty of the eluting waste liquid is greatly reduced, the environmental risk is reduced, and the treatment cost is reduced.
5. The medicament has wide sources, is common biological, chemical and other raw materials, and is widely applied to soil pollution and water pollution treatment projects; in addition, the medicament is convenient to purchase, transport and store.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1
The polluted soil is the polluted soil of an iron-making area of a certain steel mill in Hangzhou, pollutants are arsenic and fluoride, the pollution concentration is 218mg/kg of arsenic and 3200mg/kg of fluoride, and the remediation targets are 40mg/kg of arsenic and 1900mg/kg of fluoride.
Pretreatment of contaminated soil: after the air-dried soil is crushed, the crushed soil is sieved by a 100-mesh sieve, and impurities such as stones, weeds and the like are removed.
Preparing an eluent: the concentration of the citric acid solution is 0.1mol/L, the concentration of the oxalic acid solution is 0.2mol/L, the concentration of the EDTA solution is 0.05mol/L, and the concentration of the potassium dihydrogen phosphate solution is 0.2 mol/L. The eluent comprises the following components in percentage by weight: citric acid: oxalic acid: EDTA: potassium dihydrogen phosphate ═ 1: 3: 1: 2.
the application of the leacheate: and (3) putting 30g of polluted soil into a conical flask, adding 300ml of compound eluting agent, oscillating for 1h at the constant temperature of 25 ℃ and the rotating speed of 180rpm by using an oscillator, carrying out suction filtration on the mixed solution after oscillation is finished, eluting for 2 times due to the fact that the soil has more clay content, adding 300ml of compound eluting agent into the solid phase part obtained after suction filtration again, repeating the operation, oscillating for 30min, and carrying out suction filtration on the mixed solution after oscillation is finished, wherein the obtained solid phase part is the soil after elution and remediation.
The treatment effect is as follows: the arsenic concentration of the repaired soil is 28mg/kg, and the removal rate is 88%; the fluoride concentration is 660mg/kg, and the removal rate is 80 percent.
Example 2
The polluted soil is the polluted soil of a certain steel plant in Fujian province, pollutants are arsenic, lead, zinc and fluoride, the pollution concentration is 320mg/kg of arsenic, 890mg/kg of lead and 1760mg/kg of fluoride, and the restoration targets are 60mg/kg of arsenic, 800mg/kg of lead and 820mg/kg of fluoride.
Pretreating polluted soil: after the air-dried soil is crushed, the crushed soil is sieved by a 100-mesh sieve, and impurities such as stones, weeds and the like are removed.
Preparing an eluent: the concentration of the citric acid solution is 0.2mol/L, the concentration of the oxalic acid solution is 0.2mol/L, the concentration of the EDTA solution is 0.05mol/L, and the concentration of the potassium dihydrogen phosphate solution is 0.2 mol/L. The eluent comprises the following components in percentage by weight: citric acid: oxalic acid: EDTA: potassium dihydrogen phosphate ═ 1: 3: 2: 1.
the application of the leacheate: and (3) putting 30g of polluted soil into a conical flask, adding 300ml of compound eluting agent, oscillating for 1h at the constant temperature of 25 ℃ and the rotating speed of 180rpm by using an oscillator, and filtering the mixed solution after oscillation is finished to obtain a solid phase part, namely the eluted and repaired soil.
The treatment effect is as follows: the arsenic concentration of the repaired soil is 35mg/kg, and the removal rate is 89%; the lead concentration is 410mg/kg, and the removal rate is 54 percent; the fluoride concentration was 330mg/kg, and the removal rate was 81%.
Example 3
The polluted soil is the polluted soil of a certain aluminum refinery in Guangxi, pollutants are arsenic, zinc, copper and fluoride, the pollution concentration is 86mg/kg of arsenic and 2450mg/kg of fluoride, and the remediation targets are 60mg/kg of arsenic and 760mg/kg of fluoride.
Pretreatment of contaminated soil: after the air-dried soil is crushed, the crushed soil is sieved by a 100-mesh sieve, and impurities such as stones, weeds and the like are removed.
Preparing an eluent: the concentration of the citric acid solution is 0.05mol/L, the concentration of the oxalic acid solution is 0.1mol/L, the concentration of the EDTA solution is 0.05mol/L, and the concentration of the potassium dihydrogen phosphate solution is 0.2 mol/L. The eluent comprises the following components in percentage by weight: citric acid: oxalic acid: EDTA: potassium dihydrogen phosphate 2: 3: 1: 2.
the application of the leacheate: and (3) putting 30g of polluted soil into a conical flask, adding 300ml of compound eluting agent, oscillating for 1h at the constant temperature of 25 ℃ and the rotating speed of 180rpm by using an oscillator, and filtering the mixed solution after oscillation is finished to obtain a solid phase part, namely the eluted and repaired soil.
The treatment effect is as follows: the arsenic concentration of the repaired soil is 20mg/kg, and the removal rate is 77%; the fluoride concentration is 200mg/kg, and the removal rate is 74 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (7)

1. The eluting agent for remedying the arsenic-fluorine combined contaminated soil is characterized by comprising citric acid, oxalic acid, Ethylene Diamine Tetraacetic Acid (EDTA), monopotassium phosphate and water.
2. The eluting agent for remediating arsenic-fluorine combined contaminated soil as claimed in claim 1, wherein the preparation method of the eluting agent is as follows: dissolving citric acid, oxalic acid, EDTA and potassium dihydrogen phosphate in water to prepare aqueous solution, and mixing the aqueous solutions in proportion to obtain mixed solution, namely the arsenic-fluorine compound contaminated soil eluting agent.
3. The eluting agent for remediating arsenic-fluorine composite contaminated soil according to claim 2, wherein the concentration of the water solution prepared from each raw material is as follows: the concentration of the citric acid solution is 0.05-0.20mol/L, the concentration of the oxalic acid solution is 0.01-0.50mol/L, the concentration of the EDTA solution is 0.10-0.50mol/L, and the concentration of the potassium dihydrogen phosphate solution is 0.05-0.50 mol/L.
4. The eluting agent for remediating arsenic-fluorine composite contaminated soil as claimed in claim 3, wherein the raw materials are prepared into aqueous solution and then mixed according to the following mixing amount: 1-2 parts of citric acid, 3-5 parts of oxalic acid, 1-3 parts of Ethylene Diamine Tetraacetic Acid (EDTA) and 1-2 parts of monopotassium phosphate.
5. The use method of the eluting agent for remediating arsenic-fluorine compound contaminated soil as claimed in claims 1-4, wherein the eluting agent for arsenic-fluorine compound contaminated soil is prepared first, the eluting agent is added into contaminated soil to oscillate at 15-40 ℃, finally the mixed solution is filtered and separated to obtain a solid phase part, the solid phase part is detected, if the solid phase part is up to standard, the remediated soil is obtained, and if the solid phase part is not up to standard, the steps are repeated.
6. The preparation method of the eluting agent for remediating arsenic-fluorine combined contaminated soil as claimed in claim 5, wherein the ratio of the mass of the contaminated soil to the amount of the eluting agent is 1 g: (5-20) ml.
7. The preparation method of the eluting agent for remediating arsenic-fluorine combined polluted soil as claimed in claim 5, wherein the eluting oscillation time is 20-120min, and the eluting times are 1-2 times.
CN202111648242.8A 2021-12-30 2021-12-30 Eluting agent for repairing arsenic-fluorine compound contaminated soil and using method thereof Pending CN114515750A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032910A (en) * 2015-06-12 2015-11-11 湖南大学 Composite eluting agent for repairing arsenic contaminated soil and application method thereof
CN107159701A (en) * 2017-07-06 2017-09-15 广西博世科环保科技股份有限公司 It is a kind of at the same remove soil in arsenic antimony method
CN108015104A (en) * 2016-10-28 2018-05-11 中国农业科学院麻类研究所 A kind of ramie planting method of remediating heavy metal cadmium pollution soil
CN112207122A (en) * 2020-09-23 2021-01-12 内蒙古农业大学 Method for remedying heavy metal pollution of calcareous soil
CN113736469A (en) * 2021-08-06 2021-12-03 华东理工大学 Leaching agent suitable for high-concentration arsenic-antimony composite polluted soil and preparation and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105032910A (en) * 2015-06-12 2015-11-11 湖南大学 Composite eluting agent for repairing arsenic contaminated soil and application method thereof
CN108015104A (en) * 2016-10-28 2018-05-11 中国农业科学院麻类研究所 A kind of ramie planting method of remediating heavy metal cadmium pollution soil
CN107159701A (en) * 2017-07-06 2017-09-15 广西博世科环保科技股份有限公司 It is a kind of at the same remove soil in arsenic antimony method
CN112207122A (en) * 2020-09-23 2021-01-12 内蒙古农业大学 Method for remedying heavy metal pollution of calcareous soil
CN113736469A (en) * 2021-08-06 2021-12-03 华东理工大学 Leaching agent suitable for high-concentration arsenic-antimony composite polluted soil and preparation and application thereof

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陈寻峰等: "砷污染土壤复合淋洗修复技术研究", 《环境科学》 *

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