CN107824609B - Heavy metal soil remediation agent, preparation method and application - Google Patents
Heavy metal soil remediation agent, preparation method and application Download PDFInfo
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- CN107824609B CN107824609B CN201710966298.5A CN201710966298A CN107824609B CN 107824609 B CN107824609 B CN 107824609B CN 201710966298 A CN201710966298 A CN 201710966298A CN 107824609 B CN107824609 B CN 107824609B
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- 239000002689 soil Substances 0.000 title claims abstract description 185
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 153
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 112
- 238000005067 remediation Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010902 straw Substances 0.000 claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000011282 treatment Methods 0.000 claims abstract description 41
- 239000002923 metal particle Substances 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000012216 screening Methods 0.000 claims abstract description 23
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 17
- 238000007885 magnetic separation Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003466 welding Methods 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- -1 iron ions Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 235000015759 Artemisia selengensis Nutrition 0.000 description 1
- 241001168877 Artemisia selengensis Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention belongs to the technical field of soil remediation, and provides a heavy metal soil remediation agent, and a preparation method and application thereof. The method comprises the steps of firstly, crushing straws, adding the crushed straws into a ferrous sulfate solution, adding ammonia water and hydrogen peroxide to generate ferric hydroxide gel, interweaving the ferric hydroxide gel and straw cellulose, and standing, washing, filtering, drying and grinding to obtain the heavy metal soil remediation agent. The repairing agent is dispersed in soil to adsorb heavy metal particles, then laser irradiation is carried out to weld and agglomerate the particles into large particles, and then the repairing agent is removed through a magnetic separation screening machine, so that the permanent removal of the heavy metal in the soil can be realized. Compared with the traditional method, the treatment method can effectively prevent secondary pollution, the obtained repairing agent has strong adsorption capacity, high efficiency and wide application range, can permanently remove heavy metal particles in soil, and has the advantages of low cost, simple operation, easy control, no pollution and good comprehensive benefit.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and provides a heavy metal soil remediation agent, and a preparation method and application thereof.
Background
The soil not only provides mechanical support capability for plant growth, but also provides fertility factors such as water, fertilizer, gas, heat and the like required by the growth and development of the plant. In recent years, due to the rapid increase of population, the continuous acceleration of industrialization process, the unreasonable exploitation and smelting discharge of mineral resources, the long-term sewage irrigation and sludge application, the application of chemical fertilizers and pesticides and other reasons to soil, solid wastes are continuously stacked and dumped on the surface of soil, harmful wastewater continuously permeates into the soil, harmful gas and floating dust in the atmosphere continuously fall into the soil along with rainwater, and the problem of more and more serious soil pollution is caused.
The heavy metal pollution types of soil are numerous, the sources are widely distributed, the soil can cause harm to agricultural crops, and more seriously, some toxic heavy metals have concealment, long-term property and irreversibility in the process of polluting the environment of the farmland. The heavy metal pollution of the soil has the characteristics of variable form and difficult degradation.
At present, the technology for remedying the heavy metal pollution of the soil mainly comprises physical and chemical remediation and biological remediation. Wherein the physical and chemical methods comprise chemical solidification, soil leaching, electric remediation and the like; bioremediation includes microbial and phytoremediation. Among them, chemical curing, microbial remediation and phytoremediation are widely used. The chemical curing repair mainly precipitates, adsorbs, complexes and chelates the heavy metals in the soil, and has important significance for stabilizing the heavy metals; bioremediation is to degrade, convert and adsorb pollutants by using microorganisms with certain resistance to the pollutants in the physiological process of the microorganisms; phytoremediation is a method for absorbing, fixing and removing heavy metal pollutants by using naturally growing or genetically cultured plants based on the tolerance and accumulation of certain pollutants by the plants. Researchers at home and abroad have achieved certain achievements in the aspect of soil heavy metal pollution remediation, Hu and the like invent a method for treating heavy metal polluted soil, the method measures the heavy metal content value in the soil more accurately through vertical sampling and horizontal sampling, animal bone powder in the added heavy metal stabilizer has a good adsorption effect on heavy metal ions, the comprehensive effect of sodium dihydrogen phosphate, sodium lignosulfonate, potassium chloride and hydroxyapatite can solidify the chemical activity of the heavy metal ions, the adsorbed heavy metal ions and other biological nutrient substances are absorbed by roots and stems of artemisia selengensis, a soil improver is added, under the action of active substances such as microorganisms, harmful bacteria in the soil are inhibited, and the liquid microbial fertilizer improves the fertility and the growth activity of the soil. Meanwhile, Zhong et al invented a soil heavy metal restoration agent and its preparation method, the soil heavy metal restoration agent includes high molecular polymer and filler, the high molecular polymer can form stable chelate with heavy metal ion, effectively adsorb and fix free heavy metal ion in soil, reduce heavy metal activity, prevent crop from absorbing, and control its migration through the adsorption of filler. However, the above-mentioned techniques, whether biological fixation or chemical fixation, are difficult to permanently fix the heavy metals, and there is a risk of re-loss and re-entry into the soil due to environmental changes, and the preparation process is complicated and costly, which hinders the development of soil heavy metal pollution remediation.
Disclosure of Invention
Aiming at the defect that the existing soil heavy metal treatment technology is difficult to permanently fix, the invention provides a heavy metal soil remediation agent, a preparation method and application thereof. Is characterized in that ferric hydroxide and straws are prepared into gel, and then dried to form a nano-pore adsorption material which is formed by uniformly interweaving straw cellulose and ferric hydroxide, namely the heavy metal soil remediation agent. When the heavy metal soil remediation agent is used for removing heavy metals in soil, the use method is that the heavy metal soil remediation agent is dispersed in the soil, so that the heavy metal remediation agent can fully adsorb heavy metal ions, then the laser irradiation is utilized to weld and aggregate the adsorbent adsorbing the heavy metal ions to form large particles, and further the large particle adsorbent adsorbing the heavy metal ions is screened out of the soil through a magnetic separation screen. The method has the obvious advantages that the large heavy metal enriched particles are obtained by adsorption and laser welding and are screened from the soil, and the problem that the heavy metals are lost in the soil again is fundamentally solved.
The heavy metal soil remediation agent can effectively solve the problem of heavy metal pollution of soil, prevent the risk that heavy metal is lost again and enters the soil due to environmental change, has a simple preparation process and low cost, and is suitable for large-scale popularization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a heavy metal soil repairing agent is characterized in that straws are crushed and then added into a ferrous sulfate solution, ammonia water and hydrogen peroxide are added to generate ferric hydroxide gel, the ferric hydroxide gel is interwoven with straw cellulose, and the heavy metal soil repairing agent is obtained after standing, washing, filtering, drying and grinding; the preparation method comprises the following steps:
crushing straws to obtain straw particles with the length not more than 5mm, adding the straw particles into a ferrous sulfate solution, uniformly stirring, placing in a constant-temperature water bath, and continuously adding ammonia water and hydrogen peroxide under the stirring state until all ferrous ions in the system are oxidized into iron ions to form ferric hydroxide gel, and uniformly interweaving with straw cellulose; and standing for a certain time, washing with distilled water, filtering, heating in the air, drying, and grinding in a grinding machine to obtain the adsorbing material with the nano holes, namely the heavy metal soil remediation agent.
Preferably, the mass concentration of the ferrous sulfate solution is 10-15%;
preferably, the adding amount of the straw particles is 5-10% of the mass of the ferrous sulfate solution;
preferably, the temperature of the constant-temperature water bath is 70-90 ℃;
preferably, the standing time is 10-12 h;
preferably, the drying temperature is 100-120 ℃.
The heavy metal soil repairing agent is characterized in that ferric hydroxide gel prepared by the method is interwoven with straw cellulose and has a nano-porous adsorption material. It has excellent adsorption and fixation effects on heavy metals in the donation.
The application of the heavy metal soil remediation agent is characterized in that: the heavy metal soil remediation agent prepared by the method is dispersed in soil to adsorb heavy metal particles, then is subjected to laser irradiation welding and aggregation to form large particles, and then is removed by a magnetic separation screening machine, so that the permanent removal of heavy metals in the soil can be realized; the specific application method is as follows:
mixing the obtained repairing agent and soil according to a certain mass ratio and uniformly dispersing to ensure that nano holes of the repairing agent fully and effectively adsorb heavy metal particles; then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, and welding the repairing agent adsorbing heavy metal particles under the action of laser to form aggregated large particles; and then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
Preferably, the addition amount of the repairing agent is 1-3% of the mass of the soil;
preferably, the frequency of the continuous wave laser is 4.5-6.5 multiplied by 1014Hz, power density of 2-8 x 105W/cm2；
Preferably, the laser treatment time in the step (2) is 2-4 min.
In the preparation process of the repairing agent, because ferric hydroxide is generated in situ, a titration method is needed to determine a reaction end point so as to avoid excessive oxidation or existence of ferrous ions, and potassium ferricyanide and potassium ferrocyanide solutions can be used for detection so as to ensure that iron elements in a system are all converted into ferric ions and form ferric hydroxide gel. The preparation process is characterized in that the stirring is continuously carried out, on one hand, under the action of stirring shearing force, the outer wall of the straw particles is broken, the expansion of the straw particles and the escape of cellulose are promoted, on the other hand, the added ammonia water and hydrogen peroxide are uniformly dispersed in the mixture as soon as possible, the generation speed of ferric hydroxide gel is favorably increased, and the excessive addition is prevented. When the remediation agent is used for adsorbing heavy metal particles in soil, the remediation agent is firstly uniformly dispersed in the soil to prevent uneven adsorption. During laser processing, the frequency and power density of the laser should be reasonably controlled. The laser frequency is too low or the power density is too low, so that the repair agent is not completely welded, and the repair agent for adsorbing heavy metals is not completely removed. And the laser frequency is too high or the power density is too high, so that substances which are beneficial to plant growth or soil quality improvement in soil can be killed at the same time, and the soil quality is reduced.
The invention provides a heavy metal soil repairing agent, a preparation method and application thereof, compared with the prior art, the heavy metal soil repairing agent has the outstanding characteristics and excellent effects that:
1. the treatment method of the invention does not need to add chemical reagents into the soil, thereby preventing secondary pollution.
2. When the repairing agent is prepared, the straw is used as a raw material, and the cellulose and the ferric hydroxide in the straw are utilized to form an interwoven structure, so that the straw has wide sources and low cost, the recycling of the straw is promoted, and the environmental problem caused by straw treatment is reduced.
3. The repairing agent prepared by the invention has nanometer-sized holes, strong adsorption capacity and high efficiency.
4. The repairing agent adsorbing the heavy metal particles is agglomerated into large particles by laser welding and then is screened to remove the large particles, so that the heavy metal particles in the soil can be permanently removed, and the defect that the heavy metal is easily lost again and enters the soil due to environmental change in a conventional treatment method is overcome.
5. The preparation method has the advantages of low cost, simple operation, easy control, no pollution, suitability for large-scale production and good comprehensive benefit.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idle rotation is carried out for 3min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 0.5kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 15%, uniformly stirring, placing in a constant-temperature water bath at 90 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 12h, washing with distilled water, filtering, heating to 100 ℃ in air, drying for 8h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil remediation agent; and mixing 3kg of the repairing agent with 100kg of soil, and uniformly dispersing to ensure that the nano holes of the repairing agent fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 6.5 multiplied by 1014Hz, power density of 2X 105W/cm2And the treatment time is 4min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 1 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 2
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idle rotation is carried out for 3min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 1kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 10%, uniformly stirring, placing in a constant-temperature water bath at 70 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 10h, washing with distilled water, filtering, heating to 100 ℃ in the air, drying for 8h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil repairing agent; and mixing and uniformly dispersing 2kg of the obtained repairing agent and 100kg of soil, so that the nano holes of the repairing agent can fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 4.5 multiplied by 1014Hz, power density of 8 x 105W/cm2And the treatment time is 2min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 2 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 3
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idling is carried out for 2min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 0.8kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 12%, uniformly stirring, placing in a constant-temperature water bath at 80 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 11h, washing with distilled water, filtering, heating to 110 ℃ in the air, drying for 9h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil remediation agent; 1.5kg of the repairing agent is mixed with 100kg of soil and uniformly dispersed, so that the nano holes of the repairing agent can fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 5 multiplied by 1014Hz, power density of 3X 105W/cm2And the treatment time is 3min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 3 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 4
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
mounting the straw pulverizer and its motor on a base made of angle steel, idling for 3min after starting, and confirmingAnd (4) after normal operation, continuously feeding dry straws, and crushing to obtain straw particles with the length not more than 5 mm. Then adding 0.7kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 15%, uniformly stirring, placing in a constant-temperature water bath with the temperature of 70 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until all ferrous ions in the system are oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with straw cellulose. Standing for 10h, washing with distilled water, filtering, heating to 100 ℃ in the air, drying for 8h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil repairing agent; and mixing and uniformly dispersing 2.5kg of the obtained repairing agent and 100kg of soil, so that the nano holes of the repairing agent can fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 6 multiplied by 1014Hz, power density of 4X 105W/cm2And the treatment time is 4min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 4 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 5
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idling is carried out for 2min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then 0.5kg of straw particles are added into 10kg of ferrous sulfate solution with the mass concentration of 10 percent,stirring uniformly, placing in a constant temperature water bath at 70 ℃, and continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions to form ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 12h, washing with distilled water, filtering, heating to 110 ℃ in the air, drying for 10h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil remediation agent; and mixing 3kg of the repairing agent with 100kg of soil, and uniformly dispersing to ensure that the nano holes of the repairing agent fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 4.8 multiplied by 1014Hz, power density of 6X 105W/cm2And the treatment time is 2min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 5 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 6
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idle rotation is carried out for 3min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 1kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 15%, uniformly stirring, placing in a constant-temperature water bath at 90 ℃, and continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions to form ferric hydroxideGelling and uniformly interweaving with straw cellulose. Standing for 10h, washing with distilled water, filtering, heating to 100 ℃ in the air, drying for 10h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil repairing agent; and mixing and uniformly dispersing 2kg of the obtained repairing agent and 100kg of soil, so that the nano holes of the repairing agent can fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 6.2 multiplied by 1014Hz, power density of 7X 105W/cm2And the treatment time is 2.5min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 6 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Example 7
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idling is carried out for 2min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 0.8kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 13%, uniformly stirring, placing in a constant-temperature water bath at 80 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 10 hr, washing with distilled water, filtering, heating to 120 deg.C in air, oven drying for 10 hr, and grinding in a grinder to obtain the final productThe adsorption material with the nano holes is the heavy metal soil repairing agent; and mixing 1kg of the obtained repairing agent with 100kg of soil, and uniformly dispersing to ensure that the nano holes of the repairing agent fully and effectively adsorb heavy metal particles. Then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, wherein the laser frequency is 5.5 multiplied by 1014Hz, power density of 5X 105W/cm2And the treatment time is 3.5min, so that the repairing agent for adsorbing heavy metal particles is welded under the action of laser to form agglomerated large particles. And then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing the heavy metal from the soil.
The heavy metal soil remediation agent prepared as described in example 7 was used to treat heavy metal contaminated soil and the concentration of heavy metal particles before and after treatment was measured and compared to conventional treatment methods and the data obtained is shown in table 1. It can be seen that: the heavy metal soil repairing agent prepared by the method has better repairing effect, and can ensure that the residual rate of heavy metal in soil is lower than 5%.
Comparative example 1
A heavy metal soil repairing agent and a preparation method and application thereof are disclosed, wherein the concrete processes of preparing and repairing soil are as follows:
the straw crusher and the motor thereof are arranged on a base made of angle steel, idling is carried out for 2min after starting, dry straws are continuously fed after confirming to be normal, and straw particles with the length not more than 5mm are obtained through crushing. Then adding 0.8kg of straw particles into 10kg of ferrous sulfate solution with the mass concentration of 13%, uniformly stirring, placing in a constant-temperature water bath at 80 ℃, continuously adding ammonia water and hydrogen peroxide under the stirring state until the ferrous ions in the system are completely oxidized into iron ions, forming ferric hydroxide gel, and uniformly interweaving with the straw cellulose. Standing for 10h, washing with distilled water, filtering, heating to 120 ℃ in the air, drying for 10h, and grinding in a grinder to obtain an adsorbing material with nanopores, namely the heavy metal soil repairing agent; and mixing 1kg of the obtained repairing agent with 100kg of soil, and uniformly dispersing to ensure that the nano holes of the repairing agent fully and effectively adsorb heavy metal particles. And then adding the mixed soil into a magnetic separation screening machine, and screening the repairing agent from the soil.
The laser treatment was omitted from comparative example 1, and the concentrations of heavy metal particles before and after the treatment were measured and compared with the conventional treatment method, and the obtained data are shown in table 1.
Comparative example 2
The heavy metals in the soil are repaired by using plants, and the repairing period is one season. The repairing effect is shown in table 1.
Table 1:
experiments prove that the repairing agent has excellent adsorbability, and the repairing agent adsorbing heavy metals forms large particles through laser welding and is separated out through magnetic separation, so that the heavy metals are thoroughly separated from the soil. In the comparative example, the laser welding treatment is absent, so that the heavy metal adsorbing repairing agent is not separated thoroughly, and the treatment effect is influenced. The conventional plant restoring soil has selectivity to heavy metals and long treatment period, so the restoring effect is obviously lower than that of the invention.
Claims (5)
1. A preparation method of a heavy metal soil repairing agent is characterized in that straws are crushed and then added into a ferrous sulfate solution, ammonia water and hydrogen peroxide are added to generate ferric hydroxide gel, the ferric hydroxide gel is interwoven with straw cellulose, and the heavy metal soil repairing agent is obtained after standing, washing, filtering, drying and grinding; the preparation method comprises the following steps:
crushing straws to obtain straw particles with the length not more than 5mm, and then adding the straw particles into a ferrous sulfate solution, wherein the adding amount of the straw particles is 5-10% of the mass of the ferrous sulfate solution; uniformly stirring, placing in a constant-temperature water bath, and continuously adding ammonia water and hydrogen peroxide under stirring until ferrous ions in the system are completely oxidized into ferric ions to form ferric hydroxide gel, and uniformly interweaving with straw cellulose; standing for a certain time, washing with distilled water, filtering, heating in air, drying, and grinding in a grinder to obtain an adsorption material with nanopores, namely the heavy metal soil remediation agent; the temperature of the constant-temperature water bath is 70-90 ℃; standing for 10-12 hours; the drying temperature is 100-120 ℃; the mass fraction of the ferrous sulfate solution is 10-15%.
2. A heavy metal soil remediation agent characterized by being prepared by the method of claim 1.
3. The use of the heavy metal soil remediation agent of claim 2, wherein: heavy metal particles are dispersed in soil to be adsorbed, then laser irradiation is carried out to weld and agglomerate the particles into large particles, and then the repairing agent is removed through a magnetic separation screening machine, so that the permanent removal of the heavy metal in the soil can be realized; the specific application method is as follows:
mixing the obtained repairing agent and soil according to a certain mass ratio and uniformly dispersing to ensure that nano holes of the repairing agent fully and effectively adsorb heavy metal particles; then placing the mixed soil in a laser chamber, starting a continuous wave laser generator to perform irradiation treatment on the mixed soil, and welding the repairing agent adsorbing heavy metal particles under the action of laser to form aggregated large particles; then adding the mixed soil into a magnetic separation screening machine, screening the large-particle repairing agent from the soil, and permanently removing heavy metals from the soil; the frequency of the continuous wave laser is 4.5-6.5 multiplied by 1014Hz, power density of 2-8 x 105W/cm2。
4. Use according to claim 3, characterized in that: the addition amount of the heavy metal soil remediation agent is 1-3% of the soil mass.
5. Use according to claim 3, characterized in that: the laser irradiation treatment time is 2-4 min.
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