CN113649410B - Process for repairing heavy metal pollution of soil by using nano repairing material - Google Patents
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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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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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Abstract
The invention discloses a method for repairing soil heavy metal pollution by using a nano repairing materialThe composite process comprises the processes of crushing, screening, maintaining, drying, screening and magnetic separation, can be used for thoroughly removing heavy metals in soil, is simple in process and low in cost, and can be used for reducing or removing lead, cadmium, arsenic, copper, arsenic, zinc, cobalt, chromium and the like in soil at one time by recovering the nano-treatment material from the soil through magnetic separation, so that the risk of re-release of the heavy metals caused by change of soil environment is avoided. The nano treatment material of the invention is prepared by modified sepiolite and biochar loaded MnFe2O4The nanometer material is formed, the fixing treatment efficiency of heavy metal is greatly improved by matching the nanometer material and the heavy metal, a better treatment effect can be realized on various heavy metals, and the method can be used for large-scale treatment of heavy metal contaminated soil.
Description
Technical Field
The invention belongs to the technical field of environmental protection treatment, and particularly relates to a process for repairing soil heavy metal pollution by using a nano repairing material.
Background
With the continuous development of industries such as petroleum drilling, chemical engineering, metal processing, electroplating, mining and the like, the generated environmental problems are increasingly prominent, and particularly, if the wastes generated in the production process are improperly disposed, the wastes enter farmlands, rivers, oceans or seeped into stratums, and serious pollution is generated to the environment. Especially, some solid wastes generated in the production process are found to be almost all of the common heavy metals such As Pb, Cu, As, Cr, Zn, Hg and the like, if directly discharged into the stratum, the heavy metals must migrate in the soil and then are transferred to other uncontaminated soil around, and the formation water is also polluted.
The existing methods for treating heavy metals in soil mainly comprise a leaching method, a biological method and a solidification method. The leaching method is to transfer heavy metals in soil into a soil solution by using a certain liquid, including acid, alkali, salt, a surfactant, a complexing agent or a chelating agent and the like, and then to leach and remove the heavy metals in the soil solution, so that secondary pollution is easy to cause, and the leaching solution needs to be subjected to secondary treatment, but has the defects of large liquid consumption, high cost and the like. The biological method is mainly a method for leaching heavy metals in sludge by utilizing bacteria such as thiobacillus ferrooxidans and the like to generate acid and consume sulfur elements through metabolism, but the method is time-consuming, and has higher difficulty in bacterial culture and higher requirement on equipment. The cured-site technology is a waste drilling mud treatment technology that has developed in recent years. The principle is that curing agent with consolidation property is added into the waste drilling mud, so that the waste drilling mud is converted into a concrete-like solidified body to consolidate harmful components in the solidified body. However, in the solidification method, the soluble state of the heavy metal elements is not changed. Over time, heavy metal ions can escape with the exudate of the solidified body, pollute soil and underground water and still have higher risk of environmental pollution. Therefore, the process for thoroughly removing the heavy metal in the soil is developed, the risk caused by the fact that heavy metal ions still exist in the soil after the treatment by the existing solidification method is avoided, and the process has very practical significance for the existing soil heavy metal treatment process.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a process for repairing heavy metal pollution in soil by using a nano repairing material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding the polluted soil into a crushing and screening device, crushing and screening the soil, and screening large blocks and gravels mixed in the soil from the soil to obtain coarse-grained soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the water content in the soil to reach 35-40%, stirring and mixing for 2-3 hours, then adding the nano repairing material, continuing to fully stir and mix for 4-8 hours, and then standing and maintaining;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 2-4%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the superfine granular soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repairing material;
wherein the nano-repair material is prepared by loading MnFe on modified sepiolite and biochar2O4And (3) nano-material composition.
Preferably, the nano repairing material added in the step (3) accounts for 10-20% of the fine particle soil.
Preferably, the standing and maintaining time is different according to the initial content of heavy metals in different soils, and is preferably 3-7 days.
Preferably, the modified sepiolite and charcoal load MnFe2O4The mass ratio of the nano material is 1-3: 1.
Preferably, the preparation method of the modified sepiolite comprises the following steps:
(1) FeCl is added3Dissolving in water to obtain FeCl3Aqueous solution to FeCl3Adding polyethylene glycol into the aqueous solution to obtain a mixed solution;
(2) taking a sepiolite raw material, drying, crushing, sieving, adding the sieved sepiolite powder into the mixed solution obtained in the step (1), uniformly stirring, carrying out hydrothermal reaction at the temperature of 110-;
(3) adding the FeO (OH) -sepiolite compound prepared in the step (2) into a sodium diethyldithiocarbamate solution, fully stirring for 3-6 hours, and then filtering, drying, grinding and sieving to obtain the modified sepiolite.
Preferably, in step (1), the FeCl is3And the mass ratio of water to polyethylene glycol is 1-2: 2-6: 0.05-0.3.
Preferably, in the step (2), the mass ratio of the sepiolite to the mixed solution is 1-3: 5-12; the concentration of the sodium diethyldithiocarbamate solution in the step (3) is 1000-2000 mg/L.
Preference is given toThe biochar is loaded with MnFe2O4The preparation method of the nano material comprises the following steps:
(1) preparing the biochar: washing, drying and crushing a biomass raw material to obtain a granular raw material, then keeping the granular raw material at the temperature of 550-650 ℃ for 3-4 hours in a nitrogen atmosphere, cooling and taking out to obtain the biochar;
(2) biochar loaded MnFe2O4Preparing a nano material: sequentially adding biochar and FeCl into deionized water under the atmosphere of nitrogen3·6H2O and Mn (NO)3)2·4H2O; then dropping the mixed solution into 1.5mol/L NaOH solution under the condition of continuously stirring at 55 ℃, reacting for 30min, centrifuging and washing to obtain the biochar-loaded MnFe2O4And (3) nano materials.
Preferably, the biomass raw material is one or more selected from peanut shells, corn stalks, rice hulls, sawdust or bamboo shavings.
Preferably, the FeCl3·6H2O、Mn(NO3)2·4H2The molar ratio of O to NaOH was 1:0.3: 6.
Compared with the prior art, the invention has the following beneficial effects:
(1) the process for treating the heavy metal ions in the soil comprises the processes of crushing, screening, maintaining, drying, screening and magnetic separation, can be used for thoroughly removing the heavy metals in the soil, is simple in process and low in cost, and can be used for reducing or removing lead, cadmium, arsenic, copper, arsenic, zinc, cobalt, chromium and the like in the soil at one time by recovering the nano treatment material from the soil through the magnetic separation, so that the risk of re-releasing the heavy metals due to the change of the soil environment is avoided;
(2) the nano-treatment material adopted by the invention is prepared by loading modified sepiolite and biochar with MnFe2O4The modified sepiolite is prepared by compounding sepiolite with FeO (OH), and then coating sodium diethyldithiocarbamate with high chelating ability, so that the fixing and passivating effects of sepiolite on heavy metals are remarkably improvedThe modified charcoal has porosity, huge specific surface area and good adsorption capacity, and is loaded with MnFe2O4, so that the treatment type and capacity of the charcoal on heavy metal ions are remarkably improved; the two are matched for use, so that the fixed treatment efficiency of heavy metals is greatly improved, a better treatment effect can be achieved on various heavy metals, and the heavy metal treatment device can be used for large-scale treatment of heavy metal contaminated soil.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding 5Kg of polluted soil (obtained from the polluted soil in the western factory of the Utility company, Inc. of the actual industry in south of Hunan province) into crushing and screening equipment, crushing and screening the soil, and screening large blocks and broken stones mixed in the soil from the soil to obtain coarse-particle soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the moisture content in the soil to reach about 38%, stirring and mixing for 3 hours, adding 0.75Kg of nano repairing material, continuing to fully stir and mix for 6 hours, then standing and maintaining for 4 days, avoiding exposure to the sun and rain in the maintenance process, and not contacting with strong acid, strong base and strong reducing substances;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 3%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the superfine granular soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repairing material;
wherein the nano repairing material is prepared by loading MnFe on modified sepiolite and biochar2O4The nano material is composed of 2:1 by mass.
The preparation method of the modified sepiolite comprises the following steps:
(1) 200g of FeCl3Dissolving in 400g water to obtain FeCl3Aqueous solution to FeCl3Adding 15g of polyethylene glycol into the aqueous solution to obtain a mixed solution;
(2) taking 125g of sepiolite raw material, drying, crushing, sieving, adding the sieved sepiolite powder into the mixed solution in the step (1), uniformly stirring, carrying out hydrothermal reaction for 24h at 120 ℃, and then washing, drying and grinding to obtain an FeO (OH) -sepiolite compound;
(3) and (3) adding 50g of the FeO (OH) -sepiolite compound prepared in the step (2) into 1.5L of sodium diethyldithiocarbamate solution at the concentration of 1600mg/L, fully stirring for 4 hours, and then filtering, drying, grinding and sieving to obtain the modified sepiolite.
The biochar is loaded with MnFe2O4The preparation method of the nano material comprises the following steps:
(1) preparing biochar: washing bamboo dust, drying and crushing to obtain a particle raw material, then keeping the particle raw material at 600 ℃ for 3.5 hours in a nitrogen atmosphere, and taking out after cooling to obtain the biochar;
(2) biochar loaded MnFe2O4Preparing a nano material: under the nitrogen atmosphere, 80g of biochar and 27g of FeCl are sequentially added into 400ml of deionized water3·6H2O and 7.6gMn (NO)3)2·4H2O; then dropping the mixed solution into 400ml of 1.5mol/L NaOH solution under the condition of continuously stirring at the temperature of 55 ℃, reacting for 30min, centrifuging and washing to obtain the biochar-loaded MnFe2O4A nano-material.
Example 2
A process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding 5Kg of polluted soil (obtained from the polluted soil in the western factory of the Utility company, Inc. of the actual industry in south of Hunan province) into crushing and screening equipment, crushing and screening the soil, and screening large blocks and broken stones mixed in the soil from the soil to obtain coarse-particle soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the moisture content in the soil to reach about 35%, stirring and mixing for 3 hours, adding 0.75Kg of nano repairing material, continuing to fully stir and mix for 6 hours, then standing and maintaining for 4 days, avoiding exposure to the sun and rain in the maintenance process, and not contacting with strong acid, strong base and strong reducing substances;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 3%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the ultrafine particle soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repair material;
wherein the nano-repair material is prepared by loading MnFe on modified sepiolite and biochar2O4The nano material is composed of nano materials according to the mass ratio of 1: 1.
The modified sepiolite and the biochar load MnFe2O4The preparation method of the nano material is the same as that of example 1.
Example 3
A process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding 5Kg of polluted soil (obtained from polluted soil in the west factory area of the Hunan Nandina actual industry Co., Ltd.) into crushing and screening equipment, crushing and screening the soil, and screening out large blocks and crushed stones mixed in the soil to obtain coarse-particle soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the moisture content in the soil to reach about 40%, stirring and mixing for 3 hours, adding 0.75Kg of nano repairing material, continuing to fully stir and mix for 6 hours, then standing and maintaining for 4 days, avoiding exposure to the sun and rain in the maintenance process, and not contacting with strong acid, strong base and strong reducing substances;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 3%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the superfine granular soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repairing material;
wherein the nano-repair material is prepared by loading MnFe on modified sepiolite and biochar2O4The nano material is composed of 3:1 by mass.
The modified sepiolite and charcoal load MnFe2O4The preparation method of the nano material is the same as that of example 1.
Comparative example 1
A process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding 5Kg of polluted soil (obtained from polluted soil in the west factory area of the Hunan Nandina actual industry Co., Ltd.) into crushing and screening equipment, crushing and screening the soil, and screening out large blocks and crushed stones mixed in the soil to obtain coarse-particle soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the moisture content in the soil to reach about 38%, stirring and mixing for 3 hours, adding 0.75Kg of nano repairing material, continuing to fully stir and mix for 6 hours, then standing and maintaining for 4 days, avoiding exposure to the sun and rain in the maintenance process, and not contacting with strong acid, strong base and strong reducing substances;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 3%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the ultrafine particle soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repair material;
the preparation method of the modified sepiolite is the same as that in the example 1.
Comparative example 2
A process for remedying heavy metal pollution in soil by using a nano remediation material comprises the following steps:
(1) adding 5Kg of polluted soil (obtained from polluted soil in the west factory area of the Hunan Nandina actual industry Co., Ltd.) into crushing and screening equipment, crushing and screening the soil, and screening out large blocks and crushed stones mixed in the soil to obtain coarse-particle soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the moisture content in the soil to reach about 38%, stirring and mixing for 3 hours, adding 0.75Kg of nano repairing material, continuing to fully stir and mix for 6 hours, then standing and maintaining for 4 days, avoiding exposure to the sun and rain in the maintenance process, and not contacting with strong acid, strong base and strong reducing substances;
(4) drying the soil in the step (3) after maintenance is finished until the moisture content is about 3%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the superfine granular soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repairing material;
wherein the nano-repair material is biochar loaded MnFe2O4Nanomaterial, said biochar being MnFe-loaded2O4The preparation method of the nano material is the same as that of example 1.
The contents of heavy metal ions in the soil before and after treatment are respectively measured by adopting an inductively coupled plasma mass spectrometry method and a flame atomic absorption spectrophotometry method, and the results are as follows:
the contents of the heavy metal ions in the soil treated by the materials of examples 1 to 3 and comparative examples 1 to 2 were as follows:
as can be seen from the above Table 1, the nano-treatment materials prepared in the examples 1 to 3 of the present invention have a good stable curing effect on 8 heavy metal ions in heavy metal contaminated soil, the content of each heavy metal in the solid waste reaches the emission limit standard, and the effect of the nano-treatment materials of the examples is significantly better than that of the materials prepared in the comparative examples 1 to 2.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. A process for repairing soil heavy metal pollution by using a nano repairing material is characterized by comprising the following steps:
(1) adding the polluted soil into crushing and screening equipment, crushing and primarily screening the soil, and screening large blocks and gravels mixed in the soil from the soil to obtain coarse-grained soil;
(2) feeding the coarse-grained soil obtained in the step (1) into a high-frequency vibrating screen for vibrating screening to obtain fine-grained soil with the grain size of 0.25-0.5 mm;
(3) adding the fine-particle soil obtained in the step (2) into mixing and stirring equipment, then adding a certain amount of water into the soil to enable the water content in the soil to reach 35-40%, stirring and mixing for 2-3 hours, then adding the nano repairing material, continuing to fully stir and mix for 4-8 hours, and then standing and maintaining;
(4) drying the soil in the step (3) after maintenance is finished until the water content is 2-4%;
(5) feeding the soil dried in the step (4) into a high-frequency vibrating screen again for vibrating screening to obtain superfine granular soil with the grain size of less than 0.25 mm;
(6) adding the superfine granular soil obtained in the step (5) into magnetic separation equipment, and carrying out magnetic separation on the magnetic nano repairing material;
wherein the nano-repair material is prepared by loading MnFe on modified sepiolite and biochar2O4The nano material consists of 1-3:1 by mass;
the preparation method of the modified sepiolite comprises the following steps:
(1) FeCl is added3Dissolving in water to obtain FeCl3Aqueous solution to FeCl3Adding polyethylene glycol into the aqueous solution to obtain a mixed solution; the FeCl3And the mass ratio of water to polyethylene glycol is 1-2: 2-6: 0.05-0.3;
(2) taking a sepiolite raw material, drying, crushing, sieving, adding the sieved sepiolite powder into the mixed solution obtained in the step (1), uniformly stirring, carrying out hydrothermal reaction at the temperature of 110-; the mass ratio of the sepiolite to the mixed liquid is 1-3: 5-12;
(3) adding the FeO (OH) -sepiolite compound prepared in the step (2) into a sodium diethyldithiocarbamate solution with the concentration of 1000-2000mg/L, fully stirring for 3-6 hours, and then filtering, drying, grinding and sieving to obtain the modified sepiolite;
the biochar is loaded with MnFe2O4The preparation method of the nano material comprises the following steps:
(1) preparing biochar: washing, drying and crushing a biomass raw material to obtain a granular raw material, then keeping the granular raw material at the temperature of 550-650 ℃ for 3-4 hours in a nitrogen atmosphere, cooling and taking out to obtain the biochar; the biomass raw material is one or more selected from peanut shells, corn stalks, rice hulls, sawdust or bamboo dust;
(2) biochar loaded MnFe2O4Preparing a nano material: sequentially adding biochar and FeCl into deionized water under the atmosphere of nitrogen3·6H2O and Mn (NO)3)2·4H2O; then the mixed solution is dripped into 1.5mol/L NaOH solution under the condition of continuous stirring at the temperature of 55 ℃ for reaction 30After min, centrifuging and washing to obtain the biochar-loaded MnFe2O4A nanomaterial; the FeCl3·6H2O、Mn(NO3)2·4H2The molar ratio of O to NaOH was 1:0.3: 6.
2. The process for remediating heavy metal pollution of soil using nano remediation material as claimed in claim 1, wherein the nano remediation material is added in an amount of 10-20% of the fine particle soil.
3. The process for remediating heavy metal pollution of soil by using a nano remediation material as claimed in claim 1, wherein the standing maintenance time is 3-7 days.
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