CN104031651A - Passivation improver for heavy metal pollution farmland and using method thereof - Google Patents
Passivation improver for heavy metal pollution farmland and using method thereof Download PDFInfo
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Abstract
The invention provides a passivation improver for a heavy metal pollution farmland and a using method of the passivation improver. The raw materials comprise coal ash, nano iron powder, zeolite, medical stone, calcium magnesium phosphate, hydroxypropyl modified SiO2/chitosan nanoparticles and porous spherical cellulose. According to the composite passivation improver, the passivation effect on heavy metals cadmium, lead, arsenic and chromium in soil can be improved, copper and zinc in soil are well passivated, and the soil remediation effect is improved.
Description
Technical field
The present invention relates to heavy metal-polluted soil passivating technique field, relate in particular to a kind of passivation modifying agent and using method thereof for heavy metal contamination farmland.
Background technology
Agricultural resources and environment is not only the important substance basis of agriculture production, and be directly connected to the quality safety of agricultural-food, have influence on the healthy of the mankind, be related to frequency and intensity that agricultural disaster occurs, the Sustainable development of agricultural and rural economy is played to conclusive effect.Along with the increase of industry, the aggravation of municipal pollution and agrochemicals kind, quantity, the heavy metal emitting from work, agriculture, life is constantly added, and heavy metal pollution of soil is day by day serious.Heavy metal is the principal pollutant in current China farmland, and within 1980, national contaminated farmland area is 2.67 × 10
4km
2, the annual cultivated area nearly 2 × 10 that is subject to the heavy metal contaminations such as lead, cadmium, mercury in 1998
5km
2account for 1/5 of total area under cultivation, the grain drop in production 10 million ton that China in 2006 causes because of heavy metal contamination every year, nearly 1,200 ten thousand tons, contaminated by heavy metals grain, farmland soil heavy metals is polluted to have become affects agricultural products in China quality, one of major obstacle of restriction agricultural products in China trade.Heavy metal-polluted soil is by migration and conversion, the growth that not only harms the crops, the health that endangers animal and the mankind simultaneously.In order to reduce the absorption accumulation of plant to heavy metal on heavy-metal contaminated soil, mainly study at present two kinds of methods both at home and abroad: the one, the heavy metal in soil is converted into indissoluble state, be the activated state heavy metal quilt " passivation " in soil, thereby make plant be difficult to absorb; The 2nd, heavy metal is removed from soil, utilize engineering or biological method " reparation " heavy-metal contaminated soil.
The most frequently used method is deactivation method at present, traditional research method is to add white lime in soil, the chemical substances such as Calucium Silicate powder, by adding these materials, can precipitate with heavy metal element, absorption, ion-exchange, the series reaction such as humify and redox, and then Xingtai is deposited in the tax that changes heavy metal, significantly reduce its biological effectiveness and transportable property, obviously slow down the toxic action of heavy metal contamination to plant-growth, significantly reduce the absorption and accumulation of plant to heavy metal, but, these materials are inorganic substance mostly, all affect soil physical chemistry character and fertility, microorganism growth environment is caused to impact in various degree, also the degree utilized that rear soil has been repaired in impact, therefore need further to find and the heavy metal contamination original position repair materials of research to edatope close friend, the passivator of traditional organic type has concurrently heavy metal-passivated and improves two kinds of functions of soil physico-chemical property, but but exist easily and decompose, the shortcoming that passivation is not long-term, the key point of passivation recovery technique is to filter out the efficient heavy passivator with actual application value, the applicant has developed a kind of passivation modifying agent of repairing for heavy metal in soil, it passes through flyash, iron powder, zeolite and fused(calcium magnesium)phosphate mix formation, it is to the heavy metal cadmium in soil, plumbous, arsenic, chromium has good passivation effect, but the passivation effect to copper and zinc is poor, the present invention further improves on the basis of this technology, by further adding three kinds of improvement compositions, further improve the heavy metal cadmium in soil, plumbous, arsenic, the passivation effect of chromium, and the copper in soil and zinc are also had to good passivation simultaneously, improve the repairing effect to soil.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of passivation modifying agent and using method thereof for heavy metal contamination farmland, it improves the passivation effect to the heavy metal cadmium in soil, lead, arsenic, chromium, and the copper in soil and zinc are also had to good passivation simultaneously, improve the repairing effect to soil.
For solving the problems of the technologies described above, the invention provides a kind of passivation modifying agent and using method thereof for heavy metal contamination farmland, its raw material comprises flyash, nanometer iron powder, zeolite, medical stone, fused(calcium magnesium)phosphate, hydroxypropyl modification SiO
2the spherical Mierocrystalline cellulose of/chitosan nano particle and hole.
Wherein, the weight ratio of each component described in described passivation modifying agent is nanometer iron powder, flyash, zeolite, fused(calcium magnesium)phosphate, medical stone, hydroxypropyl modification SiO
2spherical Mierocrystalline cellulose=10～25 of/chitosan nano particle and hole: 15～40: 25～50: 1～10: 5～15: 5～15: 10～20.
Wherein, the weight ratio of described each component is nanometer iron powder, flyash, zeolite, fused(calcium magnesium)phosphate, medical stone, hydroxypropyl modification SiO
2spherical Mierocrystalline cellulose=20 of/chitosan nano particle and hole: 30: 40: 10: 10: 10: 15.
Wherein, described hydroxypropyl modification SiO
2the preparation method of/chitosan nano particle comprises:
The first step, by 2.5L tetraethyl silicate, 5mL dehydrated alcohol and 5L deionized water mix, return stirring 1h at 80 DEG C.Then be 5～6 with acetic acid regulator solution pH, continue to stir 1h, make SiO
2colloidal sol;
Second step, getting 8g epoxy chloropropane HCl, to be acidified to pH value be 5～6, SiO prepared by the first step
2colloidal sol disperses with 50ml dehydrated alcohol, obtains dispersion liquid, and the epoxy chloropropane of acidifying is above added dropwise in this dispersion liquid, 40 DEG C of reaction 7h of temperature control, steam and desolventize and unreacted epoxy chloropropane, obtain white solid powder, vacuum-drying 6h at 50 DEG C, obtains hydroxypropylation SiO
2;
The 3rd step, is scattered in 2kg chitosan in 40L Virahol, and 40 DEG C of constant temperature are with after 0.3g sodium hydroxide alkalization 3h, the 2.5kg hydroxypropylation SiO that adds second step to obtain
2, 45 DEG C of reaction 5h of constant temperature, cooling, suction filtration, uses respectively Virahol and water washing filter cake, and vacuum-drying 5h obtains milky hydroxypropyl modification SiO
2/ chitosan nano particle.
Wherein, described in, stating the spherical cellulosic preparation method of hole comprises:
The first step, gets 1.4kgNaOH, 2.6kg urea and 15kg water, mixes, and in stirrer, stirs, and obtains dispersion medium;
Second step, 0.8kg cotton starch plate is joined in above-mentioned dispersion medium, and above-mentioned system is discongested to 1min with stirrer, then with sonic oscillation instrument vibration 30min, and cellulose solution is chilled in advance to-12 DEG C, this solution is discongested to 10min under 8000r/min homogenizer and obtain cellulose solution;
The 3rd step, cellulose solution prepared by second step obtains vitreous fibre cellulose solution under the rotating speed of 4000r/min after room temperature evacuation and centrifugal degassing 10min, 2.7%Span-80 is dissolved in Liquid Paraffin and is stirred after 30min with 1000r/min speed, in 1h, add above-mentioned cellulose solution, gained suspension is stirring and emulsifying 5h under the stirring velocity of 1000r/min and room temperature, under these conditions, drip 10% dilute hydrochloric acid and regulate pH to 7.0, suspension solidify to form Regenerated cellulose microspheres, leave standstill, mixture system is divided into two-layer, upper strata is that Liquid Paraffin organic phase can reclaim use by washing, lower floor's water is repeatedly used washing with acetone 3 times after rinsing again with distilled water, obtain the spherical Mierocrystalline cellulose of hole, finally, adopt cooling drying to preserve spherical these holes Mierocrystalline cellulose, the mean pore size of prepared product is 55nm～65nm.
The particle diameter of described nanometer iron powder is 50～200nm.
The present invention also provides the preparation method of above-mentioned passivation modifying agent, comprising:
The first step, prepares hydroxypropyl modification SiO according to the method described above
2/ chitosan nano particle;
Second step, prepares the spherical Mierocrystalline cellulose of hole according to the method described above;
The 3rd step, is uniformly mixed each component according to above-mentioned weight ratio, obtain described composite passivated modifying agent.
Beneficial effect of the present invention:
A kind of passivation modifying agent for heavy metal contamination farmland provided by the invention, it can improve the passivation effect to the heavy metal cadmium in soil, lead, arsenic, chromium, and the copper in soil and zinc are also had to good passivation simultaneously, improve the repairing effect to soil.
Brief description of the drawings
The spherical cellulosic infrared spectrum of Fig. 1 hole;
The spherical cellulosic XRD spectra of Fig. 2 hole;
Fig. 3 hydroxypropyl modification SiO
2the infrared spectrum of/chitosan nano particle.
Embodiment
The invention provides a kind of passivation modifying agent and using method thereof for heavy metal contamination farmland, its raw material comprises flyash, nanometer iron powder, zeolite, medical stone, fused(calcium magnesium)phosphate, hydroxypropyl modification SiO
2the spherical Mierocrystalline cellulose of/chitosan nano particle and hole.
Further, described passivation modifying agent is only made up of above-mentioned raw materials.
Flyash is one of industrial residue that the current quantity discharged of China is larger, the main solid waste that power industry produces, nineteen ninety-five, flyash quantity discharged reached 1.25 hundred million tons, within 2000, be about 1.5 hundred million tons, to reach 300,000,000 tons by 2010, and cause huge pressure to the development of the national economy and the ecotope of China.Fly ash grain is multi-hole type cellular tissue, and specific surface area is larger, has higher adsorption activity, and the particle size range of particle is 0.5～300 μ m, and Zhu Bi has vesicular structure, and porosity, up to 50%～80%, has very strong water-absorbent.Utilize the feature that flyash specific surface area is large, repairing activity is high, can improve passivator repairing effect, and the comprehensive utilization of flyash also meets " comprehensive utilization of reinforcement to large solid waste " requirement in " 12 " planning.
Iron powder is a kind of most important metal-powder in industry, consumption maximum in powder metallurgy is produced.Nanoscale Iron has very strong adsorptive power to heavy metal contaminants, and adding can be by the adsorptive power of self after soil, improves the loading capacity of soil to heavy metal.For example iron energy and arsenic, manganese effect form the mixture of stable bidentate structure, thereby reduce the biological effectiveness of heavy metal.And iron powder has reductibility, can promote that the pentavalent chromium in soil is reduced into the trivalent chromium that toxicity is less, make chromium pollutant relatively stable in environment.
The present invention adopts nanometer iron powder, and its particle diameter is 50～200nm.
Zeolite is the natural silico-aluminate ore of a class, natural zeolite has pore passage structure, can produce stronger ion-exchange and adsorptive power to heavy metal ion by its silicon-oxy tetrahedron and alumina octahedral structure, the harmful elements such as lead, mercury, cadmium and chromium are had to very strong adsorptive power, thereby be used widely in heavy metal passivation reparation.
Fused(calcium magnesium)phosphate is that one contains phosphate radical (PO
4 3-) sillico aluminate glass body, without clear and definite molecular formula and molecular weight, it is Rock Phosphate (72Min BPL) and ore containing magnesium, silicon, in blast furnace or electric furnace through high-temperature fusion, shrend, dry and levigate forming.Phosphoric acid salt can form stable phosphorus chlorine mineral at soil mineral and roots of plants surface by co-precipitation, thereby the heavy metals such as Lead In Soil are produced to stronger passivation.Fused(calcium magnesium)phosphate can provide 12%～18% low phosphorus, increases soil fertility, and the mineral substance such as a large amount of silicon, calcium, magnesium can also be provided, and supplies with crop growth, has the effect of one-object-many-purposes.
Nanometer iron powder plays the effect of reductive agent to the heavy metal in soil, reduce the biological effectiveness of heavy metal at soil, fused(calcium magnesium)phosphate and zeolite play the promoter effect that reduces heavy metal biological activity, flyash plays the effect of dispersion agent, by the collaborative work of four kinds of materials, performance effect separately, regulate and the physico-chemical property of change heavy metal in soil, make it produce absorption, complexing, precipitation, the series reaction such as ion-exchange and redox, thereby reduce biological effectiveness and the transportable property of heavy metal in edatope, and then reduce heavy metal element to vegeto-animal toxicity, realize the effective passivation to heavy metal in polluted farmland soil.
Medical stone is a kind of high-quality feature of environmental protection natural minerals, be the middle persilicic rock of a kind of weathering or half weathering, it is the spongy special construction of porousness, and surface-area is large, there is strong electrostatic interaction, therefore the toxic heavy metal elements such as chromium, lead, copper, cadmium, zinc are had to stronger confinement capabilities.
Chitosan is the product after chitin deacetylase base, has the features such as wide material sources, nontoxic, easy degraded, and in molecular chain, containing a large amount of active groups can react with contents of many kinds of heavy metal ion.Active hydroxyl in its molecule and the amino functional group that waits can carry out chelating with heavy metal ion, there is adsorption, form network molecule, therefore chitosan can with heavy metal ion coordination, effectively remove the heavy metal composition in soil, but traditional chitosan exists easily decomposition, passivation time is shorter, the unconspicuous defect of adsorption effect, nanometer SiO
2there is good reticulated structure, metal ion is had to very large loading capacity, and be difficult for decomposing, will there is the group of chelating heavy metal function, be grafted to nanometer SiO
2surface, can make nanometer SiO
2have the function of better Adsorption of Heavy Metals, the present invention is by nanometer SiO
2with epichlorohydrin reaction, to SiO
2carry out modification, make hydroxypropylation SiO
2particle, then cross-linking is to the amino of chitosan, has prepared with better novel hydroxypropyl modification SiO chemical bonds, dispersed
2/ chitosan nano particle, by carrying out SiO by chitosan
2modification, can improve passivation time, promotes adsorption effect.
Described hydroxypropyl modification SiO
2the preparation method of/chitosan nano particle is specially:
The first step, by 2.5L tetraethyl silicate, 5mL dehydrated alcohol and 5L deionized water mix, return stirring 1h at 80 DEG C.Then be 5～6 with acetic acid regulator solution pH, continue to stir 1h, make SiO
2colloidal sol;
Second step, getting 8g epoxy chloropropane HCl, to be acidified to pH value be 5～6, SiO prepared by the first step
2colloidal sol disperses with 50ml dehydrated alcohol, obtains dispersion liquid, and the epoxy chloropropane of acidifying is above added dropwise in this dispersion liquid, 40 DEG C of reaction 7h of temperature control, steam and desolventize and unreacted epoxy chloropropane, obtain white solid powder, vacuum-drying 6h at 50 DEG C, obtains hydroxypropylation SiO
2;
The 3rd step, is scattered in 2kg chitosan in 40L Virahol, and 40 DEG C of constant temperature are with after 0.3g sodium hydroxide alkalization 3h, the 2.5kg hydroxypropylation SiO that adds second step to obtain
2, 45 DEG C of reaction 5h of constant temperature, cooling, suction filtration, uses respectively Virahol and water washing filter cake, and vacuum-drying 5h obtains milky hydroxypropyl modification SiO
2/ chitosan nano particle.
Mierocrystalline cellulose is natural hydrophilic superpolymer, there is the features such as good biocompatibility, nontoxic, chemical modifiability and degradable regenerative, it is desirable sorbent material, and the present invention is prepared into porous shape by cellulose materials by specific preparation method, more strengthen its absorption property, aspect Adsorption of Heavy Metals element, had a significant effect.
The present invention also provides above-mentioned hole spherical cellulosic preparation method, and it comprises:
The first step, gets 1.4kgNaOH, 2.6kg urea and 15kg water, mixes, and in stirrer, stirs, and obtains dispersion medium;
Second step, 0.8kg cotton starch plate is joined in above-mentioned dispersion medium, and above-mentioned system is discongested to 1min with stirrer, then with sonic oscillation instrument vibration 30min, and cellulose solution is chilled in advance to-12 DEG C, this solution is discongested to 10min under 8000r/min homogenizer and obtain cellulose solution;
The 3rd step, cellulose solution prepared by second step obtains vitreous fibre cellulose solution under the rotating speed of 4000r/min after room temperature evacuation and centrifugal degassing 10min, 2.7%Span-80 is dissolved in Liquid Paraffin and is stirred after 30min with 1000r/min speed, in 1h, add above-mentioned cellulose solution, gained suspension is stirring and emulsifying 5h under the stirring velocity of 1000r/min and room temperature, under these conditions, drip 10% dilute hydrochloric acid and regulate pH to 7.0, suspension solidify to form Regenerated cellulose microspheres, leave standstill, mixture system is divided into two-layer, upper strata is that Liquid Paraffin organic phase can reclaim use by washing, lower floor's water is repeatedly used washing with acetone 3 times after rinsing again with distilled water, obtain the spherical Mierocrystalline cellulose of hole, finally, adopt cooling drying to preserve spherical these holes Mierocrystalline cellulose, the mean pore size of prepared product is 55nm～65nm.
By the multiple material that can play passivation to heavy metal element is used in conjunction with, make every kind of material synergy, maximize favourable factors and minimize unfavourable ones, improve the passivation effect to the heavy metal cadmium in soil, lead, arsenic, chromium, and the copper in soil and zinc are also had to good passivation simultaneously, improve the repairing effect to soil.
The present invention also provides the preparation method of above-mentioned passivation modifying agent, comprising:
The first step, prepares hydroxypropyl modification SiO according to the method described above
2/ chitosan nano particle;
Second step, prepares the spherical Mierocrystalline cellulose of hole according to the method described above;
The 3rd step, is uniformly mixed each component according to above-mentioned weight ratio, obtain described passivation modifying agent.
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.
The spherical cellulosic preparation of embodiment 1 hole
Get 1.4kgNaOH, 2.6kg urea and 15kg water, mix, in stirrer, stir, obtain dispersion medium, 0.8kg cotton starch plate is joined in above-mentioned dispersion medium, and above-mentioned system is discongested to 1min with stirrer, use again sonic oscillation instrument vibration 30min, and cellulose solution is chilled in advance to-12 DEG C, this solution is discongested to 10min under 8000r/min homogenizer and obtain cellulose solution, the cellulose solution of preparation is obtained to vitreous fibre cellulose solution under the rotating speed of 4000r/min after room temperature evacuation and centrifugal degassing 10min, 2.7%Span-80 is dissolved in Liquid Paraffin and is stirred after 30min with 1000r/min speed, in 1h, add above-mentioned cellulose solution, gained suspension is stirring and emulsifying 5h under the stirring velocity of 1000r/min and room temperature, under these conditions, drip 10% dilute hydrochloric acid and regulate pH to 7.0, suspension solidify to form Regenerated cellulose microspheres, leave standstill, mixture system is divided into two-layer, upper strata is that Liquid Paraffin organic phase can reclaim use by washing, lower floor's water is repeatedly used washing with acetone 3 times after rinsing again with distilled water, obtain the spherical Mierocrystalline cellulose of hole, finally, adopt cooling drying to preserve spherical these holes Mierocrystalline cellulose, the mean pore size of prepared product is 58.3nm.
Physical properties detects
The product examination of infrared spectrum obtaining carries out on FT-IR spectrometer (IVICOLET IS10SMART ITR), and the preparation of sample adopts KBr pressed disc method.The XRD figure spectrum of magnetic microsphere is measured with DS-Advance type x-ray diffractometer (Bruker, USA).
The spherical cellulosic FT-IR of hole is shown in Fig. 1.1100cm
-1and 1370cm
-1the peak at place is Mierocrystalline cellulose characteristic peak; 1622cm
-1and 2928cm
-1the peak at place can be attributed to respectively carbonyl in cellulosic molecule and the stretching vibration peak of saturated carbon hydrogen bond; 3437cm
-1and 3342cm
-1peak be in molecule and the stretching vibration peak of intermolecular O-H (comprising hydrogen bond).
The spherical Mierocrystalline cellulose X-ray diffractogram of hole of producing by in-situ compositing is shown in Fig. 2.
Embodiment 2 hydroxypropyl modification SiO
2the preparation of/chitosan nano particle
By 2.5L tetraethyl silicate, 5L dehydrated alcohol and 5L deionized water mix, and then return stirring 1h at 80 DEG C is 6 with acetic acid regulator solution pH, continue to stir 1h, make SiO
2colloidal sol, getting 8g epoxy chloropropane HCl, to be acidified to pH value be 6, by the SiO preparing above
2colloidal sol disperses with 50L dehydrated alcohol, obtains dispersion liquid, and the epoxy chloropropane of acidifying is above added dropwise in this dispersion liquid, 40 DEG C of reaction 7h of temperature control, steam and desolventize and unreacted epoxy chloropropane, obtain white solid powder, vacuum-drying 6h at 50 DEG C, obtains hydroxypropylation SiO
2, 2kg chitosan is scattered in 40L Virahol, 40 DEG C of constant temperature, with after 0.3kg sodium hydroxide alkalization 3h, add the 2.5kg hydroxypropylation SiO obtaining above
2, 45 DEG C of reaction 5h of constant temperature, cooling, suction filtration, uses respectively Virahol and water washing filter cake, and vacuum-drying 5h obtains milky hydroxypropyl modification SiO
2/ chitosan nano particle.
Hydroxypropyl modification SiO
2the infrared spectrum of/chitosan nano particle is as Fig. 3.
The preparation of the composite passivated modifying agent 1 of embodiment 3
By the nanometer iron powder 2kg of 90nm particle diameter, flyash 3kg, zeolite 4kg, fused(calcium magnesium)phosphate 1kg, medical stone 1kg, hydroxypropyl modification SiO
2the spherical Mierocrystalline cellulose 1.5kg of hole prepared by/chitosan nano particle 1kg and embodiment 1 evenly mixes, and obtains composite passivated modifying agent 1.
Effect proves
Apply composite passivated modifying agent 1 prepared by the embodiment 1 of 0.5cm thickness on the surface of heavy-metal contaminated soil, then repair the thick pollution-free soil mixing of medicament Surface mulch 20cm in heavy-metal contaminated soil.
Repair: through 1 month, heavy metal cadmium in heavy-metal contaminated soil, lead, arsenic, chromium are reduced into immobilized heavy metal at a low price, lose its biological effectiveness, realize the original position reparation of heavy-metal contaminated soil, and very good to the in-situ passivation effect of heavy metal copper and zinc, the heavy metal cadmium in the Chinese cabbage of plantation, lead, arsenic, chromium content meet the requirement of " pollutants in food limitation " GB2762-2005 of country.
The results are shown in Table 1.
Table 1
The preparation of comparative example 1 passivation modifying agent 2
The nanometer iron powder 2kg of 90nm particle diameter, flyash 3kg, zeolite 4kg, fused(calcium magnesium)phosphate 1kg are evenly mixed, obtain passivation modifying agent 2.
Effect proves
Apply composite passivated modifying agent 2 prepared by the comparative example 1 of 0.5cm thickness on the surface of heavy-metal contaminated soil, then repair the thick pollution-free soil mixing of medicament Surface mulch 20cm in heavy-metal contaminated soil.
Repair: through 1 month, heavy metal cadmium in heavy-metal contaminated soil, lead, arsenic, chromium are reduced into immobilized heavy metal at a low price, lose its biological effectiveness, realize the original position reparation of heavy-metal contaminated soil, and poor to the in-situ passivation effect of heavy metal copper and zinc, the heavy metal cadmium in the Chinese cabbage of plantation, lead, arsenic, chromium content meet the requirement of " pollutants in food limitation " GB2762-2005 of country.
The results are shown in Table 2.
Table 2
The preparation of comparative example 2 passivation modifying agents 3
By the nanometer iron powder 2kg of 90nm particle diameter, flyash 3kg, zeolite 4kg, fused(calcium magnesium)phosphate 1kg, medical stone 1kg and hydroxypropyl modification SiO
2/ chitosan nano particle 1kg evenly mixes, and obtains passivation modifying agent 3.
Effect proves
Apply composite passivated modifying agent 3 prepared by the comparative example 2 of 0.5cm thickness on the surface of heavy-metal contaminated soil, then repair the thick pollution-free soil mixing of medicament Surface mulch 20cm in heavy-metal contaminated soil.
Repair: through 1 month, heavy metal cadmium in heavy-metal contaminated soil, lead, arsenic, chromium are reduced into immobilized heavy metal at a low price, lose its biological effectiveness, realize the original position reparation of heavy-metal contaminated soil, and also better to the in-situ passivation effect of heavy metal copper and zinc, the heavy metal cadmium in the Chinese cabbage of plantation, lead, arsenic, chromium content meet the requirement of " pollutants in food limitation " GB2762-2005 of country.
The results are shown in Table 3.
Table 3
The preparation of comparative example 3 passivation modifying agents 4
The spherical Mierocrystalline cellulose 1.5kg of hole prepared by the nanometer iron powder 2kg of 90nm particle diameter, flyash 3kg, zeolite 4kg, fused(calcium magnesium)phosphate 1kg, medical stone 1kg and embodiment 1 evenly mixes, and obtains passivation modifying agent 4.
Effect proves
Apply composite passivated modifying agent 4 prepared by the comparative example 3 of 0.5cm thickness on the surface of heavy-metal contaminated soil, then repair the thick pollution-free soil mixing of medicament Surface mulch 20cm in heavy-metal contaminated soil.
Repair: through 1 month, heavy metal cadmium in heavy-metal contaminated soil, lead, arsenic, chromium are reduced into immobilized heavy metal at a low price, lose its biological effectiveness, realize the original position reparation of heavy-metal contaminated soil, and also better to the in-situ passivation effect of heavy metal copper and zinc, the heavy metal cadmium in the Chinese cabbage of plantation, lead, arsenic, chromium content meet the requirement of " pollutants in food limitation " GB2762-2005 of country.
The results are shown in Table 4.
Table 4
The preparation of comparative example 4 passivation modifying agents 5
The nanometer iron powder 2kg of 90nm particle diameter, flyash 3kg, zeolite 4kg, fused(calcium magnesium)phosphate 1kg, medical stone 1kg are evenly mixed, obtain passivation modifying agent 5.
Effect proves
Apply composite passivated modifying agent 5 prepared by the comparative example 4 of 0.5cm thickness on the surface of heavy-metal contaminated soil, then repair the thick pollution-free soil mixing of medicament Surface mulch 20cm in heavy-metal contaminated soil.
Repair: through 1 month, heavy metal cadmium in heavy-metal contaminated soil, lead, arsenic, chromium are reduced into immobilized heavy metal at a low price, lose its biological effectiveness, realize the original position reparation of heavy-metal contaminated soil, and also better to the in-situ passivation effect of heavy metal copper and zinc, the heavy metal cadmium in the Chinese cabbage of plantation, lead, arsenic, chromium content meet the requirement of " pollutants in food limitation " GB2762-2005 of country.
The results are shown in Table 5.
Table 5
Can find out from table 1 to table 5, adopt passivation modifying agent provided by the invention best to the passivation effect of heavy metal cadmium, lead, arsenic, chromium, copper, zinc.
All above-mentioned these intellecture properties of primary enforcement, do not set restriction this product innovation of other forms of enforcement and/or novel method.Those skilled in the art will utilize this important information, and foregoing amendment, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on product innovation of the present invention.
The above, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. for passivation modifying agent and the using method thereof in heavy metal contamination farmland, it is characterized in that: raw material comprises flyash, nanometer iron powder, zeolite, medical stone, fused(calcium magnesium)phosphate, hydroxypropyl modification SiO
2the spherical Mierocrystalline cellulose of/chitosan nano particle and hole.
2. composite passivated modifying agent as claimed in claim 1, is characterized in that: the weight ratio of described each component is nanometer iron powder, flyash, zeolite, fused(calcium magnesium)phosphate, medical stone, hydroxypropyl modification SiO
2spherical Mierocrystalline cellulose=10～25 of/chitosan nano particle and hole: 15～40: 25～50: 1～10: 5～15: 5～15: 10～20.
3. composite passivated modifying agent as claimed in claim 1 or 2, is characterized in that: the weight ratio of described each component is nanometer iron powder, flyash, zeolite, fused(calcium magnesium)phosphate, medical stone, hydroxypropyl modification SiO
2spherical Mierocrystalline cellulose=20 of/chitosan nano particle and hole: 30: 40: 10: 10: 10: 15.
4. the composite passivated modifying agent as described in claims 1 to 3, is characterized in that: described hydroxypropyl modification SiO
2the preparation method of/chitosan nano particle comprises:
The first step, by 2.5L tetraethyl silicate, 5mL dehydrated alcohol and 5L deionized water mix, return stirring 1h at 80 DEG C.Then be 5～6 with acetic acid regulator solution pH, continue to stir 1h, make SiO
2colloidal sol;
Second step, getting 8g epoxy chloropropane HCl, to be acidified to pH value be 5～6, SiO prepared by the first step
2colloidal sol disperses with 50ml dehydrated alcohol, obtains dispersion liquid, and the epoxy chloropropane of acidifying is above added dropwise in this dispersion liquid, 40 DEG C of reaction 7h of temperature control, steam and desolventize and unreacted epoxy chloropropane, obtain white solid powder, vacuum-drying 6h at 50 DEG C, obtains hydroxypropylation SiO
2;
The 3rd step, is scattered in 2kg chitosan in 40L Virahol, and 40 DEG C of constant temperature are with after 0.3g sodium hydroxide alkalization 3h, the 2.5kg hydroxypropylation SiO that adds second step to obtain
2, 45 DEG C of reaction 5h of constant temperature, cooling, suction filtration, uses respectively Virahol and water washing filter cake, and vacuum-drying 5h obtains milky hydroxypropyl modification SiO
2/ chitosan nano particle.
5. the composite passivated modifying agent as described in claim 1 to 4, is characterized in that: described in state the spherical cellulosic preparation method of hole and comprise:
The first step, gets 1.4kgNaOH, 2.6kg urea and 15kg water, mixes, and in stirrer, stirs, and obtains dispersion medium; Second step, 0.8kg cotton starch plate is joined in above-mentioned dispersion medium, and above-mentioned system is discongested to 1min with stirrer, then with sonic oscillation instrument vibration 30min, and cellulose solution is chilled in advance to-12 DEG C, this solution is discongested to 10min under 8000r/min homogenizer and obtain cellulose solution;
The 3rd step, cellulose solution prepared by second step obtains vitreous fibre cellulose solution under the rotating speed of 4000r/min after room temperature evacuation and centrifugal degassing 10min, 2.7%Span-80 is dissolved in Liquid Paraffin and is stirred after 30min with 1000r/min speed, in 1h, add above-mentioned cellulose solution, gained suspension is stirring and emulsifying 5h under the stirring velocity of 1000r/min and room temperature, under these conditions, drip 10% dilute hydrochloric acid and regulate pH to 7.0, suspension solidify to form Regenerated cellulose microspheres, leave standstill, mixture system is divided into two-layer, upper strata is that Liquid Paraffin organic phase can reclaim use by washing, lower floor's water is repeatedly used washing with acetone 3 times after rinsing again with distilled water, obtain the spherical Mierocrystalline cellulose of hole, finally, adopt cooling drying to preserve spherical these holes Mierocrystalline cellulose, the mean pore size of prepared product is 55nm～65nm.
6. the composite passivated modifying agent as described in claim 1 to 5, is characterized in that: the particle diameter of described nanometer iron powder is 50～200nm.
7. the preparation method of composite passivated modifying agent described in claim 1 to 6, is characterized in that, comprising:
The first step, prepares hydroxypropyl modification SiO in accordance with the method for claim 4
2/ chitosan nano particle;
Second step, prepares the spherical Mierocrystalline cellulose of hole in accordance with the method for claim 5;
The 3rd step, is uniformly mixed each component according to above-mentioned weight ratio, obtain described composite passivated modifying agent.
8. the application of described composite passivated modifying agent in heavy metal-polluted soil is processed described in claim 1 to 7.
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