CN114988826A - Heavy metal combined contaminated soil solidification stabilization repair material and preparation method and use method thereof - Google Patents
Heavy metal combined contaminated soil solidification stabilization repair material and preparation method and use method thereof Download PDFInfo
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- CN114988826A CN114988826A CN202210683369.1A CN202210683369A CN114988826A CN 114988826 A CN114988826 A CN 114988826A CN 202210683369 A CN202210683369 A CN 202210683369A CN 114988826 A CN114988826 A CN 114988826A
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- Prior art keywords
- cement
- parts
- repair material
- fly ash
- carbide slag
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 43
- 239000002689 soil Substances 0.000 title claims abstract description 43
- 230000008439 repair process Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000006641 stabilisation Effects 0.000 title claims abstract description 16
- 238000011105 stabilization Methods 0.000 title claims abstract description 16
- 238000007711 solidification Methods 0.000 title claims abstract description 13
- 230000008023 solidification Effects 0.000 title claims abstract description 13
- 239000004568 cement Substances 0.000 claims abstract description 94
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 239000010881 fly ash Substances 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 31
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 28
- 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 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000019738 Limestone Nutrition 0.000 claims description 12
- 239000006028 limestone Substances 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000005696 Diammonium phosphate Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound 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 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 238000011418 maintenance treatment Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 229910052785 arsenic Inorganic materials 0.000 description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 11
- 230000000087 stabilizing effect Effects 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 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 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/10—Cements, e.g. Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a heavy metal combined pollution soil solidification stabilization repair material and a preparation method and a use method thereof, wherein the repair material comprises the following components: cement-based curing agent, iron-based material, hydroxyapatite, active carbon and adsorption auxiliary agent; the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement; the mass ratio of the fly ash fired cement to the carbide slag fired cement is (1-5): 1. The repairing material utilizes the synergistic effect among the components, simultaneously solidifies and stabilizes the heavy metal in the polluted soil, and can reduce the leaching concentration of the heavy metal, thereby further reducing the mobility of the heavy metal, having repairing effect on various heavy metals, being not influenced by soil matrix and pH value, and having long-term stable repairing effect and no secondary pollution.
Description
Technical Field
The invention belongs to the field of contaminated soil solidification/stabilization repair, and particularly relates to a heavy metal composite contaminated soil solidification stabilization repair material, and a preparation method and a use method thereof.
Background
The soil heavy metal pollution is that the content of trace metal elements in soil exceeds a background value due to human activities, industrial production and the like, soil heavy metal pollutants mainly comprise chromium, arsenic, mercury, cadmium, lead, antimony, iron, manganese, zinc and the like, heavy metals in soil cannot be decomposed by soil microorganisms, are easy to accumulate and are converted into methyl compounds with higher toxicity, and even are accumulated in a human body at harmful concentration through a food chain, so that the human health is seriously harmed, and the quality of the ecological environment is deteriorated. Therefore, the method has important significance for properly treating the heavy metal contaminated soil in the aspects of ecological environment, human health and the like.
At present, the method for treating the heavy metal contaminated soil mainly comprises excavation, stabilization/solidification, chemical leaching, heat treatment, bioremediation and the like. Among them, the stabilization/solidification treatment is a method which converts pollutants into a state or form in which the pollutants are not easily dissolved, have a small migration ability or toxicity, and realize the harmlessness or reduce the risk of harmfulness to an ecosystem, and is the most widely used method. CN111303888A discloses a heavy metal combined pollution soil stabilization restoration agent with low environmental risk, a preparation method and an application thereof, wherein the restoration agent comprises the following components by weight: the repairing agent is prepared by mixing 37-60% of natural clay mineral, 37-60% of modified clay mineral and 3-26% of phosphorus-based fertilizer, grinding and sieving the raw materials. The repairing agent is safe and reliable, is convenient to use, and has a stabilizing repairing effect on various heavy metals. However, the modified clay mineral is sodium bentonite, so that the storage capacity is small and the cost is high; CN104004520B discloses a stabilizer for arsenic contaminated site soil remediation, which takes the quality of arsenic contaminated soil as a benchmark, and comprises: 1 to 5 percent of bentonite, 0.1 to 1 percent of calcium sulfate, iron powder and 2 to 8 percent of plant ash, and the stabilizer is obtained after mixing the raw materials, dry mixing and adding water for mixing. The stabilizer is simple to prepare and good in stabilizing effect, but plant ash can be obtained only by burning plants, the obtaining is not easy and high in cost, and secondary pollution is easily caused by burning.
At present, the heavy metal pollution of soil is diversified, multiple heavy metal combined pollution often exists, and most of soil stabilizing/curing agents are narrow in application range, so that the polluted soil repairing material which is cheap and easy to obtain, convenient to use, environment-friendly, efficient and capable of having a repairing effect on multiple heavy metals is provided, and the technical problem to be solved urgently by technical personnel in the field is still solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a heavy metal composite polluted soil solidification and stabilization repairing material, a preparation method and a use method thereof.
In order to achieve the technical effect, the invention adopts the following technical scheme:
in a first aspect, the invention provides a heavy metal combined pollution soil solidification and stabilization repair material, which comprises the following components: cement-based curing agent, iron-based material, hydroxyapatite, active carbon and adsorption auxiliary agent;
the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement;
the mass ratio of the fly ash burnt cement to the carbide slag burnt cement is (1-5): 1, and may be, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
According to the invention, the repairing material utilizes the synergistic effect among the components, simultaneously solidifies and stabilizes the heavy metal in the polluted soil, and efficiently reduces the leaching concentration of the heavy metal, thereby further reducing the mobility of the heavy metal and avoiding the phenomena of toxicity rebound and the like. The cement-based curing agent adopts high-calcium fly ash and carbide slag as raw materials, so that the resource utilization of solid wastes is realized; the high-calcium fly ash contains metal oxides such as aluminum oxide, magnesium oxide and the like, and is a good heavy metal ion fixing agent. In the hydration reaction process of the cement-based curing agent, heavy metals can react with the cement-based curing agent in various ways such as adsorption, chemical absorption, sedimentation, ion exchange and the like, and finally stay on the surface of a hydrated silicate colloid formed by the cement-based curing agent in a hydroxide or complex way, and meanwhile, the use of the cement-based curing agent also provides an alkaline environment for polluted soil, so that the migration of the heavy metals is reduced.
As a preferable technical scheme of the invention, the repair material comprises the following components in parts by weight:
the cement-based curing agent may be present in an amount of 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or 11 parts by weight, the iron-based material may be present in an amount of 32 parts, 36 parts, 40 parts, 44 parts, 48 parts, 52 parts, or 54 parts by weight, the hydroxyapatite may be present in an amount of 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts by weight, the activated carbon may be present in an amount of 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, or 25 parts by weight, the adsorption aid may be present in an amount of 2 parts, 4 parts, 6 parts, 8 parts, or 10 parts by weight, but the present invention is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the repair material comprises the following components in parts by weight:
the cement-based curing agent may be present in an amount of 7 parts, 8 parts, 9 parts, 10 parts, or 11 parts by weight, the iron-based material may be present in an amount of 40 parts, 42 parts, 44 parts, 46 parts, or 48 parts by weight, the hydroxyapatite may be present in an amount of 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, or 36 parts by weight, the activated carbon may be present in an amount of 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, or 18 parts by weight, the adsorption aid may be present in an amount of 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or 9 parts by weight, and the like, but the present invention is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
In the present invention, the mass ratio of the cement-based curing agent, the iron-based material, the hydroxyapatite, the activated carbon and the adsorption aid is (8-9): 41-43): 28-32): 14-16): 4-8, and for example, 8:41:32:14:8, 8.5:42:30:15:6 or 9:43:28:16:4, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
In a preferred embodiment of the present invention, the particle size of the fly ash calcined cement is 200 to 250 mesh, and may be, for example, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, or 250 mesh, but is not limited to the above-mentioned values, and other values not listed in the numerical range are also applicable.
Preferably, the particle size of the carbide slag-fired cement is 200 to 250 meshes, for example, 200 meshes, 210 meshes, 220 meshes, 230 meshes, 240 meshes, 250 meshes, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the raw material of the fly ash burnt cement comprises 50-75% of fly ash, 10-15% of clay and 10-40% of limestone by mass, the mass percentage of the fly ash can be 50%, 55%, 60%, 65%, 70% or 75%, the mass percentage of the clay can be 10%, 11%, 12%, 13%, 14% or 15%, the mass percentage of the limestone can be 10%, 15%, 20%, 25%, 30%, 35% or 40%, but the invention is not limited to the recited values, and other values in the range of the values are also applicable.
Preferably, the raw material of the carbide slag-fired cement includes, by mass, 55 to 76% of carbide slag, 0.6 to 1.6% of iron ore, and 23.4 to 44.4% of limestone, the carbide slag may be 55%, 57%, 59%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, or 76%, the iron ore may be 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, or 1.6%, and the limestone may be 23.4%, 25.4%, 30.4%, 35.4%, 40.4%, or 44.4%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned ranges are also applicable.
In the present invention, the raw material of the carbide slag contains 1.2 to 2.4% by mass of sulfur, 0.6 to 1.1% by mass of phosphorus, and 1.27 to 1.36% by mass of magnesium oxide, the sulfur may be 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, or 2.4% by mass, the phosphorus may be 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, or 1.1% by mass, and the magnesium oxide may be 1.27%, 1.28%, 1.29%, 1.30%, 1.31%, 1.32%, 1.33%, 1.34%, 1.35%, or 1.36% by mass, but the present invention is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the preparation method of the cement-based curing agent comprises the following steps: and grinding and mixing the fly ash fired cement and the carbide slag fired cement, and performing heat treatment to obtain the cement-based curing agent.
Preferably, the heat treatment temperature is 400 to 600 ℃, for example, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃, but not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the heat treatment time is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred embodiment of the present invention, the iron-based material includes any one or at least two combinations of iron powder, ferrous chloride, ferrous sulfate or polymeric ferric sulfate, and the combinations are exemplified by, but not limited to: a combination of iron powder and ferrous chloride, a combination of ferrous sulfate and ferric chloride, or a combination of ferrous sulfate and polymeric ferric sulfate, and the like.
Preferably, the particle size of the iron powder is 20 to 50 μm, and may be, for example, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the invention, the iron-based material does not contain arsenic, antimony, cadmium and zinc elements.
In the present invention, the purity of the ferrous chloride is 80 to 85%, and may be, for example, 80%, 81%, 82%, 83%, 84%, 85%, or the like, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the present invention, the purity of the ferrous sulfate is 75 to 86%, and may be, for example, 75%, 77%, 79%, 80%, 82%, 84%, or 86%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the present invention, the polymeric ferric sulfate is prepared by direct oxidation, and has a purity of more than 85%, for example, 86%, 88%, 90%, 92%, 94%, 96%, or 98%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the iron-based material mainly replaces hydroxyl on the surface of an oxide by arsenic, cadmium and other ions adsorbed by iron oxide, and simultaneously generates amorphous or indissolvable secondary oxidation state minerals; meanwhile, the ferric hydroxide colloid generated by hydrolysis of the iron ions can adsorb heavy metal ions in the polluted soil, so that the aim of coprecipitation is fulfilled, and the mobility of the heavy metal ions is reduced.
As a preferable technical scheme of the invention, the preparation method of the hydroxyapatite comprises the following steps: mixing calcium nitrate and diammonium phosphate, heating, aging, adjusting pH, and roasting to obtain the hydroxyapatite.
Preferably, the molar ratio of calcium nitrate to diammonium phosphate is (1.67-2.00):1, and may be, for example, 1.67:1, 1.70:1, 1.75:1, 1.80:1, 1.85:1, 1.90:1, 1.95:1, or 2.00:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the heating temperature is 30 to 85 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃ and the like, but the heating temperature is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the heating time is 0.5 to 5 hours, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the aging temperature is 20 to 80 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pH is adjusted to 5 to 11, for example, 5, 6, 7, 8, 9, 10 or 11, but not limited to the values listed, and other values not listed within the range of values are also applicable.
Preferably, the baking temperature is 500 to 1000 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, but not limited to the cited values, and other values not listed in the numerical range are also applicable.
Preferably, the time for the calcination is 0.5 to 2.5 hours, for example, 0.5 hour, 1.0 hour, 1.5 hour, 2.0 hour, 2.5 hour, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the hydroxyapatite mainly has the functions of adsorption and heavy metal reaction to form precipitate.
In a preferred embodiment of the present invention, the particle size of the activated carbon is 180-200 mesh, such as 180 mesh, 185 mesh, 190 mesh, 195 mesh or 200 mesh, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the invention, the activated carbon is formed by sintering a shell and/or a coconut shell.
Preferably, the sorption adjuvant comprises any one or a combination of at least two of zeolite powder, montmorillonite powder or shell powder, typical but non-limiting examples being: the zeolite powder and the shell powder are preferably selected from the group consisting of a combination of zeolite powder and montmorillonite, a combination of montmorillonite and shell powder, a combination of zeolite powder and shell powder, and the like.
In a second aspect, the present invention provides a method for preparing the repair material of the first aspect, the method comprising the steps of:
mixing a cement-based curing agent, an iron-based material and hydroxyapatite to obtain a component A;
mixing activated carbon and an adsorption auxiliary agent to obtain a component B;
and mixing and stirring the component A and the component B to obtain the repairing material.
In the invention, the component A is a main curing and stabilizing component, and the component B is an auxiliary adsorbing, curing and stabilizing component.
In a preferred embodiment of the present invention, the particle size of the component a is 180 to 200 mesh, for example, 180 mesh, 185 mesh, 190 mesh, 195 mesh or 200 mesh, but the particle size is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the particle size of the component B is 150 to 200 meshes, such as 150 meshes, 160 meshes, 170 meshes, 180 meshes, 190 meshes or 200 meshes, but the particle size is not limited to the enumerated value, and other unrecited values in the numerical range are also applicable.
Preferably, the stirring time is 15-25 min, for example, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min or 25min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the rotation speed of the stirring is 100-200 r/min, such as 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200r/min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a third aspect, the present invention also provides a use method of the repair material prepared by the preparation method of the second aspect, the use method including: and mixing the repairing material, the polluted soil and water, and then carrying out maintenance treatment.
In the present invention, the contaminated soil has various heavy metals such as arsenic, antimony, cadmium, zinc, and the like.
As a preferable technical scheme of the invention, the mass ratio of the repairing material to the polluted soil to water is (0.03-0.05): 1: (0.15 to 0.25), for example, it may be 0.03:1:0.15, 0.035:1:0.17, 0.04:1:0.20, 0.045:1:0.23 or 0.05:1:0.25, but is not limited to the above-mentioned values, and other values not mentioned in the numerical range are also applicable, and (0.03 to 0.05): 1: (0.15-0.20).
Preferably, the curing treatment temperature is 0 to 35 ℃, for example, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The curing treatment is preferably carried out for a period of 6 days or more, for example, for 6 days, 8 days, 10 days, 12 days, 14 days, 16 days, 18 days, or 20 days, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and preferably for 6 to 15 days.
The water content of the curing treatment is preferably 0.15 to 0.20 wt%, and may be, for example, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, or 0.20 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
the repairing material provided by the invention utilizes the synergistic effect among the components, simultaneously solidifies and stabilizes the heavy metals in the polluted soil, can reduce the leaching concentration of the heavy metals, further reduces the mobility of the heavy metals, has repairing effect on various heavy metals, is not influenced by soil matrix and pH value, has long-term stable repairing effect and no secondary pollution, and can respectively reduce the leaching concentrations of arsenic, antimony, cadmium and zinc to be below 0.1mg/L, 0.01mg/L and 2.0 mg/L; the repair material has the advantages of low price, easy obtaining, moderate dosage, convenient use, environmental protection, high efficiency and the like.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a heavy metal combined pollution soil solidification stabilization repair material and a preparation method and a using method thereof, wherein the repair material comprises 8 parts of a cement-based curing agent, 42 parts of an iron-based material, 32 parts of hydroxyapatite, 18 parts of activated carbon and 4 parts of an adsorption auxiliary agent, the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement, and the mass ratio of the fly ash fired cement to the carbide slag fired cement is 3: 1;
the preparation method of the cement-based curing agent comprises the following steps: mixing fly ash fired cement with the particle size of 230 meshes and carbide slag fired cement with the particle size of 230 meshes, and carrying out heat treatment at 500 ℃ for 1h, wherein the fly ash fired cement comprises 65% of fly ash, 13% of clay and 22% of limestone in percentage by mass, and the carbide slag fired cement comprises 65% of carbide slag, 1.0% of iron ore and 34% of limestone in percentage by mass;
the iron-based material is 25 mu m iron powder;
the preparation method of the hydroxyapatite comprises the following steps: calcium nitrate and diammonium phosphate are mixed according to the molar ratio of 1.80:1, the obtained mixture is heated at 60 ℃ for 3 hours, after aging at 50 ℃, the pH is adjusted to 8, and then the mixture is roasted at 750 ℃ for 1.5 hours;
the particle size of the activated carbon is 190 meshes;
the adsorption auxiliary agent is zeolite powder and shell powder in a mass ratio of 1: 2;
the preparation method comprises the following steps: mixing a cement-based curing agent, an iron-based material and hydroxyapatite to obtain a component A, mixing activated carbon and an adsorption auxiliary agent to obtain a component B, mixing the component A and the component B, and stirring at a rotating speed of 150r/min for 20min to obtain the repairing material, wherein the particle size of the component A is 190 meshes, and the particle size of the component B is 190 meshes;
the application method comprises the following steps: the repairing material, the polluted soil and water in a mass ratio of 0.04:1:0.17 are mixed, and curing treatment is carried out for 10 days at 15 ℃, wherein the water content of the curing treatment is 0.17 wt%.
Example 2
The embodiment provides a heavy metal combined pollution soil solidification stabilization repair material and a preparation method and a using method thereof, wherein the repair material comprises 6 parts of a cement-based curing agent, 32 parts of an iron-based material, 45 parts of hydroxyapatite, 10 parts of activated carbon and 6 parts of an adsorption auxiliary agent, the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement, and the mass ratio of the fly ash fired cement to the carbide slag fired cement is 1: 1;
the preparation method of the cement-based curing agent comprises the following steps: mixing fly ash fired cement with the particle size of 200 meshes and carbide slag fired cement with the particle size of 200 meshes, and carrying out heat treatment at 400 ℃ for 2h, wherein the fly ash fired cement comprises 50% of fly ash, 15% of clay and 35% of limestone in percentage by mass, and the carbide slag fired cement comprises 55% of carbide slag, 0.6% of iron ore and 44.4% of limestone in percentage by mass;
the iron-based material is ferrous chloride with the purity of 85 percent;
the preparation method of the hydroxyapatite comprises the following steps: calcium nitrate and diammonium phosphate are mixed according to the molar ratio of 1.67:1, the obtained mixture is heated at 30 ℃ for 5 hours, after aging at 20 ℃, the pH is adjusted to 5, and then the mixture is roasted at 500 ℃ for 2.5 hours;
the particle size of the active carbon is 180 meshes;
the adsorption adjuvant is montmorillonite;
the preparation method comprises the following steps: mixing a cement-based curing agent, an iron-based material and hydroxyapatite to obtain a component A, mixing activated carbon and an adsorption auxiliary agent to obtain a component B, mixing the component A and the component B, and stirring at the rotating speed of 100r/min for 25min to obtain the repairing material, wherein the particle size of the component A is 180 meshes, and the particle size of the component B is 180 meshes;
the application method comprises the following steps: the repairing material, the polluted soil and water in a mass ratio of 0.03:1:0.15 are mixed, and curing treatment is carried out for 15 days at the temperature of 5 ℃, wherein the water content of the curing treatment is 0.15 wt%.
Example 3
The embodiment provides a heavy metal combined pollution soil solidification stabilization repair material and a preparation method and a using method thereof, wherein the repair material comprises 11 parts of a cement-based curing agent, 54 parts of an iron-based material, 20 parts of hydroxyapatite, 25 parts of activated carbon and 8 parts of an adsorption auxiliary agent, the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement, and the mass ratio of the fly ash fired cement to the carbide slag fired cement is 5: 1;
the preparation method of the cement-based curing agent comprises the following steps: mixing fly ash fired cement with the particle size of 250 meshes and carbide slag fired cement with the particle size of 250 meshes, and carrying out heat treatment at 600 ℃ for 1.5h, wherein the fly ash fired cement comprises 75% of fly ash, 10% of clay and 15% of limestone by mass percentage, and the carbide slag fired cement comprises 74% of carbide slag, 1.6% of iron ore and 24.4% of limestone by mass percentage;
the iron-based material is ferrous sulfate with the purity of 80%;
the preparation method of the hydroxyapatite comprises the following steps: mixing calcium nitrate and diammonium phosphate according to a molar ratio of 2.00:1, heating the obtained mixture at 85 ℃ for 0.5h, aging at 80 ℃, adjusting the pH to 11, and roasting at 1000 ℃ for 0.5 h;
the particle size of the active carbon is 200 meshes;
the adsorption auxiliary agent is shell powder;
the preparation method comprises the following steps: mixing a cement-based curing agent, an iron-based material and hydroxyapatite to obtain a component A, mixing activated carbon and an adsorption auxiliary agent to obtain a component B, mixing the component A and the component B, and stirring at a rotating speed of 200r/min for 15min to obtain the repairing material, wherein the particle size of the component A is 200 meshes, and the particle size of the component B is 200 meshes;
the application method comprises the following steps: the repairing material, the polluted soil and water in a mass ratio of 0.05:1:0.25 are mixed, and curing treatment is carried out for 6 days at 35 ℃, wherein the water content of the curing treatment is 0.20 wt%.
Example 4
This example is different from example 1 only in that the conditions are the same as example 1 except that the cement-based curing agent is 3 parts by weight.
Example 5
This example is different from example 1 only in that the conditions are the same as example 1 except that the cement-based curing agent is 14 parts by weight.
Example 6
This example is different from example 1 only in that the conditions are the same as example 1 except that the weight part of the iron-based material is 30 parts.
Example 7
This example differs from example 1 only in that the conditions are the same as example 1 except that the weight part of the iron-based material is 56 parts.
Example 8
This example is different from example 1 only in that the conditions are the same as example 1 except that the weight part of the hydroxyapatite is 15 parts.
Example 9
This example is different from example 1 only in that the conditions are the same as example 1 except that the weight part of the hydroxyapatite is 50 parts.
Example 10
The present example is different from example 1 only in that the conditions are the same as example 1 except that the weight part of the activated carbon is 8 parts.
Example 11
This example is different from example 1 only in that the conditions are the same as example 1 except that the weight part of the activated carbon is 30 parts.
Comparative example 1
This comparative example is different from example 1 only in that the conditions are the same as example 1 except that the mass ratio of the fly ash burnt cement to the carbide slag burnt cement is 0.5: 1.
Comparative example 2
The comparative example differs from example 1 only in that the conditions are the same as example 1 except that the mass ratio of the fly ash-fired cement to the carbide slag-fired cement is 6: 1.
Comparative example 3
This comparative example differs from example 1 only in that the conditions are the same as example 1 except that the repair material does not contain a cement-based curing agent.
Comparative example 4
This comparative example differs from example 1 only in that the conditions are the same as example 1 except that the repair material does not contain an iron-based material.
Comparative example 5
This comparative example differs from example 1 only in that the conditions are the same as example 1 except that the repair material does not contain hydroxyapatite.
Comparative example 6
This comparative example differs from example 1 only in that the conditions are the same as example 1 except that the repair material does not contain activated carbon.
Comparative example 7
This comparative example differs from example 1 only in that the conditions are the same as example 1 except that the repair material does not contain an adsorption aid.
The performance test methods and results of the above examples and comparative examples are as follows:
and (3) performance testing: the test was carried out according to the solid waste leaching toxicity leaching method horizontal oscillation method (HJ 557-. Wherein the toxic leaching concentrations of arsenic, antimony, cadmium and zinc are respectively A1, B1, C1 and D1 (mg/L); the concentrations of arsenic, antimony, cadmium and zinc in the solid-stabilized toxic leaching solution are respectively A2, B2, C2 and D2 (mg/L).
TABLE 1
From table 1, the following points can be derived:
(1) the repairing material prepared in the embodiment 1-3 has good repairing effect on the polluted soil, and the curing and stabilizing toxic leaching concentrations of arsenic, antimony, cadmium and zinc are respectively reduced to be below 0.1mg/L, 0.01mg/L and 2.0 mg/L;
(2) in example 4, the addition amount of the cement-based curing agent is too low, so that the curing effect is obviously weakened; in example 5, the alkalinity of the stabilizing system is too high due to too high addition amount of the cement-based curing agent, and further the leaching concentration of part of heavy metal elements is increased;
(3) in example 6, the addition amount of the iron-based material is too low, so that the iron-based stabilization capability is insufficient and the alkalinity of the stabilization system is too high; in example 7, the addition amount of the iron-based material is too high, which causes the acidity of the system to be too high, and further causes the leaching concentration of part of heavy metal elements to be increased;
(4) in example 8, the addition amount of hydroxyapatite was too low, resulting in insufficient phosphorus-based stabilizing active material; in example 9, the addition amount of the hydroxyapatite is too high, so that a large amount of arsenic and antimony elements are dissolved out;
(5) in the embodiment 10, the addition amount of the activated carbon is too low, so that the overall adsorption capacity of the material is greatly reduced; in example 11, the addition amount of the activated carbon is too high, so that the activated carbon is adsorbed by other active substances in soil, and the leaching concentration of heavy metal elements is further increased;
(6) as can be seen from the comparison between example 1 and comparative examples 1-2, when the mass ratio of the fly ash-fired cement to the carbide slag-fired cement is too low or too high, the activity imbalance synergistically promoted by the fly ash-fired cement and the carbide slag-fired cement is caused, and further the leaching concentration of part of heavy metal elements is increased;
(7) as can be seen from comparison between example 1 and comparative examples 3 to 7, since comparative example 3 does not contain a cement-based curing agent, comparative example 4 does not contain an iron-based material, comparative example 5 does not contain hydroxyapatite, comparative example 6 does not contain activated carbon, and comparative example 7 does not contain an adsorption adjuvant, the curing and stabilizing effect on the contaminated soil is reduced, so that the leaching concentration of part of heavy metals is increased, which indicates that there is a synergistic effect between the components, and the curing and stabilizing effect on the contaminated soil is deteriorated due to the absence of any one of the repairing components.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The heavy metal combined contaminated soil solidification and stabilization repair material is characterized by comprising the following components: cement-based curing agent, iron-based material, hydroxyapatite, active carbon and adsorption auxiliary agent;
the cement-based curing agent comprises a mixture of fly ash fired cement and carbide slag fired cement;
the mass ratio of the fly ash fired cement to the carbide slag fired cement is (1-5): 1.
2. The repair material of claim 1, comprising the following components in parts by weight:
preferably, the repair material comprises the following components in parts by weight:
3. the repair material according to claim 1 or 2, wherein the particle size of the fly ash fired cement is 200 to 250 mesh;
preferably, the particle size of the carbide slag fired cement is 200-250 meshes;
preferably, the raw materials of the fly ash fired cement comprise, by mass, 50-75% of fly ash, 10-15% of clay and 10-40% of limestone;
preferably, the raw materials of the cement fired by the carbide slag comprise, by mass, 55-76% of the carbide slag, 0.6-1.6% of iron ore and 23.4-44.4% of limestone;
preferably, the preparation method of the cement-based curing agent comprises the following steps: mixing fly ash fired cement and carbide slag fired cement, and performing heat treatment to obtain the cement-based curing agent;
preferably, the temperature of the heat treatment is 400-600 ℃;
preferably, the time of the heat treatment is 1-2 h.
4. The repair material of any one of claims 1 to 3, wherein the ferrous based material comprises any one or a combination of at least two of iron powder, ferrous chloride, ferrous sulfate, or polymeric ferric sulfate;
preferably, the particle size of the iron powder is 20-50 μm.
5. The repair material according to any one of claims 1 to 4, wherein the hydroxyapatite is prepared by a method comprising: mixing calcium nitrate and diammonium phosphate, heating, aging, adjusting pH, and roasting to obtain hydroxyapatite;
preferably, the molar ratio of calcium nitrate to diammonium phosphate is (1.67-2.00) to 1;
preferably, the heating temperature is 30-85 ℃;
preferably, the heating time is 0.5-5 h;
preferably, the aging temperature is 20-80 ℃;
preferably, the pH is adjusted to 5-11;
preferably, the roasting temperature is 500-1000 ℃;
preferably, the roasting time is 0.5-2.5 h.
6. The repair material according to any one of claims 1 to 5, wherein the activated carbon has a particle size of 180 to 200 mesh;
preferably, the adsorption adjuvant comprises any one or combination of at least two of zeolite powder, montmorillonite or shell powder, preferably zeolite powder and shell powder.
7. A method for the preparation of a repair material according to any one of claims 1 to 6, characterized in that it comprises the following steps:
mixing a cement-based curing agent, an iron-based material and hydroxyapatite to obtain a component A;
mixing activated carbon and an adsorption auxiliary agent to obtain a component B;
and mixing and stirring the component A and the component B to obtain the repairing material.
8. The preparation method according to claim 7, wherein the particle size of the A component is 180 to 200 mesh;
preferably, the particle size of the component B is 150-200 meshes;
preferably, the stirring time is 15-25 min;
preferably, the rotating speed of the stirring is 100-200 r/min.
9. A method for using the repair material produced by the production method according to claim 7 or 8, characterized by comprising: and mixing the repairing material, the polluted soil and water, and then carrying out maintenance treatment.
10. The use method according to claim 9, wherein the mass ratio of the repairing material, the contaminated soil and the water is (0.03-0.05): 1: (0.15-0.25), preferably (0.03-0.05): 1: (0.15 to 0.20);
preferably, the temperature of the maintenance treatment is 0-35 ℃;
preferably, the curing treatment time is more than or equal to 6 days, and preferably 6-15 days;
preferably, the water content of the curing treatment is 0.15-0.20 wt%.
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Application publication date: 20220902 |