CN114316993A - Soil pollution repairing agent and repairing method thereof - Google Patents
Soil pollution repairing agent and repairing method thereof Download PDFInfo
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- CN114316993A CN114316993A CN202210036638.5A CN202210036638A CN114316993A CN 114316993 A CN114316993 A CN 114316993A CN 202210036638 A CN202210036638 A CN 202210036638A CN 114316993 A CN114316993 A CN 114316993A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 71
- 238000003900 soil pollution Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002689 soil Substances 0.000 claims abstract description 52
- 238000005067 remediation Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 37
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 31
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 25
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 25
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 24
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 24
- 239000004113 Sepiolite Substances 0.000 claims abstract description 22
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 22
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims description 31
- 239000010902 straw Substances 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 18
- 240000008042 Zea mays Species 0.000 claims description 14
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 14
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 14
- 235000005822 corn Nutrition 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000001090 Papaver somniferum Species 0.000 description 1
- 235000008753 Papaver somniferum Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention belongs to the field of soil remediation, and particularly relates to a soil pollution remediation agent and a remediation method thereof. The preparation method of the repairing agent comprises the steps of uniformly mixing sepiolite powder, magnesite powder and biomass raw materials to obtain a mixture A; preparing a mixed solution B of potassium permanganate, lanthanum nitrate and samarium nitrate, adding the mixture A into the mixed solution B, ultrasonically dispersing, evaporating to dryness in a constant-temperature water bath, preserving heat at 350-400 ℃ for 2-4h in an oxygen-containing atmosphere, preserving heat at 550-650 ℃ for 2-4h, and cooling to room temperature to obtain the soil pollution remediation agent. The obtained repairing agent can quickly solidify heavy metals in soil, has high removal rate, low cost and small usage amount, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of soil remediation. And more particularly, to a soil pollution remediation agent and a remediation method thereof.
Background
With the acceleration of industrialization and urbanization, the soil environment is continuously deteriorated, especially the pollution of heavy metals in the soil becomes a problem which seriously affects human health and environmental safety. The cultivated land polluted by heavy metals such As cadmium (Cd), arsenic (As), mercury (Hg), copper (Cu), zinc (Zn) and the like in China has about 1000 maha, and the direct economic loss of 200 billions of yuan is caused by over 1000 million tons of grains (such As cadmium rice, arsenic rice and the like) polluted by heavy metals every year. The method is characterized in that poppy and the like investigate and analyze the total amount and the form of Cd, Pb, Zn and Cu in the greenbelt soil of residents in the Zhuhui area of the Hengyang city, and find that the content of Cu, Cd and Pb is 1-5 times of the secondary standard of the national soil environment quality, so that the problem that the soil is subjected to composite pollution by heavy metals of Cd, Pb, Zn and Cu is increasingly prominent, and the method has great influence on the global soil quality, the soil ecology and the human health. Due to the complexity of the inherent matrix of the soil, complex interactions exist among various heavy metals and between the heavy metals and the soil interface, and challenges are brought to pollution remediation and curing agent selection. How to properly restore the heavy metal pollution of the soil, especially the soil with multiple heavy metal compound pollution, has attracted wide social attention.
Biochar is a porous, high specific surface area, difficult degradation and rich carbon-containing material, has high stability in soil, can exist for thousands of millions of years, researches show that biochar has high adsorption performance on pollutants, has great potential in soil pollution remediation, nearly ten years, researchers highly pay attention to the influence of biochar on heavy metal in soil, and mostly concentrate on the research of fixing soil heavy metal by biochar, influencing heavy metal leaching and adsorption-desorption, changing heavy metal form and the influence of biochar on heavy metal bioavailability, many research results show that biochar can effectively adsorb and fix soil heavy metal, so that heavy metal is converted from an effective state to a stable state, the bioavailability of heavy metal is reduced, and the mechanism has two aspects: on one hand, the biochar has high electronegativity and high cation exchange capacity, has abundant functional groups (-OH, -COOH, -C ═ O-and C ═ N and the like) on the surface, contains mineral elements, and therefore can directly interact with heavy metals, such as electrostatic attraction, ion exchange, complexation and precipitation, and on the other hand, the biochar indirectly influences the heavy metal form in the soil by influencing the physical and chemical properties of the soil, and further influences the biological effectiveness of the biochar.
CN110373199A discloses a composite soil repairing agent and a preparation method and a repairing method thereof, wherein the repairing agent is composed of a hydroxyapatite-calcium silicate composite material and biological carbon, the mass ratio of the hydroxyapatite-calcium silicate composite material to the biological carbon is 4:6-9:1, and the biological carbon is poplar-based biological carbon. The preparation method comprises the following steps: respectively preparing a calcium chloride dispersion liquid and a sodium silicate dispersion liquid, then dropwise adding a calcium chloride solution into the sodium silicate solution under ultrasonic waves, reacting, washing with deionized water after the reaction is finished, filtering to obtain a calcium silicate hydrate precipitate, then adding the calcium silicate hydrate precipitate into a phosphate solution, reacting, filtering to obtain a hydroxyapatite-calcium silicate composite material, and mixing biochar with the composite material according to a mass ratio to obtain the soil remediation agent. When the ratio of the two is 4:6, the materials are mutually promoted to generate a synergistic effect, the composite repairing agent can achieve long-term and high-efficiency repairing effect on severe and composite metal polluted soil, and has the advantages of low cost, small usage amount and environmental protection.
CN111234827A discloses a heavy metal contaminated soil remediation agent, which comprises: magnesium-modified montmorillonite having MgO-H groups and-Si-O-groups. The preparation method of the heavy metal contaminated soil remediation agent comprises the following steps: and calcining precipitates obtained by fully reacting glucose, basic magnesium carbonate and montmorillonite at the temperature of 60-70 ℃. The heavy metal contaminated soil remediation agent is applied to remediation of heavy metal contaminated soil. The heavy metal contaminated soil remediation agent can efficiently remediate copper, cadmium, lead and zinc contaminated soil, and has the advantages of low cost, simple operation, high efficiency and environmental friendliness.
After the research on the remediation of the polluted soil is conducted, the remediation agent still has the problems of long curing period and low removal rate, and how to develop a new soil remediation agent to solve the problems of long curing period and low removal rate is still a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems of long curing period and low removal rate in the prior art and provides a soil pollution repairing agent and a repairing method thereof.
The invention aims to provide a soil pollution remediation agent. The preparation method of the repairing agent comprises the steps of uniformly mixing sepiolite powder, magnesite powder and biomass raw materials to obtain a mixture A; preparing a mixed solution B of potassium permanganate, lanthanum nitrate and samarium nitrate, adding the mixture A into the mixed solution B, ultrasonically dispersing, evaporating to dryness in a constant-temperature water bath, preserving heat at 350-400 ℃ for 2-4h in an oxygen-containing atmosphere, preserving heat at 550-650 ℃ for 2-4h, and cooling to room temperature to obtain the soil pollution remediation agent.
It is another object of the present invention to provide a remediation method using the soil contamination remediation agent.
The above purpose of the invention is realized by the following technical scheme:
a soil pollution repairing agent is prepared by the following steps:
(1) uniformly mixing sepiolite powder, magnesite powder and biomass raw materials to obtain a mixture A;
(2) preparing a mixed solution B of potassium permanganate, lanthanum nitrate and samarium nitrate;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion, evaporating in a constant-temperature water bath to dryness, then performing heat preservation for 2-4h at 350-400 ℃ in an inert atmosphere with the oxygen content of 0.05-0.2% by volume, then performing heat preservation treatment for 2-4h at 550-650 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Preferably, in the step (1), the mass ratio of the sepiolite powder to the magnesite powder to the biomass raw material is 1:0, 2-0, and 4: 3-6. Further preferably, the mass ratio of the sepiolite powder, the magnesite powder and the biomass raw material is 2 g: 0.4-0.8 g: 6g to 12 g.
Preferably, in the step (1), the biomass raw material is rice straw, wheat straw or corn straw.
Preferably, in the step (2), the molar ratio of the potassium permanganate to the lanthanum nitrate to the samarium nitrate is 1:1, 2-1, 4; 1, 2-1, 4. Further preferably, the concentration of the potassium permanganate is 0.1 mol/L; the concentration of lanthanum nitrate is 0.12-0.14 mol/L; the concentration of the samarium nitrate is 0.12-0.14 mol/L; the volume of the mixed solution B is 100 mL.
Preferably, the ratio of the mixture A to the mixed solution B is 8.4 g-14.8 g: 100 mL.
Preferably, in the step (3), the ultrasonic dispersion time is 2-4 h; the temperature of the constant-temperature water bath is 80-100 ℃.
Preferably, in the step (3), the inert atmosphere is one or more of nitrogen, helium and neon.
The soil pollution repairing agent repairing method based on the above is characterized in that: and fully mixing the repairing agent with the heavy metal contaminated soil, maintaining the water content of the soil to be 20-40%, repairing for 7-50 days, wherein the adding amount of the repairing agent is 1-3 wt%.
Preferably, the heavy metals include lead, cadmium and/or copper.
The invention has the following beneficial effects:
(1) the magnesite is carbonate mineral containing magnesium, and the chemical formula of the magnesite is MgCO347.81% of MgO; CO 2252.19 percent; often contains a small amount of impurities such as iron, manganese, silicon, calcium and the like, which start to decompose at 350 ℃ to generate CO2And MgO, and CO2The release of the manganese-containing carbon material can play a role in reaming, so that the pore channel structures of the sepiolite and the carbon material are enriched, the specific surface area and the content of functional groups of the biochar material can be improved by MgO, the increase of oxygen-containing groups of the carbon material can be further promoted by the existence of a small amount of impurities, and the existence of iron and manganese can form a magnetic material, so that the repairing agent has certain magnetism, and the adsorption of heavy metals is promoted;
(2) by adding manganese, lanthanum and samarium, the adsorption capacity of the biochar can be obviously improved, oxygen-containing groups are increased, the mutual synergistic effect among metals is found to be improved, the adsorption of heavy metals is further promoted by utilizing the mutual synergy of the components, the solidification period is shortened, and the removal rate of the heavy metals is improved;
(3) by controlling the calcining atmosphere, the oxygen-containing groups of the biochar can be improved in the presence of a small amount of oxygen, so that the increase of the adsorption capacity is facilitated, the curing period is shortened, and the removal rate of heavy metals is improved;
(4) by means of sectional heat treatment, the CO release of magnesite can be controlled2The speed of the method is high, the pore structure of the sepiolite and the pore structure of the carbon material are enriched, the specific surface area is further improved, and the adsorption capacity and the heavy metal removal capacity are improved.
In conclusion, the soil pollution remediation agent prepared by the invention has the advantages of enlarged specific surface area, abundant pore channel structures and higher adsorption capacity, and is an ideal material for soil pollution remediation.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Example 2
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.8g of magnesite powder and 6g of rice straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.14mol/L, and the concentration of the samarium nitrate is 0.12 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 4h, evaporating to dryness in a constant-temperature water bath at 100 ℃, then performing heat preservation for 2h at 400 ℃ under a helium atmosphere with the oxygen content of 0.2% by volume, then performing heat preservation treatment for 2h at 650 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Example 3
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.4g of magnesite powder and 12g of wheat straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.12mol/L, and the concentration of the samarium nitrate is 0.14 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 2h, evaporating to dryness in a constant-temperature water bath at 80 ℃, then performing heat preservation for 4h at 350 ℃ under a neon atmosphere with the oxygen content of 0.05% by volume, then performing heat preservation treatment for 4h at 550 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 1
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesium carbonate and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 2
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, and the concentration of the samarium nitrate is 0.26 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 3
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate and lanthanum nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, and the concentration of the lanthanum nitrate is 0.26 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 4
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the lanthanum nitrate is 0.23mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 5
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.23mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 6
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.23 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 7
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate and lanthanum nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.23mol/L, and the concentration of the lanthanum nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 8
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 9
A soil pollution repairing agent is prepared by the following steps:
(1) 2g of sepiolite powder, 0.6g of magnesite powder and 9g of corn straw are uniformly mixed to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) and (2) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation treatment for 6h at 600 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 10
A soil pollution repairing agent is prepared by the following steps:
(1) uniformly mixing 2.6g of sepiolite powder and 9g of corn straws to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Comparative example 11
A soil pollution repairing agent is prepared by the following steps:
(1) uniformly mixing 2.6g of magnesite powder and 9g of corn straws to obtain a mixture A;
(2) potassium permanganate, lanthanum nitrate and samarium nitrate are prepared and dissolved in 100mL of deionized water to obtain a mixed solution B, wherein the concentration of the potassium permanganate is 0.1mol/L, the concentration of the lanthanum nitrate is 0.13mol/L, and the concentration of the samarium nitrate is 0.13 mol/L;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion for 3h, evaporating to dryness in a constant-temperature water bath at 90 ℃, then performing heat preservation for 3h at 380 ℃ in a nitrogen atmosphere with the oxygen content of 0.1% by volume, then performing heat preservation treatment for 3h at 600 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
Before being used in a stabilization experiment, the soil is naturally air-dried, impurities are removed, the soil is ground and sieved by a 4-mesh sieve, and after uniform mixing, the physical and chemical properties of the soil are measured as follows: pH 7.46 (soil-water ratio of 1: 2.5, according to agricultural industry Standard of the people's republic of China-determination of soil pH NY/T1377-2007), organic matter 8.26 g.kg-1According to the method for measuring the total metal content in the soil (USEPA method 3051A) specified by the United States Environmental Protection Agency (USEPA), the contents of Cd, Pb, Zn and Cu in the soil are all lower than the detection limit (0.1 mg.kg)-1)。
Taking out the concentration of 0.02 g.L-1Cd (NO)3)2、1.3g·L-1Pb (NO) of3)2And 2.6 g.L-1Cu (NO) of3)2Adding 1L of each solution into 5.2kg of the prepared soil sample, adding heavy metal solution while stirring, mixing, air drying, aging for 6 months, sieving with 2mm sieve to test heavy metalAnd (4) compounding the polluted soil. The actual measured values of Cd, Pb and Cu in the soil with composite pollution are respectively 3.8, 248, 1451 and 511 mg/kg-1Respectively reach the soil environmental quality standard (GB 15618-2008) agricultural land (pH)>7.5, vegetable plot) second-level standard values for environmental quality of inorganic contaminants (0.6, 50, 300, 100 mg-kg)-1) 6.3, 5.0, 4.8 and 5.1 times of.
200g of contaminated soil is weighed and placed in 500mL beakers, adsorption treatment is repeated for 3 times each time, 4g of the soil contamination repairing agents in examples 1 to 3 and comparative examples 1 to 11 are respectively and fully mixed with the contaminated soil according to the proportion, each beaker is sealed by a preservative film with holes, the beaker is placed at room temperature for immobilization reaction, and deionized water is supplemented into the beaker every 5 days in the reaction process to keep the water content of the soil at about 30%.
The immobilization effect of the soil pollution adsorbents of examples 1 to 3 and comparative examples 1 to 11 on the soil heavy metals after 20 days and 25 days was evaluated by the TCLP method, and the specific results are shown in tables 1 to 2, wherein the TCLP determination was performed by a method in the environmental protection industry standard of the people's republic of china (HJ/T300-2007), that is, leaching with acetic acid and sodium hydroxide buffer solution, and the leaching process was: adding 30mL of TCLP extract (solid-to-liquid ratio 1: 20) into 1.5g of soil, and stirring at 30 r.min-1Is reacted for 18h on a flip-flop oscillator and then at 2000 r.min-1Centrifuging at speed for 20min, filtering with 0.45 μm filter membrane, and measuring heavy metal concentration in the supernatant by inductively coupled plasma emission spectrometry (ICP). The preparation method of the TCLP extracting solution comprises the following steps: adding 5.7mL of glacial acetic acid into distilled water, and adopting 1 mol. L-1NaOH and HNO of3The pH value of the solution is adjusted to 4.9, and the volume is adjusted to 1L for standby.
TABLE 1 immobilization Effect for 20 days of examples 1 to 3 and comparative examples 1 to 11
TABLE 2 immobilization Effect for 25 days for examples 1-3 and comparative examples 1-11
| Cd removal after 25d (%) | Pd removal after 25d (%) | Cu removal after 25d (%) | |
| Example 1 | 92.3 | 97.6 | 90.3 |
| Example 2 | 91.4 | 96.9 | 88.3 |
| Example 2 | 91.8 | 97.3 | 89.5 |
| Comparative example 1 | 89.3 | 95.4 | 86.9 |
| Comparative example 2 | 90.2 | 95.9 | 87.2 |
| Comparative example 3 | 90.6 | 96.2 | 87.5 |
| Comparative example 4 | 85.3 | 90.4 | 83.4 |
| Comparative example 5 | 91.1 | 96.4 | 87.9 |
| Comparative example 6 | 84.9 | 89.7 | 82.9 |
| Comparative example 7 | 90.9 | 96.3 | 97.6 |
| Comparative example 8 | 89.9 | 95.7 | 86.3 |
| Comparative example 9 | 91.2 | 96.7 | 87.6 |
| Comparative example 10 | 90.8 | 95.5 | 87.1 |
| Comparative example 11 | 82.2 | 84.2 | 79.9 |
From the comparison of examples 1 to 3 with comparative examples 1 to 11, it can be seen that the components of the present application have a synergistic effect, and the synergistic effect of the components simultaneously enables the repairing agent of the present application to have an excellent curing effect and a high heavy metal removal effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A soil pollution repairing agent is characterized in that: the preparation method of the repairing agent comprises the following steps:
(1) uniformly mixing sepiolite powder, magnesite powder and biomass raw materials to obtain a mixture A;
(2) preparing a mixed solution B of potassium permanganate, lanthanum nitrate and samarium nitrate;
(3) adding the mixture A obtained in the step (1) into the mixed solution B, performing ultrasonic dispersion, evaporating in a constant-temperature water bath to dryness, then performing heat preservation for 2-4h at 350-400 ℃ in an inert atmosphere with the oxygen content of 0.05-0.2% by volume, then performing heat preservation treatment for 2-4h at 550-650 ℃, and cooling to room temperature to obtain the soil pollution remediation agent.
2. The soil pollution remediation agent of claim 1, wherein: in the step (1), the mass ratio of the sepiolite powder to the magnesite powder to the biomass raw material is 1:0, 2-0, and 4: 3-6.
3. The soil pollution remediation agent of claim 1, wherein: in the step (1), the biomass raw material is rice straw, wheat straw or corn straw.
4. The soil pollution remediation agent of claim 1, wherein: in the step (2), the molar ratio of the potassium permanganate to the lanthanum nitrate to the samarium nitrate is 1:1, 2-1, 4; 1, 2-1, 4.
5. The soil pollution remediation agent of claim 1, wherein: in the step (3), the ultrasonic dispersion time is 2-4 h; the temperature of the constant-temperature water bath is 80-100 ℃.
6. The soil pollution remediation agent of claim 1, wherein: in the step (3), the inert atmosphere is one or more of nitrogen, helium and neon.
7. A remediation method using a soil pollution remediation agent as claimed in any one of claims 1 to 6, wherein: and fully mixing the repairing agent with the heavy metal contaminated soil, maintaining the water content of the soil to be 20-40%, repairing for 7-50 days, wherein the adding amount of the repairing agent is 1-3 wt%.
8. The repair method according to claim 7, characterized in that: the heavy metals include lead, cadmium and/or copper.
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