CN105542775A - Passivating agent for weakly acidic cadmium contaminated soil and application thereof - Google Patents
Passivating agent for weakly acidic cadmium contaminated soil and application thereof Download PDFInfo
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- CN105542775A CN105542775A CN201510949602.6A CN201510949602A CN105542775A CN 105542775 A CN105542775 A CN 105542775A CN 201510949602 A CN201510949602 A CN 201510949602A CN 105542775 A CN105542775 A CN 105542775A
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- soil
- passivator
- slightly acidic
- passivating agent
- cadmium
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- 239000002689 soil Substances 0.000 title claims abstract description 116
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 71
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 title abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000003337 fertilizer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 230000008901 benefit Effects 0.000 claims abstract description 5
- 238000003971 tillage Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000010881 fly ash Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011365 complex material Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000010902 straw Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 210000003608 fece Anatomy 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 3
- 235000015097 nutrients Nutrition 0.000 abstract description 2
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 abstract 1
- 235000021393 food security Nutrition 0.000 abstract 1
- 235000016709 nutrition Nutrition 0.000 abstract 1
- 230000035764 nutrition Effects 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 description 33
- 238000002161 passivation Methods 0.000 description 20
- 239000003610 charcoal Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 9
- 241000209140 Triticum Species 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 235000021307 Triticum Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000009418 renovation Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006388 chemical passivation reaction Methods 0.000 description 2
- 231100000749 chronicity Toxicity 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003895 organic fertilizer Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000195940 Bryophyta Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a passivating agent for weakly acidic cadmium contaminated soil and application thereof. The passivating agent is compounded and mixed from modified biological carbon, and mineral materials including calcium oxide, a calcium magnesium phosphate fertilizer and a silicon fertilizer beneficial to the soil. The passivating agent is applied to the surface of the weakly acidic cadmium contaminated farmland soil, and the application amount of passivating agent is controlled at more than 1.5 wt% of the soil; and then soil and passivating agent rotary tillage is carried out on a plough layer 20cm above the land surface, and the maximum field water holding capacity is maintained at more than 70% stably for more than ten days to complete the in situ remediation of the weakly acidic cadmium contaminated soil. The passivating agent can effectively reduce the content of available cadmium in soil, restore agricultural function of the polluted land, and ensure food security; the passivating agent contains a lot of organic matters and other nutrients, can provide abundant nutrition for the growth of crops, and has the advantages of environment-friendliness, high repair rate, long-term stability, and high application value.
Description
Technical field
The present invention relates to heavy metal pollution of soil and administer field, particularly a kind of passivator for slightly acidic cadmium pollution soil and application thereof.
Background technology
Soil is the valuable source of mankind's physical environment of depending on for existence and agriculture production, but environmental pollution and ecological damage increasingly serious, badly influence health and the existence of the mankind, wherein heavy metal element to the pollution of environment and destruction particularly serious, heavy metal in soil can produce toxic action to crop, not only affect the safety of agricultural-food, but also serious threat can be produced by food chain to human and animal's health, the area having become current facing mankind is the widest, endanger one of environmental problem maximum and urgently to be resolved hurrily.
For the soil of big area heavy metal contamination, especially mild or moderate contaminated soil, in-situ chemical passivation recovery technique have implement simple, with low cost and administer fireballing advantage.Passivator conventional at present comprises lime, zeolite, hydroxyapatite, siliceous fertilizer, blast furnace quarrel, flyash, clay, Fe/Mn oxide compound, phosphoric acid salt, sulfide, artificial preparation biological carbon and organic compost or soil ulmin etc.The passivation effect that these passivator are had nothing in common with each other because of soil type and pollutant kind, general all have larger specific surface area and flourishing microvoid structure, can active adsorption, heavy metal-passivated ion, or raising soil pH, increase the stability of heavy metal ion, reduce its activity, thus minimizing heavy metal-polluted soil moves in plant materials.
The fixing-stable recovery technique of current heavy metal cadmium soil, has had a large amount of results of study, but almost not for the passivating method that slightly acidic heavy metal cadmium soil is permanently effective.Meng Lingyang is by greenhouse pot culture test and soil incubation test, the peat composed of rotten mosses is added in research heavy metal cadmium soil (pH=5.5), gac and weathered coal 3 kinds of materials are on the impact of soil heavy metal cadmium occurrence patterns and biological effectiveness, inquire into its feasibility as heavy metal cadmium soil-repairing agent, this result of study shows that 3 kinds of organic carbon materials all reduce soil pH value, after heavy metal cadmium soil adds different inert organic carbon renovation agent, in soil, the change of bound residue cadmium content is not obvious, three kinds of renovation agents add on the contrary makes cadmium content in object (" different inert organic carbon material is on the impact of Cadmium in Soil occurrence patterns and biological effectiveness ", Meng Lingyang etc., agro-environment science journal, 2011), Dai Yunchao passes through the earth culture experimental study difference of the different modifying agent of interpolation to China's Cadmium Pollution in Soils improved effect of different nature, result shows the organic passivation that can realize heavy metal-polluted soil such as chicken manure, lime can realize the improvement to acid soil by the pH increasing soil, but also only have about 55.5% (" lime and the organic impact on cadmium validity in different properties cadmium pollution soil ", in generation, permits superfine, agro-environment science journal, 2014), some researchs in recent years show, use feces of livestock and poultry, agricultural crop straw can the absorption of soil heavy metal as fertilizer, reduce the content of soil available heavy metal, but because organism is unstable, easily be degraded by microorganisms, the heavy metal after absorption is easily again discharged in environment and goes the passivation effect of therefore heavy metal unsatisfactory.
The core of in-situ chemical passivation reparation is the selection of passivator, select suitable passivator particularly important for soil type and pollutant kind, current existing a large amount of passivator can realize the fixing-stable reparation of heavy metal cadmium pollution soil, but the long-term effectiveness of passivator is difficult to ensure.Very large ratio is occupied in the acid farmland of this external China heavy metal contamination, but but never has the passivation that a kind of permanently effective passivator can realize heavy metal.Therefore a kind of passivator permanently effective reduction heavy metal in soil cadmium bio-available Zn concentration for heavy metal contamination slightly acidic soil (pH=4-6) of exploitation just seem be urgent.
Summary of the invention
For the problems referred to above, the invention provides a kind of eco-friendly, by modification biological carbon and be rich in the elements such as calcium, magnesium, silicon complex material as passivator, the fixing-stable method of the slightly acidic heavy metal in soil that heavy metal (Cd) is polluted, realize the heavy metal cadmium in permanently effective passivation soil, this passivator has that repair rate is high, permanent stability good, the simple advantage of application process, and the present invention is achieved in that
For a passivator for slightly acidic cadmium pollution soil, this passivator obtains like this:
A) mixing solutions biological carbon being placed in sodium sulphite and sulfuric acid soaks 3-5h; In described mixing solutions, sodium sulphite concentration is 1mol/L, and the massfraction of sulfuric acid is 10%;
B) 400 ~ 800W, supersound washing 20-30min, then in 600 ~ 1000W microwave chemical reactor reaction 10-20min;
C) suction filtration reactant, with deionized water, biological carbon washing is extremely neutral, 70 DEG C of oven dry, obtain modification biological carbon;
D) calcium oxide, magnesium oxide, silicon oxide are mixed with flyash, obtain complex material, be calculated in mass percent, in complex material, calcium oxide accounts for 30-40%, and magnesium oxide accounts for 5-10%, and silicon oxide accounts for 15-25%, and surplus is flyash;
By step C) the modification biological carbon that obtains and complex material in mass ratio 1:1-3 mix, namely obtain described passivator.
Further, the present invention is used for the passivator preparation process A of slightly acidic cadmium pollution soil) in, the mass ratio of biological carbon and mixing solutions is 1:3-5.
Further, the present invention is used for the passivator preparation process A of slightly acidic cadmium pollution soil) in, described biological carbon, refers to that by agricultural crop straw, wood chip or animal dung be raw material, prepares in the anaerobic environment of 300-500 DEG C.
The application in slightly acidic cadmium pollution soil repaired in position by passivator as described herein.
Further, to repair the concrete steps applied in slightly acidic cadmium pollution soil in position as follows for passivator of the present invention: evenly spread fertilizer over the fields by passivator in slightly acidic cadmium pollution soil, then by soil rotary tillage 20cm; Water to irrigate and be not less than 70% of maxmun field capacity to soil water content, keep 10d, namely complete the in-situ immobilization to this slightly acidic cadmium pollution soil.
Further, in application of the present invention, the amount of spreading fertilizer over the fields of passivator is the 0.5%-1.5% of soil dry weight.
Further, in application of the present invention, the pH value of slightly acidic cadmium pollution soil is 4-6.
Further, in application of the present invention, the amount of spreading fertilizer over the fields of acid soil cadmium passivator is that the 0.5%-1.5%(of agricultural land soil dry weight calculates according to the soil weight, is namely equivalent to 800 ~ 2400kg/ mu).
Further, steps A of the present invention) described in biological carbon, the agriculture production wastes such as preferred agricultural crop straw, wood chip, feces of livestock and poultry are that Raw material processing is obtained, and preparation condition is anaerobic environment 300-500 DEG C.
The passivator that the present invention obtains is in alkalescence, can by improving the pH value of soil, realize Cadmium in Soil ion from exchangeable species to more stable form transformation, improve cadmium ion stability in soil, realize low acid farmland of polluting in heavy metal cadmium and carry out stabilization reparation.Modification biological charcoal is the main constitutive material of passivator of the present invention, charcoal has huge specific surface area and flourishing microvoid structure, can active adsorption, fixing heavy metal cadmium ion, charcoal can increase the organic content in soil simultaneously, coordination is produced with Cadmium in Soil, free metal ion combines with the soil organism, thus improves the stability of heavy metal ion, therefore has efficient passivation effect for slightly acidic heavy-metal contaminated soil.
Compared to existing passivator, beneficial effect of the present invention is embodied in:
(1) passivator of the present invention's acquisition, in-situ passivation reparation is carried out for the cadmium pollution in slightly acidic soil, the efficient passivation to the available Cd in slightly acidic soil can be realized, when passivator applied amount is in soil dry weight more than 1.5%, can realize reaching more than 90% to available Cd passivation, higher by more than 20% than common passivator remediation efficiency, meet the demand that cadmium pollution slightly acidic soil is efficiently repaired fast.
(2) passivator provided by the invention is prepared from the complex material being rich in the elements such as calcium, magnesium, silicon by the modification biological carbon that chemical property is extremely stable, can be permanently effective exist in soil, overcoming existing passivator can not the shortcoming of passivation Cadmium in Soil long-term effectively, and therefore this passivator has the passivation effect of permanent stability to the cadmium in soil.
(3) passivator of the present invention is with low cost, application process simple, and containing a large amount of organic and other nutritive element, for plant-growth provides abundant nutrient.
Accompanying drawing explanation
The different passivator of Fig. 1 is to slightly acidic soil available Cd passivation effect.
The different passivator applied amount of Fig. 2 is to slightly acidic soil available cadmium passivation effect.
Fig. 3 differential responses time passivator is to soil available Cd passivation effect.
The different passivator applied amount of Fig. 4 is on the impact of cadmium content in wheat grain.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to following embodiment.
Material, instrument source is related in embodiment:
Biological carbon purchased from Desheng, Liyang City of Jiangsu Province gac factory, is that raw material is prepared in the 300-500 DEG C of anaerobic environment do not waited by stalk respectively;
Flyash takes from Nanjing Cogeneration Power Plant;
Fused(calcium magnesium)phosphate (magnesium oxide) is purchased from shimen Hunan rural area phosphate fertilizer limited liability company;
The native siliceous fertilizer of benefit (silicon oxide) is purchased from the level in Anshan city, liaoning province Qin and agricultural science and technology company limited;
Biological organic fertilizer is purchased from the biochemical company limited in oasis, Fujian;
Pedotheque: Nanjing Vegetable Base taken from by slightly acidic cadmium pollution soil sample, this soil pH is slightly acidic (Ph=4.56), principal pollutant are heavy metal cadmium 2.67mg/kg, exceed the highest permissible level 0.3mg/kg of cadmium contaminants in China's soil environment quality secondary standard agricultural land soil, meeting is to agriculture production, and HUMAN HEALTH forms very large harm;
Ultrasonic Cleaners is KQ-800KDE type, purchased from Kunshan Ultrasonic Instruments Co., Ltd.;
Microwave chemical reactor is MG08S type, grinds microwave system engineering company limited purchased from Nan Jinghui.
Embodiment 1 prepares passivator ND-1
(1) get 100g in the straw biological carbon of 300 DEG C of preparations, grinding is broken, crosses 80 order nylon mesh;
(2) biological carbon is immersed in the mixing solutions 3 hours that final concentration is 1mol/L sodium sulphite and 10% sulfuric acid, the mass ratio of biological carbon and mixing solutions is 1:3;
(3) mixed system after above-mentioned immersion is placed in Ultrasonic Cleaners, ultrasonic reaction 20min, ultrasonic power is 400W; Then reaction system is placed in microwave chemical reactor microwave reaction 10min, microwave power 600W;
(4) by the mixed system that above-mentioned microwave reaction completes, by suction filtration, biological carbon is separated with mixing solutions, with deionized water, biological carbon is washed till neutrality, 70 DEG C of oven for drying, obtain modifier carbon;
(5) calcium oxide, flyash, fused(calcium magnesium)phosphate, beneficial native siliceous fertilizer that will buy, compositely according to a certain percentage obtain the matrix material being rich in calcium, magnesium, silicon, make to be calculated in mass percent in matrix material, calcium oxide accounts for 30%, magnesium oxide accounts for 5%, silicon oxide accounts for 15%, and surplus is the mineral materials such as flyash;
(6) modification biological carbon step (4) obtained and matrix material (5) ratio 1:1 mix, and namely obtain passivator, and the passivator that the present embodiment obtains is from called after ND-1.
Embodiment 2 prepares passivator ND-2
(1) get 100g preparation temperature be 400 DEG C straw biological charcoal, grinding is broken, crosses 100 order nylon mesh:
(2) charcoal is immersed in 1mol/L sodium sulphite and 10% sulfuric acid mixed solution 4 hours, the mass ratio of charcoal and mixing solutions is 1:4;
(3) mixed system after immersion is placed in Ultrasonic Cleaners, ultrasonic reaction 25min, ultrasonic power is 600W; Then reaction system is placed in microwave chemical reactor microwave reaction 15min, microwave power 800W;
(4) mixed system completed by microwave reaction, is separated charcoal with mixing solutions by suction filtration, with deionized water, charcoal is washed till neutrality, 70 DEG C of oven for drying, obtains modification biological charcoal;
(5) calcium oxide, flyash, fused(calcium magnesium)phosphate, beneficial native siliceous fertilizer that will buy, compositely according to a certain percentage obtain the matrix material being rich in calcium, magnesium, silicon, make to be calculated in mass percent in matrix material, calcium oxide accounts for 35%, magnesium oxide accounts for 8%, silicon oxide accounts for 20%, and surplus is the mineral materials such as flyash;
(6) modification biological carbon step (4) obtained and matrix material (5) ratio 1:2 mix, and namely obtain passivator, and the passivator that the present embodiment obtains is from called after ND-2.
Embodiment 3 prepares passivator ND-3
(1) get the straw biological charcoal that 100g preparation temperature is about 500 DEG C, grinding is broken, crosses 100 order nylon mesh;
(2) charcoal is immersed in 1mol/L sodium sulphite and 10% sulfuric acid mixed solution 5 hours, the mass ratio of charcoal and mixing solutions is 1:5;
(3) above-mentioned mixed system is placed in Ultrasonic Cleaners, ultrasonic reaction 30min, ultrasonic power is 800W; Then reaction system is placed in microwave chemical reactor microwave reaction 20min, microwave power 1000W;
(4) mixed system completed by microwave reaction, is separated charcoal with mixing solutions by suction filtration, with deionized water, charcoal is washed till neutrality, 70 DEG C of oven for drying, obtains modification biological charcoal;
(5) calcium oxide, flyash, fused(calcium magnesium)phosphate, beneficial native siliceous fertilizer that will buy, compositely according to a certain percentage obtain the matrix material being rich in calcium, magnesium, silicon, make to be calculated in mass percent in matrix material, calcium oxide accounts for 40%, magnesium oxide accounts for 10%, silicon oxide accounts for 25%, and surplus is the mineral materials such as flyash;
(6) modification biological carbon step (4) obtained and matrix material (5) ratio 1:3 mix, and namely obtain passivator, and the passivator that the present embodiment obtains is from called after ND-3.
Embodiment 4 passivator Piglet s colibacillosis
Pedotheque is dried at shady and cool ventilation place, crosses ten order nylon mesh for subsequent use.
For the passivator and conventional passivation agent of investigating embodiment 1-3 acquisition compare, pollute slightly acidic soil remediation effect for cadmium (Cd), the present embodiment experiment is divided into two groups:
Passivator ND-1, ND-2 and ND-3 that experimental group uses embodiment 1-3 to obtain respectively;
Control group selects fused(calcium magnesium)phosphate (shimen Hunan rural area phosphate fertilizer limited liability company), silicon oxide (beneficial native siliceous fertilizer, the level in Anshan city, liaoning province Qin and agricultural science and technology company limited), lime, biological organic fertilizer and charcoal (preparation temperature 400 DEG C) respectively; Set up the original soil be left intact as blank simultaneously.
Control group is mixed with pedotheque by the quality of pedotheque dry weight 1% respectively with experimental group, and keeps more than 70% 10 day of maximum water holding capacity.
At passivator and soil stabilization after 10 days, adopt Tessier branch extraction method (TessierA, CampbellPGC, BissonM.Sequentialextractionprocedureforthespeciationofp articulatetracemetals [J] .AnalyticalChemistry, 1979,51 (7): 844-851.), 1mol/lMgCl is adopted
2as extraction agent, available Cd in pedotheque is extracted, application atomic absorption spectroscopy determination cadmium content.As shown in Figure 1, as seen from Figure 1, the several frequently seen cadmium stabilizer of control group all can realize the stabilization of slightly acidic soil heavy metal cadmium to detected result, and the best lime stabilization of effect reaches 48.6%; Experimental group passivator (ND-1 ~ ND-3) is to the available Cd passivation in soil far above control group, and soil available Cd reduces about 70.7%, and soil available Cd content drops to 0.38mg/kg.
The different applied amount of embodiment 5 is on passivation effect impact test
In order to investigate the applied amount of different passivator to the impact of soil available Cd Cd passivation under solutions of weak acidity, using the passivator ND-2 of embodiment 2 acquisition as research object, ND-2 is mixed with pedotheque with 0.1% of dry ground quality, 0.3%, 0.5%, 1%, 1.5%, 3% respectively, keeps 70% of maximum water holding capacity to stablize 20 days.
Application adopts Tessier branch extraction method, adopts 1mol/lMgCl
2as extraction agent, available Cd in pedotheque is extracted, application atomic absorption spectroscopy determination cadmium content.The results are shown in Figure 2, as seen from Figure 2 when passivator ND-2 and soil stabilization are after 20 days, along with the increase of ND-2 applied amount in slightly acidic soil, soil available Cd clearance constantly increases, when ND-2 applied amount is soil dry weight more than 1.5% time, ND-2 reaches more than 95% to soil available Cd passivation.Illustrate that passivator of the present invention is under less amount of application condition, still can realize there is efficient stabilization effect to cadmium pollution acid soil.
Embodiment 6 passivator application effect chronicity is tested
In order to investigate passivator applying after long-term effectiveness to the passivation of slightly acidic soil available Cd, the passivator ND-2 obtained with embodiment 2 is for research object, the amount that ND-2 weighs 1.5% with dry ground is mixed with pedotheque, keep 70% of maximum water holding capacity, sampling analysis soil available Cd content 10 days, 50 days, 100 days, 200 days, 300,400 days time respectively.
Adopt Tessier branch extraction method, with 1mol/lMgCl
2respectively available Cd in fixing-stableization 10 days, 50 days, 100 days, 200 days, 300 days, 400 days pedotheques is extracted as extraction agent, application atomic absorption spectroscopy determination cadmium content.Test-results is shown in Fig. 3, as seen from Figure 3, passivator ND-2 has efficient stability, all efficient stable state is kept within the time of 10 days to 200 days, when ND-2 addition is 1.5% time, soil available cadmium deactivation rate is about 90%, and in soil, bioavailable state cadmium content is at below 0.1mg/kg.This is because biological carbon is as the main raw material(s) of passivator ND-2, in soil, there are permanent stability, be not easily degraded by microorganisms, the chronicity of stablizer fixed effect in soil that this project is researched and developed can be ensured.
Embodiment 7 passivator field experiment
In order to investigate the applied amount of passivator to cadmium pollution slightly acidic soil remediation effect, in October, 2014 carries out reparation pilot in heavy metal contamination farmland, Nanjing using passivator of the present invention as renovation agent, in the soil repaired, plant wheat.
The passivator ND-2 that the present embodiment obtains using embodiment 2 is as research object, more than the 20 centimeters arable layers on earth's surface, the amount that ND-2 weighs 0.1%, 0.3%, 0.5%, 1%, 1.5%, 3% with dry ground is respectively mixed with cadmium pollution soil, keeps more than 70% of maximum water holding capacity to stablize 10 days.Then the farmland planting wheat (Luo Mai-23) repaired, adopts normal field management pattern, treats harvesting wheat season, gathers wheat grain sample, detects cadmium content in seed.
In wheat grain, the mensuration of cadmium content adopts wet method (HNO
3-HClO
4) clear up, application atomic absorption spectroscopy determination cadmium content.The results are shown in Figure 4, as seen from Figure 4 along with the increase of passivator applied amount in soil, in wheat grain, cadmium content reduces, when passivator applied amount is 1.5% of soil quality, and the 0.1mg/kg that in wheat grain, cadmium content specifies lower than GB2762-2012 " in food heavy metal limit standard ".Therefore passivator of the present invention not only can realize significantly reducing cadmium in acid soil can also to realize cadmium in crop kernels up to standard, can not produce harm to human security.
This is because the reduction of Cadmium in Soil available state, can be reduced by the cadmium content that farm crop are extracted in soil, the Ca while of causing in passivator material of the present invention
2+, Mg
2+plasma has antagonistic action to cadmium ion in soil, and the absorption site participated in the competition on root system of plant, can suppress the absorption of plant heavy metal cadmium, thus reduces the absorption of plant heavy metal, reaches repairing effect.
The above embodiment only have expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some improvement, these improvement all belong to protection scope of the present invention.
Claims (7)
1. for a passivator for slightly acidic cadmium pollution soil, it is characterized in that, described passivator obtains like this:
A) mixing solutions biological carbon being placed in sodium sulphite and sulfuric acid soaks 3-5h; In described mixing solutions, sodium sulphite concentration is 1mol/L, and the massfraction of sulfuric acid is 10%;
B) 400 ~ 800W, supersound washing 20-30min, then in 600 ~ 1000W microwave chemical reactor reaction 10-20min;
C) suction filtration reactant, with deionized water, biological carbon washing is extremely neutral, 70 DEG C of oven dry, obtain modification biological carbon;
D) mixing of calcium oxide, fused(calcium magnesium)phosphate and benefit soil siliceous fertilizer is obtained complex material, be calculated in mass percent, in complex material, calcium oxide accounts for 30-40%, and magnesium oxide accounts for 5-10%, and silicon oxide accounts for 15-25%, and surplus is flyash;
By step C) the modification biological carbon that obtains and complex material in mass ratio 1:1-3 mix, namely obtain described passivator.
2. a kind of passivator for slightly acidic cadmium pollution soil according to claim 1, is characterized in that, steps A) in, the mass ratio of biological carbon and mixing solutions is 1:3-5.
3. a kind of passivator for slightly acidic cadmium pollution soil according to claim 2, it is characterized in that, steps A of the present invention) described in biological carbon, refer to that by agricultural crop straw, wood chip or animal dung be raw material, prepare in the anaerobic environment of 300-500 DEG C.
4. as described in one of claim 1-3, the application in slightly acidic cadmium pollution soil repaired in position by passivator.
5. application according to claim 4, is characterized in that, concrete steps are as follows: evenly spread fertilizer over the fields by passivator in slightly acidic cadmium pollution soil, then by soil rotary tillage 20cm; Water to irrigate and be not less than 70% of maxmun field capacity to soil water content, keep 10d, namely complete the in-situ immobilization to this slightly acidic cadmium pollution soil.
6. application according to claim 5, is characterized in that, the amount of spreading fertilizer over the fields of described passivator is the 0.5%-1.5% of soil dry weight.
7. application according to claim 6, is characterized in that, the pH value of described slightly acidic cadmium pollution soil is 4-6.
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Application publication date: 20160504 Assignee: JIANGSU TIANXIANG BIOLOGICAL TECHNOLOGY CO.,LTD. Assignor: NANJING University Contract record no.: X2023320000133 Denomination of invention: A passivation agent for weakly acidic cadmium contaminated soil and its application Granted publication date: 20190222 License type: Common License Record date: 20230331 |