CN111676022B - Method for remedying heavy metal pollution of soil - Google Patents
Method for remedying heavy metal pollution of soil Download PDFInfo
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- CN111676022B CN111676022B CN202010332763.1A CN202010332763A CN111676022B CN 111676022 B CN111676022 B CN 111676022B CN 202010332763 A CN202010332763 A CN 202010332763A CN 111676022 B CN111676022 B CN 111676022B
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- soil
- heavy metal
- polyvinyl alcohol
- weight
- metal contaminated
- Prior art date
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- 239000002689 soil Substances 0.000 title claims abstract description 199
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 86
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 78
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 78
- 238000005067 remediation Methods 0.000 claims abstract description 67
- 239000000440 bentonite Substances 0.000 claims abstract description 44
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 44
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000005291 magnetic effect Effects 0.000 claims abstract description 37
- 239000004005 microsphere Substances 0.000 claims abstract description 35
- 239000000805 composite resin Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003750 conditioning effect Effects 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 235000011996 Calamus deerratus Nutrition 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 229920002488 Hemicellulose Polymers 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
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- 235000019698 starch Nutrition 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 230000005415 magnetization Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
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- 239000000126 substance Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
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- 229910052785 arsenic Inorganic materials 0.000 abstract description 23
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052793 cadmium Inorganic materials 0.000 abstract description 23
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 238000002161 passivation Methods 0.000 abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052753 mercury Inorganic materials 0.000 abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- 239000011572 manganese Substances 0.000 abstract description 7
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- 239000000853 adhesive Substances 0.000 abstract description 3
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- 238000013268 sustained release Methods 0.000 abstract description 2
- 239000012730 sustained-release form Substances 0.000 abstract description 2
- 241000209495 Acorus Species 0.000 abstract 1
- 238000003900 soil pollution Methods 0.000 abstract 1
- 244000205574 Acorus calamus Species 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
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- 235000007164 Oryza sativa Nutrition 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- 235000006480 Acorus calamus Nutrition 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IERLNRXXTLBBLK-UHFFFAOYSA-N [S].[Si].[Fe] Chemical compound [S].[Si].[Fe] IERLNRXXTLBBLK-UHFFFAOYSA-N 0.000 description 2
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- 229910001629 magnesium chloride Inorganic materials 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
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- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
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- 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
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Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/70—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting wettability, e.g. drying agents
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of soil remediation, in particular to a method for remedying heavy metal pollution of soil, and firstly provides a heavy metal soil pollution remediation agent which is composed of a soil conditioning precursor and an adhesive component, wherein the soil conditioning precursor is composed of magnetic polyvinyl alcohol microspheres, iron magnesium acorus carbon and bentonite/polyvinyl alcohol composite resin, and the weight ratio of the magnetic polyvinyl alcohol microspheres to the bentonite/polyvinyl alcohol composite resin is 1.0: 3.0-5.0: 1.5-3.0; and applying the repairing agent to the surface of the heavy metal contaminated soil, turning over and mixing uniformly, slightly spraying water and maintaining to finish repairing the heavy metal contaminated soil. The repairing agent can efficiently repair heavy, medium and light heavy metal polluted soil, complete passivation and degradation of heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel, manganese and the like in the soil, improve the water retention capacity of the soil, increase the soil moisture value, enhance the soil quality, perform the sustained-release passivation and degradation effect on the heavy metal elements, prolong the action time and reduce the cost.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a method for remedying heavy metal pollution of soil.
Background
The soil inorganic pollutants are relatively prominent in heavy metals, and the heavy metals are easy to accumulate and are converted into methyl compounds with higher toxicity because the heavy metals cannot be decomposed by soil microorganisms, and even some of the heavy metals are accumulated in a human body at harmful concentration through a food chain and seriously harm the health of the human body. The heavy metal pollutants in soil mainly include mercury, cadmium, lead, copper, chromium, arsenic, nickel, iron, manganese, zinc, etc., although arsenic is not a heavy metal, it is usually discussed as being classified as a heavy metal because its behavior, source and harm are similar to those of heavy metals. As far as the needs for plants are concerned, the metallic elements can be classified into 2 types: the plant growth and development does not need elements, such as cadmium, mercury, lead and the like, which are obviously harmful to human health. Secondly, elements required by normal growth and development of plants have certain physiological functions to human bodies, such as copper, zinc and the like, but too much elements can cause pollution and hinder the growth and development of the plants.
Since the same metals have different forms in soil, and have different migration and transformation characteristics and different pollution properties, when the harm of heavy metals in soil is researched, attention is paid not only to the total content of the metals, but also to the content of various forms. Heavy metals are not easy to be leached with water in soil and can not be decomposed by soil microorganisms; on the contrary, organisms can enrich heavy metals, the heavy metals are often gradually accumulated in the soil environment, even some heavy metal elements can be converted into methyl compounds with higher toxicity in the soil, and the methyl compounds can be accumulated in human bodies at harmful concentration through food chains, so that the human health is seriously harmed. Compared with the pollution of water environment, the pollution of heavy metal to the soil environment is more difficult to treat and has more pollution hazard.
For the remediation of heavy metal compound contaminated soil, the stabilization remediation is mainly adopted at home at present. The stabilization restoration is to add a stabilizer into the soil, reduce the biological effectiveness and the mobility of the heavy metal through a series of reactions such as adsorption, precipitation, complexation, ion exchange, oxidation reduction and the like, thereby achieving the purpose of restoring the soil polluted by the heavy metal. Therefore, the key of the stabilization repair is to find a cheap and easily available efficient stabilizer without secondary pollution. Common stabilizers include alkaline substances such as lime and the like, and phosphorus-containing materials such as hydroxyapatite, ground phosphate rock, phosphate fertilizer and the like. The traditional stabilizers have the problems of high cost, certain environmental risk and the like, for example, excessive phosphorus-containing materials added into soil can cause eutrophication of water bodies. In recent years, the method for stabilizing and repairing heavy metals in soil by using shell powder has achieved certain results abroad, particularly in korea. Shells are a natural, readily available material. The shellfish production in china is the first world and exceeds 1000 million t per year, and the large amount of waste shells produced therewith are piled as solid waste in dumps or landfills. The waste shells are used for repairing the polluted soil, and the resource utilization of waste can be realized.
Aiming at the remediation of heavy metal contaminated soil, the prior art is a Chinese patent with an authorization publication number of CN105713619B, and discloses a preparation method of an iron-silicon-sulfur multi-element composite biochar soil heavy metal conditioner. The method comprises the following steps: adding silicate into agricultural waste, calcining in an air-isolated mode, adsorbing iron-containing salt on kaolin, adsorbing sulfate on bentonite, then uniformly mixing the 3 materials according to a certain proportion, adding diatomite and starch, and granulating to obtain the iron-silicon-sulfur multi-element composite biochar soil heavy metal conditioner. The conditioner can be widely applied to the heavy metal pollution treatment of paddy field soil, can simultaneously passivate cadmium, arsenic, lead and other compound pollution under the condition of acid or alkaline soil, and reduces the absorption and accumulation of rice so as to realize the safe utilization of polluted farmlands. However, the method can only passivate three heavy metal pollutants of cadmium, arsenic and lead, has no response passivation effect on other heavy metals of mercury, copper, chromium, nickel, manganese and the like, can only be applied to the remediation of medium and light heavy metal polluted soil, and has limited application range.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
In view of the above, the present invention aims to provide a heavy metal contaminated soil remediation agent and a method for remediating heavy metal contaminated soil by using the same, wherein the remediation method is simple and easy to implement, can efficiently remediate heavy, medium and light heavy metal contaminated soil, can complete passivation and degradation of heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel and manganese in the soil, can also improve water retention capacity of the soil, increase soil moisture value, enhance soil quality, perform sustained-release passivation and degradation effects on the heavy metal elements, prolong action time and reduce cost.
In order to achieve the above object, the present invention provides the following technical solutions.
[1] A heavy metal contaminated soil remediation agent, the remediation agent comprising:
a soil conditioning precursor consisting of magnetic polyvinyl alcohol microspheres, acorus gramineus carbon and bentonite/polyvinyl alcohol composite resin in a weight ratio of 1.0: 3.0-5.0: 1.5-3.0; and
a binder component;
wherein the saturation magnetization intensity of the magnetic polyvinyl alcohol microspheres is not less than 3.0 A.m2·kg-1。
According to some embodiments of the invention, the weight ratio of the magnetic polyvinyl alcohol microspheres, the iron-magnesium biomass charcoal and the bentonite/polyvinyl alcohol composite resin is preferably 1.0: 4.0-5.0: 1.5-2.0, more preferably 1.0: 4.0-4.5: 1.5-2.0, and most preferably 1.0:4.5: 1.5.
The soil conditioning precursor ternary structure composed of the magnetic polyvinyl alcohol microspheres, the acorus gramineus carbon and the bentonite/polyvinyl alcohol composite resin is used as an effective component of the heavy metal polluted soil repairing agent, the raw materials of the soil conditioning precursor ternary structure are wide in sources of polyvinyl alcohol, ferromagnetic powder, biomass carbon, bentonite and the like, the soil conditioning precursor ternary structure is easy to degrade in soil, and soil quality can be increased after heavy metal pollution is repaired; the heavy metal polluted soil restoration agent is a compound soil restoration agent containing multiple elements such as iron, magnesium, silicon and the like, can be used for efficiently restoring heavy, medium and light heavy metal polluted soil, can be used for passivating heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel, manganese and the like in the soil, can be used for fertilizing the soil, achieves the purpose of simultaneously developing the restoration of the heavy metal soil and the agricultural safety production, obviously improves the problem of agricultural soil waste caused by multiple heavy metal pollution in China at present, and further improves the urgent situation that the heavy metal content of crops exceeds the standard.
According to some embodiments of the invention, the binder component is comprised of diatomaceous earth and starch.
According to some embodiments of the invention, the magnetic polyvinyl alcohol microspheres are prepared by a method comprising:
1) 0.3-0.5 weight part of gelatin is completely dissolved in sufficient distilled water at room temperature;
2) sequentially adding 0.3-0.5 part by weight of benzoyl peroxide, 8-10 parts by weight of liquid wax, 8-10 parts by weight of divinylbenzene and 25-40 parts by weight of polyvinyl alcohol under stirring, and continuously stirring for at least 45 min;
3) heating to 48-50 ℃, preserving the temperature for at least 10min, and adding 0.6-0.8 part by weight of sodium carbonate and 1.5-2.0 parts by weight of magnesium sulfate;
4) heating to 70-78 ℃, preserving heat for at least 15min, adding 2.5-4.0 parts by weight of magnetic powder, and preserving heat for at least 4 h;
5) heating to 90-98 ℃, keeping the temperature for at least 2h, cooling the solution to below 80 ℃, washing, filtering, drying in vacuum, crushing, and sieving with at least 100-mesh sieve.
According to some embodiments of the invention, the stirring rate in the step 2) is 120 to 180 r/min.
According to some embodiments of the invention, the polyvinyl alcohol of step 2) has a weight average molecular weight not higher than 20000.
According to some embodiments of the present invention, the temperature rising rate of the steps 3) to 5) is 0.5 to 1.0 ℃/min.
According to some embodiments of the invention, the magnetic powder of step 4) is Fe3O4And (4) magnetic powder.
According to further embodiments of the present invention, the magnetic powder of step 4) is modified by the following steps: equal weight of Fe3O4Adding the magnetic powder and the silane coupling agent into 50-75% ethanol solution which is at least 50 times of the weight of the magnetic powder and the silane coupling agent, uniformly dispersing, slowly heating to 42-45 ℃ under the protection of nitrogen, stirring for at least 18 hours at 800-1200 r/min, washing for multiple times by using ethanol and deionized water, and drying in vacuum at 60 ℃ for at least 48 hours.
According to other embodiments of the present invention, the silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris (β -methoxyethoxy) silane.
According to some embodiments of the invention, the vacuum drying of step 5) refers to drying at not higher than 60 ℃ under vacuum for at least 24 hours.
Silane coupling agent is used as surfactant to modify Fe3O4The magnetic powder particle surface can make the final magnetic polyvinyl alcohol microsphere more regular, obtain narrower particle size distribution and better dispersity, is favorable for improving the magnetization intensity of the magnetic polyvinyl alcohol microsphere, and plays a positive role in strengthening heavy metal pollution soil repairing agent passivation heavy metal.
According to some embodiments of the invention, the acorus gramineus carbon is prepared by a process comprising the following steps:
1) pulverizing cleaned and dried rhizoma Acori Calami, and sieving to obtain sawdust with size not greater than 0.5 mm;
2) preparation of a composition containing Fe3+、Fe2+And Mg2+The mixed impregnation stabilizing solution of (1);
3) under nitrogen, soaking the sawdust in the step 1) into the mixed soaking stable solution in the step 2) for at least 2 hours according to the weight ratio of the sawdust to the metal cations of 100: 1.0-3.0;
4) heating the mixed solution obtained in the step 3) to 550-580 ℃ under nitrogen, and pyrolyzing for at least 1.5 h;
5) and (5) washing ash on the biochar in the step 4) for multiple times, drying, crushing and sieving by a 100-mesh sieve to obtain the biological carbon.
According to some embodiments of the invention, the Fe in step 2)3+、Fe2+And Mg2+Can respectively select Fe2(SO4)3·9H2O、FeSO4·7H2O、MgCl2·6H2And (O) preparation.
According to some embodiments of the invention, the Fe in step 2)3+、Fe2+And Mg2+The amount ratio of the substances (A) is 2-3: 1: 0.3-1.
According to some embodiments of the invention, the temperature increase rate of the step 4) is 5-8 ℃/min.
The calamus biochar is used as a structure, the obtained iron-magnesium calamus carbon is prepared by carrying iron-magnesium ions, and is compounded with magnetic polyvinyl alcohol microspheres and bentonite/polyvinyl alcohol composite resin, so that the soil heavy metal passivation effect is excellent, the iron-magnesium calamus carbon is rich in iron and magnesium elements, the element proportion in soil can be enriched, in addition, the iron-magnesium calamus carbon also has the function of enriching nitrogen and phosphorus in a soil solution, and the iron-magnesium calamus carbon after nitrogen and phosphorus enrichment can be used as a nitrogen and phosphorus slow release fertilizer to further increase the soil fertility.
According to some embodiments of the present invention, the bentonite/polyvinyl alcohol composite resin is prepared by a method comprising the steps of:
1) at room temperature, adding sufficient oxalic acid solution into natural bentonite, soaking, reacting for at least 2 hours in a shaking table for 120-150 times/min, adding hemicellulose alkali liquor and sodium bisulfite, and performing ultrasonic dispersion for at least 20 min;
2) and (3) rapidly heating to 55-60 ℃, adding a polyvinyl alcohol aqueous solution, reacting at a constant temperature for at least 30min under stirring, flocculating and washing a product with ethanol, drying, fully grinding, extracting with acetone for 12h, and drying to obtain the product.
According to some specific embodiments of the present invention, in the preparation method of the bentonite/polyvinyl alcohol composite resin, the weight ratio of the natural bentonite, the oxalic acid, the hemicellulose, the sodium bisulfite and the polyvinyl alcohol is 1: 0.8-1.0: 0.3-0.5: 0.01-0.015: 0.3-0.6.
According to some embodiments of the present invention, in the preparation method of the bentonite/polyvinyl alcohol composite resin, the ultrasonic frequency of ultrasonic dispersion is 50 to 80KHz, and the ultrasonic energy density is 0.6 to 0.8w/cm2。
According to some embodiments of the present invention, in the method for preparing the bentonite/polyvinyl alcohol composite resin, the weight average molecular weight of polyvinyl alcohol is not higher than 25000.
According to some embodiments of the present invention, in the preparation method of the bentonite/polyvinyl alcohol composite resin, the drying temperature is 60 to 70 ℃, and the drying time is at least 12 hours.
According to some embodiments of the present invention, the bentonite/polyvinyl alcohol composite resin is prepared by sufficiently grinding to pass through a 120-mesh sieve.
The bentonite/polyvinyl alcohol composite resin is prepared by modifying natural bentonite with oxalic acid, adding hemicellulose and a reducing agent sodium bisulfite for reaction, and finally introducing polyvinyl alcohol into a hemicellulose/bentonite system, so that the three-dimensional network structure of the resin is improved, the bentonite/polyvinyl alcohol composite resin has excellent water absorbability, water retentivity, salt tolerance and thermal stability, is easy to degrade and free of pollution, and is compounded with magnetic polyvinyl alcohol microspheres and acorus gramineus carbon to form the heavy metal polluted soil repairing agent, so that the heavy metal polluted soil repairing agent is beneficial to increasing the water retention and water retention capacity of soil, increasing the soil moisture value of the soil, and can enhance the soil quality after degradation, and the higher salt adsorption effect can also obviously enhance the heavy metal element gathering capacity of the repairing agent, so that heavy metal ions are adsorbed to the periphery of the repairing agent and are degraded and removed by the repairing agent, the heavy metal degrading capacity is remarkably improved, on the other hand, the bentonite/polyvinyl alcohol composite resin can also coat the magnetic polyvinyl alcohol microspheres, so that a good slow-release effect can be achieved in the gradual degradation process, the heavy metal degrading effect of the heavy metal contaminated soil repairing agent is improved to the fourth season, and the cost is remarkably reduced.
[2] A method for producing the heavy metal-contaminated soil remediation agent of item [1], the method comprising:
1) preparing magnetic polyvinyl alcohol microspheres;
2) preparing iron magnesium calamus carbon;
3) preparing bentonite/polyvinyl alcohol composite resin;
4) fully mixing the materials prepared in the steps 1), 2) and 3) according to the weight ratio of 1.0: 3.0-5.0: 1.5-3.0 to obtain a soil conditioning precursor;
5) uniformly mixing the soil conditioning precursor prepared in the step 4) with diatomite and starch according to the mass ratio of 100: 1-10, spraying water for granulation, and drying to obtain the heavy metal contaminated soil remediation agent.
According to some embodiments of the invention, the particle size of the heavy metal contaminated soil remediation agent is 3-5 mm.
The soil conditioning precursor ternary structure composed of magnetic polyvinyl alcohol microspheres, acorus gramineus carbon and bentonite/polyvinyl alcohol composite resin is used as an effective component, diatomite and starch are granulated to prepare the heavy metal polluted soil repairing agent, the production process is simple and can be produced in a large scale, the raw materials including polyvinyl alcohol, ferromagnetic powder, biomass carbon, bentonite and the like are wide in source and easy to degrade in soil, and soil quality can be increased after heavy metal pollution is repaired; the soil polluted by heavy, medium and light heavy metals can be efficiently restored, and meanwhile, the passivation of heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel, manganese and the like in the soil is completed, and the soil is fertilized; the soil fertilizer is rich in iron and magnesium elements, can enrich the element proportion in soil, has the function of enriching nitrogen and phosphorus in a soil solution, and can be used as a nitrogen and phosphorus slow release fertilizer after the nitrogen and phosphorus are enriched to further increase the soil quality; the bentonite/polyvinyl alcohol composite resin can also coat the magnetic polyvinyl alcohol microspheres, the outside is further bonded by the adhesive, a good slow release effect can be achieved in the gradual degradation process, the effect of the heavy metal polluted soil repairing agent on degrading heavy metals is improved to the fourth season, and the cost is obviously reduced.
[3] The use of the heavy metal contaminated soil remediation agent according to any one of items [1] to [2] for remediation of heavy metal contamination of soil.
[4] A method of remediating heavy metal contamination of soil, the method comprising:
applying any one of the heavy metal contaminated soil remediation agents [1] to [2] with the thickness of 0.2-1 cm on the surface of the heavy metal contaminated soil, uniformly mixing soil layers at least 15cm deep away from the surface layer of the soil in a turning mode, and slightly spraying water to maintain for 3-5 months to complete remediation of the heavy metal contaminated soil.
The invention has the beneficial effects that:
1) the soil conditioning precursor ternary structure composed of magnetic polyvinyl alcohol microspheres, acorus gramineus carbon and bentonite/polyvinyl alcohol composite resin is used as an effective component, diatomite and starch are granulated to prepare the heavy metal polluted soil repairing agent, the production process is simple and can be produced in a large scale, the raw materials including polyvinyl alcohol, ferromagnetic powder, biomass carbon, bentonite and the like are wide in source and easy to degrade in soil, and soil quality can be increased after heavy metal pollution is repaired;
2) the soil polluted by heavy, medium and light heavy metals can be efficiently restored, and meanwhile, the passivation of heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel, manganese and the like in the soil is completed, and the soil is fertilized; the soil fertilizer is rich in iron and magnesium elements, can enrich the element proportion in soil, has the function of enriching nitrogen and phosphorus in a soil solution, and can be used as a nitrogen and phosphorus slow release fertilizer after the nitrogen and phosphorus are enriched to further increase the soil quality;
3) the bentonite/polyvinyl alcohol composite resin, the magnetic polyvinyl alcohol microspheres and the acorus calamus carbon are compounded into the heavy metal polluted soil restoration agent, so that the water retention capacity of soil is improved, the soil moisture value of the soil is increased, the soil quality can be enhanced after degradation, the capability of the restoration agent for gathering heavy metal elements can be obviously enhanced due to the higher salt adsorption effect, heavy metal ions are adsorbed to the periphery of the restoration agent and then degraded and removed, and the capability of degrading heavy metals is obviously improved;
4) the heavy metal contaminated soil remediation agent can play a good slow release role in the gradual degradation process, the heavy metal degradation effect of the heavy metal contaminated soil remediation agent is improved to the fourth season, the effect aging is prolonged, and the cost is obviously reduced.
The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of the detection of the magnetization property of magnetic polyvinyl alcohol microspheres in some embodiments of the present invention;
FIG. 2 is a schematic diagram illustrating the passivation effect of the repairing agent of some embodiments of the present invention on heavy metal cadmium in soil in four seasons;
FIG. 3 is a schematic diagram illustrating the passivation effect of the remediation agent of some embodiments of the present invention on heavy metal arsenic in soil in four seasons;
FIG. 4 is a schematic diagram of the passivation effect of the repairing agent of some embodiments of the present invention on heavy metal lead in soil through four seasons.
Detailed Description
Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5(1 to 5)" is described, the described range is understood to include ranges of "1 to 4(1 to 4)", "1 to 3(1 to 3)", "1 to 2(1 to 2) and 4 to 5(4 to 5)", "1 to 3(1 to 3) and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges, and all integers and fractions within the ranges.
When the term "about" is used to describe a numerical value or an end point value of a range, the disclosure should be understood to include the specific value or end point referred to.
Furthermore, "or" means "or" unless expressly indicated to the contrary, rather than "or" exclusively. For example, condition a "or" B "applies to any of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The present invention is described in detail below.
Example 1: a heavy metal contaminated soil remediation agent:
the embodiment provides a heavy metal contaminated soil remediation agent, which comprises:
a soil conditioning precursor consisting of magnetic polyvinyl alcohol microspheres, acorus calamus carbon and bentonite/polyvinyl alcohol composite resin in a weight ratio of 1:4.5: 1.5; and
an adhesive component consisting of bentonite and starch;
wherein the magnetization intensity of the magnetic polyvinyl alcohol microspheres is not less than 2.5 A.m2/kg。
The heavy metal contaminated soil remediation agent is prepared by a method comprising the following steps.
1) Preparing magnetic polyvinyl alcohol microspheres:
1.1) 0.4 weight part of gelatin is completely dissolved in enough distilled water at room temperature;
1.2) adding 0.5 part by weight of benzoyl peroxide, 10 parts by weight of liquid wax, 10 parts by weight of divinylbenzene and 30 parts by weight of polyvinyl alcohol (weight-average molecular weight 16000) in sequence under the stirring of 120r/min, and continuing to stir for 45 min;
1.3) heating to 50 ℃ at the speed of 1.0 ℃/min and preserving the temperature for 10min, and adding 0.8 part by weight of sodium carbonate and 1.5 parts by weight of magnesium sulfate;
1.4) heating to 75 ℃ at a rate of 1.0 ℃/min and holding for 15min, adding 3 parts by weight of Fe3O4Magnetic powder is subjected to heat preservation for 4 hours;
1.5) heating to 95 ℃ at the speed of 1.0 ℃/min, preserving heat for 2 hours, cooling the solution to 78 ℃, washing, filtering, drying in vacuum at 60 ℃, crushing and sieving with a 100-mesh sieve to obtain the product;
the magnetic powder is modified by the following steps: 1 part by weight of Fe3O4Magnetic powder and 1 part by weightAdding vinyl trimethoxy silane into 100 parts by weight of 65% ethanol solution, uniformly dispersing, slowly heating to 42 ℃ under the protection of nitrogen, stirring for 18h at 1000r/min, washing with ethanol and deionized water for multiple times, and vacuum drying at 60 ℃ for 48 h.
2) Preparing iron magnesium calamus carbon:
2.1) crushing the cleaned and dried calamus, and screening to obtain wood chips with the size of not more than 0.5 mm;
2.2) with Fe respectively2(SO4)3·9H2O、FeSO4·7H2O、MgCl2·6H2O preparing Fe with the mass ratio of 4:2:13+、Fe2+And Mg2+Mixing the impregnation stabilizing solution;
2.3) under nitrogen, soaking the wood chips obtained in the step 2.1) into the mixed soaking stable solution obtained in the step 2.2) for 2 hours according to the weight ratio of the wood chips to the metal cations of 50: 1;
2.4) under nitrogen, heating the mixed solution in the step 2.3) to 560 ℃ at the speed of 8 ℃/min for pyrolysis for 2 h;
2.5) washing ash content on the biochar in the step 2.4) for 5 times, drying, crushing and sieving by a 100-mesh sieve to obtain the biological carbon.
3) Preparing bentonite/polyvinyl alcohol composite resin;
3.1) adding sufficient oxalic acid solution into natural bentonite for soaking at room temperature, reacting in a shaking table for 150 times/min for 2h, adding hemicellulose alkali liquor and sodium bisulfite, 60KHz and 0.6w/cm2Ultrasonic dispersing for 20 min;
3.2) rapidly heating to 60 ℃, adding a polyvinyl alcohol (with the weight average molecular weight of 20000) water solution, stirring and reacting at constant temperature for 45min, flocculating and washing a product with ethanol, drying at 65 ℃ for 12h, fully grinding and sieving with a 120-mesh sieve, extracting with acetone for 12h and drying to obtain the product;
wherein the weight ratio of the natural bentonite to the oxalic acid to the hemicellulose to the sodium bisulfite to the polyvinyl alcohol is 1:1:0.5:0.012: 0.4.
4) Compounding:
fully mixing the materials prepared in the steps 1), 2) and 3) according to the formula amount to obtain a soil conditioning precursor;
5) and (3) granulation:
uniformly mixing the soil conditioning precursor prepared in the step 4) with diatomite and starch according to the mass ratio of 50:1:4, spraying water for granulation to obtain a particle size of 4.0 +/-0.5 mm, and drying to obtain the heavy metal contaminated soil remediation agent.
Wherein, the diatomite has the pH value of 7.5, the specific surface area of 2.6 and the thickness of 325 meshes and is purchased from Shijiazhuang Hualang mineral product trade company; the pH value of the bentonite is 8.0, the whiteness is 55, the density is 1.3g/cm3, and the granularity is 180-220 meshes, and the bentonite is purchased from Nanjing Hengfeng calcium carbonate factory.
Example 2: the other heavy metal contaminated soil remediation agent comprises:
the composition, the proportion and the preparation method of the other heavy metal contaminated soil remediation agent provided by the embodiment are basically the same as those of the embodiment 1, and the difference is that the soil conditioning precursor of the embodiment does not contain the magnetic polyvinyl alcohol microspheres.
Example 3: the other heavy metal contaminated soil remediation agent comprises:
the present embodiment provides another heavy metal contaminated soil remediation agent, which has substantially the same components, proportions and preparation method as those in embodiment 1, except that the soil conditioning precursor of the present embodiment does not contain Acorus calamus carbon.
Example 4: the other heavy metal contaminated soil remediation agent comprises:
the present embodiment provides another heavy metal contaminated soil remediation agent, which has substantially the same components, proportions and preparation method as those in embodiment 1, except that the soil conditioning precursor of the present embodiment does not contain bentonite/polyvinyl alcohol composite resin.
Example 5: the other heavy metal contaminated soil remediation agent comprises:
the composition, the proportion and the preparation method of the other heavy metal contaminated soil remediation agent provided by the embodiment are basically the same as those in embodiment 1, except that the weight ratio of the magnetic polyvinyl alcohol microspheres, the acorus calamus carbon and the bentonite/polyvinyl alcohol composite resin in the soil conditioning precursor is 1:1: 1.
Example 6: the other heavy metal contaminated soil remediation agent comprises:
the present example provides another heavy metal contaminated soil remediation agent, which has substantially the same components, mixture ratio and preparation method as those in example 1, except that in the preparation of the magnetic polyvinyl alcohol microspheres, the polyvinyl alcohol is replaced by polystyrene with a weight average molecular weight of 16000.
Example 7: the other heavy metal contaminated soil remediation agent comprises:
the other heavy metal contaminated soil remediation agent provided by the embodiment has the same components, proportion and preparation method as those of the embodiment 1, and the difference is that the Fe content is Fe content when the magnetic polyvinyl alcohol microspheres are prepared3O4The magnetic powder is used for preparing the magnetic polyvinyl alcohol microspheres without any modification of a silane coupling agent.
Example 8: the other heavy metal contaminated soil remediation agent comprises:
the other heavy metal contaminated soil remediation agent provided by the embodiment has the same components, proportion and preparation method as those of the embodiment 1, except that in the embodiment, the iron-magnesium cotton straw charcoal is prepared by using cotton straws instead of calamus, and the heavy metal contaminated soil remediation agent is prepared by using the cotton straw charcoal, the magnetic polyvinyl alcohol microspheres and the bentonite/polyvinyl alcohol composite resin according to the proportion and the method of the embodiment 1.
Example 9: the other heavy metal contaminated soil remediation agent comprises:
the present example provides another heavy metal contaminated soil remediation agent, which has substantially the same components, proportions and preparation method as those of example 1, except that the mixed impregnation stabilizing solution does not contain Fe during the preparation of Acorus calamus Linn charcoal3+。
Example 10: the other heavy metal contaminated soil remediation agent comprises:
the present example provides another heavy metal contaminated soil remediation agent, which has substantially the same components, proportions and preparation method as those of example 1, except that the mixed impregnation stabilizing solution does not contain Fe during the preparation of Acorus calamus Linn charcoal2+。
Example 11: the other heavy metal contaminated soil remediation agent comprises:
the present example provides another heavy metal contaminated soil remediation agent, which has substantially the same components, proportions and preparation method as those of example 1, except that the mixed impregnation stabilizing solution does not contain Mg during the preparation of Acorus calamus Linn charcoal2+。
Example 12: the other heavy metal contaminated soil remediation agent comprises:
the composition, the proportion and the preparation method of the other heavy metal contaminated soil remediation agent are basically the same as those in example 1, except that in the preparation of the bentonite/polyvinyl alcohol composite resin, natural bentonite is not soaked in oxalic acid solution, hemicellulose alkali solution and sodium bisulfite are added after the natural bentonite is dispersed in water, and the heavy metal contaminated soil remediation agent is prepared through the same subsequent steps and other steps as those in example 1.
Experimental example 1: physical and chemical detection of the magnetic polyvinyl alcohol microspheres:
the magnetic property of the magnetic polyvinyl alcohol microspheres can be detected by a VSM-4HF type vibration sample magnetometer, and the magnetic polyvinyl alcohol microspheres can be subjected to Fe by thermogravimetric analysis3O4The magnetic properties and the coating ratios of examples 1, 6 and 7 were measured, respectively, and the results are shown in FIG. 1 and Table 1.
TABLE 1 results of physicochemical examination of magnetic polyvinyl alcohol microspheres
| Example group | Fe3O4Coating ratio (%) |
| Example 1 | 8.89 |
| Example 6 | 6.62 |
| Example 7 | 4.15 |
As can be seen from FIG. 1 and Table 1, Fe is present in place of polyvinyl alcohol by polystyrene3O4Maximum saturation magnetization intensity and Fe of powder body not modified by silane coupling agent to magnetic polyvinyl alcohol microsphere3O4The coating rate has more remarkable influence, wherein the maximum saturation magnetization of the magnetic polyvinyl alcohol microspheres prepared without modification by the silane coupling agent is even lower than 3.0 A.m2/kg。
Experimental example 2: detection of passivation effect of heavy metal polluted acid soil by heavy metal polluted soil remediation agent:
in the experimental example, the heavy metal contaminated acidic soil is collected from surface soil of a heavy metal contaminated farmland in Zhejiang province, and is naturally air-dried and then sieved by a 10-mesh sieve, and the pH value is about 4.5, the total cadmium content is 48.52ppm, the total arsenic content is 435.65ppm, the total lead content is 865.33pm, and the heavy metal contaminated acidic soil belongs to heavy metal contaminated soil. Dividing the soil into 12 groups, placing 10kG of each group into plastic barrels with the inner diameter of 40cm, respectively paving the repairing agents in the embodiments 1-12 into the 12 groups of plastic barrels, paving the repairing agents with the thickness of 0.5cm, then uniformly mixing the soil in the groups of plastic barrels, respectively spraying 500g of clear water, standing the mixture indoors for 3 months, analyzing the content of heavy metals such as cadmium, arsenic and lead, and calculating the reduction value of the soil compared with the control soil which is not treated by the repairing agents. And (4) planting the rice after ploughing again, collecting samples when harvesting the rice, analyzing the content of heavy metal cadmium, arsenic and lead in grains, and calculating the reduction value of the heavy metal cadmium, arsenic and lead in the grains compared with the control soil which is not treated by the repairing agent. The statistics are shown in table 2.
TABLE 2 passivating effects of remediation agents of various examples on heavy metal contaminated acidic soil with cadmium, arsenic and lead
As can be seen from table 2, the repairing agent in example 1 of the preferred embodiment of the present application not only can significantly reduce the content of cadmium, arsenic, and lead in the heavy metal contaminated acidic soil, but also can effectively block the migration of the three heavy metals to rice grains, thereby reducing the absorption accumulation effect of rice on the heavy metal contaminated soil and ensuring human health.
Experimental example 3: detection of the passivation effect of the heavy metal polluted soil remediation agent on heavy metal polluted alkaline soil:
in the experimental example, the heavy metal contaminated acidic soil is collected from surface soil of a heavy metal contaminated farmland in Zhejiang province, and is naturally air-dried and then sieved by a 10-mesh sieve, and the pH value is about 8.0, the total cadmium content is 62.58ppm, the total arsenic content is 502.84ppm, the total lead content is 755.59pm, and the heavy metal contaminated acidic soil belongs to heavy metal contaminated soil. In the same method as in experimental example 2, the remediation agents in examples 1 to 12 were used to remediate the soil, the contents of heavy metals cadmium, arsenic and lead were analyzed, and the reduction values were calculated in comparison with control soil that was not treated with the remediation agents. And planting and harvesting the rice, collecting samples, analyzing the content of heavy metals such as cadmium, arsenic and lead in grains, and calculating the reduction value of the heavy metals compared with the control soil which is not treated by the repairing agent. The statistics are shown in table 3.
TABLE 3 passivating effects of remediation agents of various examples on cadmium, arsenic, and lead in heavy metal contaminated alkaline soils
As can be seen from table 3, the repairing agent in example 1 of the preferred embodiment of the present application can be applied to the repairing work of heavy metal contaminated alkaline soil, and when the heavy metal contaminated soil is repaired, the absorption and accumulation effects of heavy metals cadmium, arsenic and lead in the heavy metal contaminated alkaline soil of rice are reduced, so as to ensure the health of human body.
Experimental example 4:
contaminated soil, which was simultaneously enriched in heavy metals such as cadmium (32.68ppm), arsenic (322.50ppm), lead (558.84ppm), mercury (12.55ppm), copper (598.65ppm), chromium (45.26ppm), nickel (22.69ppm) and manganese (458.33ppm), was collected from a field near a mine in Zhejiang province, and the reduction value was calculated in comparison with control soil which was not treated with a remediation agent, following the remediation method of example 2. The statistics are shown in table 4.
TABLE 4 passivation of heavy Metal contaminated soil with remediation Agents of different examples
As can be seen from table 4, the remediation agent in embodiment 1 of the present application can effectively passivate and remove heavy metal elements such as cadmium, arsenic, lead, mercury, copper, chromium, nickel, manganese, etc. in soil, thereby simply and rapidly remedying heavy metal contaminated soil, improving the existing agricultural soil waste problem caused by multiple heavy metal contamination in China, and further improving the urgent situation that the heavy metal content of crops exceeds the standard.
Experimental example 5:
on the basis of the experimental example 3, the method includes selecting the example 1, the example 6, the example 7 and the example 12, continuously detecting the continuous repairing effect of the corresponding repairing agent on the heavy metal contaminated soil, and respectively detecting the heavy metal content in the soil before the rice is planted in the first season, the second season, the third season and the fourth season (2 seasons per year), wherein the statistical results are respectively shown in fig. 2-4. It can be obviously known that the remediation agent in the preferred embodiment of the application, namely the remediation agent in example 1, can efficiently and continuously passivate heavy metals in soil, can continuously act on four growth agents, and has higher passivation efficiency and longer acting time than common iron-based biochar; it should also be seen that bentonite is soaked with oxalic acid and the silane coupling agent modified Fe3O4The magnetic powder has a greater influence on the action of the repairing agent for continuously passivating the heavy metals.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by examples 1 to 12 and experimental examples 1 to 5.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
Claims (6)
1. A preparation method of a heavy metal contaminated soil remediation agent is characterized by comprising the following steps:
1) preparing magnetic polyvinyl alcohol microspheres: 0.3-0.5 weight part of gelatin is completely dissolved in sufficient distilled water at room temperature; sequentially adding 0.3-0.5 part by weight of benzoyl peroxide, 8-10 parts by weight of liquid wax, 8-10 parts by weight of divinylbenzene and 25-40 parts by weight of polyvinyl alcohol under stirring, and continuously stirring for at least 45 min; heating to 48-50 ℃, preserving the temperature for at least 10min, and adding 0.6-0.8 part by weight of sodium carbonate and 1.5-2.0 parts by weight of magnesium sulfate; heating to 70-78 deg.C, keeping the temperature for at least 15min, adding 2.5-4.0 weight parts of Fe modified by silane coupling agent3O4Magnetic powder is subjected to heat preservation for at least 4 hours; heating to 90-98 ℃, preserving heat for at least 2 hours, washing and filtering when the temperature of the solution is reduced to below 80 ℃, drying in vacuum, crushing and sieving with at least 100-mesh sieve to obtain the product; the saturation magnetization intensity of the magnetic polyvinyl alcohol microspheres is not less than 3.0 A.m2·kg-1，
2) Preparing iron magnesium calamus carbon: pulverizing cleaned and dried rhizoma Acori Calami, and sieving to obtain sawdust with size not greater than 0.5 mm; preparation of a composition containing Fe3+、Fe2+And Mg2+The mixed impregnation stabilizing solution of (1); under nitrogen, wood chips are dipped into the mixed dipping stable solution for at least 2 hours according to the weight ratio of 100: 1.0-3.0 of the wood chips to the metal cations; heating the mixed solution to 550-580 ℃ under nitrogen, and pyrolyzing for at least 1.5 h; washing ash on the obtained biochar for multiple times, drying, crushing and sieving by a 100-mesh sieve to obtain the biological carbon;
3) preparing bentonite/polyvinyl alcohol composite resin: at room temperature, adding sufficient oxalic acid solution into natural bentonite, soaking, reacting for at least 2 hours in a shaking table for 120-150 times/min, adding hemicellulose alkali liquor and sodium bisulfite, and performing ultrasonic dispersion for at least 20 min; rapidly heating to 55-60 ℃, adding a polyvinyl alcohol aqueous solution, stirring and reacting at constant temperature for at least 30min, flocculating and washing a product with ethanol, drying and then fully grinding, extracting with acetone for 12h and drying to obtain the product;
4) fully mixing the materials prepared in the steps 1), 2) and 3) according to the weight ratio of 1.0: 3.0-5.0: 1.5-3.0 to obtain a soil conditioning precursor;
5) uniformly mixing the soil conditioning precursor prepared in the step 4) with diatomite and starch according to the mass ratio of 100: 1-10, spraying water for granulation, and drying to obtain the heavy metal contaminated soil remediation agent.
2. The method of claim 1, wherein: said Fe3O4The magnetic powder modification step is as follows: equal weight of Fe3O4Adding the magnetic powder and the silane coupling agent into 50-75% ethanol solution which is at least 50 times of the weight of the magnetic powder and the silane coupling agent, uniformly dispersing, slowly heating to 42-45 ℃ under the protection of nitrogen, stirring for at least 18 hours at 800-1200 r/min, washing for multiple times by using ethanol and deionized water, and drying in vacuum at 60 ℃ for at least 48 hours.
3. The method according to claim 1 or 2, characterized in that: fe in the step 2)3+、Fe2+And Mg2+The amount ratio of the substances (A) is 2-3: 1: 0.3-1.
4. The heavy metal contaminated soil remediation agent prepared by the method of any one of claims 1 to 3.
5. The use of the heavy metal contaminated soil remediation agent of claim 4 for remediating heavy metal contaminated soil.
6. A method for remediating heavy metal contaminated soil, comprising:
applying the heavy metal contaminated soil remediation agent of claim 4 to the surface of the heavy metal contaminated soil with a thickness of 0.2-1 cm, uniformly mixing a soil layer at least 15cm deep from the surface layer of the soil in a turning mode, slightly spraying water, and then maintaining for 3-5 months to complete remediation of the heavy metal contaminated soil.
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