CN105295938A - Heavy metal passivator for reducing bio-availability of cadmium in soil - Google Patents
Heavy metal passivator for reducing bio-availability of cadmium in soil Download PDFInfo
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Abstract
The invention discloses a heavy metal passivator for reducing the bio-availability of cadmium in soil. The heavy metal passivator is prepared by mixing the following components in percentage by weight: 70 to 90 percent of biochar and 10 to 30 percent of modified sodium alginate. The heavy metal passivator disclosed by the invention not only has a function of passivating the heavy metal in the soil in situ, but also is capable of improving the soil structure and increasing the soil porosity, the pH (Potential of Hydrogen) of the soil is increased to a larger extent, and the function of repairing acidified soil is also obtained.
Description
Technical field
The present invention relates to a kind of heavy metal deactivator, particularly a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness.
Background technology
Due to the accelerated development of industrialization and urbanization, China's part agricultural land soil various degrees cadmium (Cd) Pollution risk.It is reported, in China's topsoil soils, the average input rate of Cd is annual 0.004mg/kg, is one of excessive risk heavy metal element.In soil, harmful heavy metal runs up to a certain degree, and Soil degradation, crop yield and quality not only can be caused to decline, and may direct poisonous plant or healthy by food chain approach harm humans.
At present to the existing a lot of report of the research of heavy metal pollution of soil recovery technique, various countries researcher successively explores deep ploughing, casting method, soil moved in improve the original method, thermal desorption method, heat treating process, electrochemical process and the various physical/chemical restorative procedure such as chemical flush method, chemical original position deactivation method.In view of aforesaid method has certain limitation, desirable reclamation activities could not be become, also do not obtain large scale application.As casting method and soil moved in improve the original method, because every mu of soil is up to 150,000 kg, traffic capacity is huge, and cost is too high, and mishandlingly can cause secondary pollution, considers, can not become main flow recovery technique from economy and method angle.Now the most frequently used physical/chemical restorative procedure is the in-situ passivation method of heavy metal-polluted soil, and has begun to take shape the soil heavy metal passivant of the eight large classifications such as alkaline species material, organic materials and composite passivant such as clay mineral, phosphate fertilizer class material, iron and manganese oxides, silicon element class material, trace element fertilizer, iron and manganese oxides.The method adds passivator in contaminated soil, by changing the effective concentration of heavy metal in soil or redox state, thus reducing the effective concentration of heavy metal in soil, reducing the toxicity to organism.In-situ passivation recovery technique is a kind of controlling area-source pollution technology of economical and efficient, due to easy to operate quick with effect, make it in contaminated soil governance process, have not replaceable effect, meet the needs of China's sustainable agriculture development, be subject to soil, environmentalist pays close attention to more and more widely.Such as, utilize industrial waste and agricultural wastes (as red mud, rape stalk, maize straw etc.) in recent years as in-situ passivation agent to reduce the biological effectiveness of Cd in soil, and then prevent its research shifted in food chain from having been reported.Its principle is by changing the existence of heavy metal in soil, making it change stable state into by activated state, thus reduce its toxic action.Charcoal is the high stability solid matter of a class that biomass produce through pyrolysis charring under restriction Oxygen Condition.The raw material sources preparing charcoal are extensive, as agricultural wastes, bamboo wood forest, shell etc.As a kind of novel absorption material, the fine and closely woven porous of its molecule, surface-area is huge, has superpower adsorptive power, is widely used in fields such as environment protection, soil geology and atmospheric sciences.The aspects such as the fresh-keeping and room health care of purification of water quality, air deodorization, damping are usually used in daily life.
Summary of the invention
The object of the present invention is to provide a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness, not only there is the function of in-situ passivation heavy metal-polluted soil, and Soil structure, increase soil porosity can also be improved, improve soil pH value greatly, have the function of repairing acidified soil concurrently.
The technical solution adopted for the present invention to solve the technical problems is:
Reduce a heavy metal deactivator for Cadmium in Soil biological effectiveness, be mixed by the component of following weight percent meter: charcoal 70-90%, modified sodium alginate 10-30%.
The present invention gives full play to the good characteristic of charcoal, heavy metal deactivator is prepared with it, by proper ratio, itself and the mixing of common chemical nitrogen fertilizer are applied to soil, the effect suppressing fertilizer nitrogen volatilization, realize nitrogen slowly-releasing can be played, to alleviation widespread pollution from the overuse of fertilizers and pesticides in rural area, there is very important scientific meaning.
The present invention adopt charcoal and modified sodium alginate composite, charcoal energy passivation Adsorption of Heavy Metals, modified sodium alginate more can directly and heavy metal adsorption react, thus the bio-available Zn concentration of Cadmium in Soil can be reduced, thus reduce plant to the absorbed dose of cadmium.
As preferably, described charcoal is mixed according to the weight ratio of 3:2:1 by bamboo charcoal, pecan shell charcoal and Pericarppium arachidis hypogaeae charcoal.
Contriver is through studying discovery for a long period of time, combine with the charcoal of particular types, especially the charcoal that the waste of this Hangzhou local characteristic of pecan shell charcoal is processed is selected, the combination of these three kinds of charcoals, comprehensive onset, formed charcoal hole, specific surface area etc. in can passivation better, adsorbing heavy metal cadmium.
As preferably, described charcoal uses after dilute alkaline soln process.
As preferably, dilute alkaline soln process is specially: charcoal is placed in the sodium hydroxide solution that concentration is 0.3-0.7mol/L, is heated to 30-40 DEG C, heat-insulation soaking 5-8h, clean with distilled water flushing after taking-up, dries.The present invention passes through, by charcoal through specific dilute alkaline soln treatment process, to control paper mill wastewater, treatment time and temperature, thus changes the surface functional group of charcoal, improves the ability of charcoal passivation, adsorbing heavy metal cadmium.
As preferably, the preparation method of described bamboo charcoal is: by bamboo in oxygen-free environment, cracking 90-120min at 500-700 DEG C and obtaining; The preparation method of described pecan shell charcoal is: by pecan shell in oxygen-free environment, cracking 90-120min at 500-600 DEG C and obtaining; The preparation method of described Pericarppium arachidis hypogaeae charcoal is: by Pericarppium arachidis hypogaeae in oxygen-free environment, cracking 90-120min at 350-500 DEG C and obtaining.The charcoal that the present invention is different adopts different specified temp cracking to produce, the charcoal of formation can passivation better, adsorbing heavy metal cadmium.
As preferably, preparation method's step of described modified sodium alginate is as follows:
(1) by the sodium alginate soln making mass concentration 5-10% soluble in water for sodium alginate;
(2) in sodium alginate soln, add hydrogen peroxide, be heated to 45-50 DEG C, insulation reaction 3-5h under ultrasound condition;
(3) in the sodium alginate soln after step (2) process, gac is added, activated carbon dosage is the 3-5% of the sodium alginate soln weight after step (2) process, stir 1-3h, cross filtering gac, filtrate adds mass concentration 95% ethanol of 6-8 times of volume, alcohol precipitation 8-10h, obtains alcohol hypostasis after suction filtration; Activated carbon treatment can remove partial impurities.
(4) by water-soluble for the alcohol hypostasis alcohol hypostasis solution making mass concentration 10-15%, and regulate pH to 6.0-6.5, alcohol hypostasis solution is mixed with the liquor zinci chloridi of mass concentration 30-50%, be heated to 55-65 DEG C, insulation reaction 15-18h under agitation condition, centrifugal, supernatant liquor obtains modified sodium alginate after vacuum concentration, lyophilize.Alcohol hypostasis (oligosaccharides) and metal-salt (zinc chloride) chelatropic reaction, obtain oligosaccharides-metal complexes and modified sodium alginate, remove heavy metal cadmium effective.
The present invention is by sodium alginate (45-50 DEG C) degraded under hydrogen peroxide, specified temp, be aided with supersound process simultaneously, contribute to the fracture degraded of macromole sodium alginate, auxiliary sodium alginate is degraded to oligosaccharides, for next step DeR is ready, the oligosaccharides polymerization degree prepared is better, is beneficial to the oligosaccharides-metal complexes prepared below, removes heavy metal cadmium better effects if.
As preferably, in step (2), hydrogen peroxide consumption is the 8-10% of sodium alginate soln cumulative volume, and hydrogen peroxide mass concentration is 10-20%.
As preferably, the volume ratio=1:0.5-1 of alcohol hypostasis solution and liquor zinci chloridi in step (4).
The invention has the beneficial effects as follows:
1, not only there is the function of in-situ passivation heavy metal-polluted soil, and Soil structure, increase soil porosity can also be improved, improve soil pH value greatly, have the function of repairing acidified soil concurrently, being applicable to the rice soil that various soil parent material is grown, is a kind of multifunctional broad-spectrum type environmentfriendly products.
2, raw material sources of the present invention are extensive, and preparation method is simple, and application is convenient, are easy to promote, have significant environmental benefit and economic benefit.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Embodiment 1:
Reduce a heavy metal deactivator for Cadmium in Soil biological effectiveness, be mixed by the component of following weight percent meter: charcoal 70%, modified sodium alginate 30%.
Charcoal uses after dilute alkaline soln process, and dilute alkaline soln process is specially: charcoal is placed in the sodium hydroxide solution that concentration is 0.3mol/L, is heated to 30 DEG C, heat-insulation soaking 8h, clean with distilled water flushing after taking-up, dries.
Charcoal is mixed according to the weight ratio of 3:2:1 by bamboo charcoal, pecan shell charcoal and Pericarppium arachidis hypogaeae charcoal.The preparation method of described bamboo charcoal is: by bamboo in oxygen-free environment, cracking 120min at 500 DEG C and obtaining; The preparation method of described pecan shell charcoal is: by pecan shell in oxygen-free environment, cracking 120min at 500 DEG C and obtaining; The preparation method of described Pericarppium arachidis hypogaeae charcoal is: by Pericarppium arachidis hypogaeae in oxygen-free environment, cracking 120min at 350 DEG C and obtaining.
Preparation method's step of described modified sodium alginate is as follows:
(1) by the sodium alginate soln making mass concentration 5% soluble in water for sodium alginate (commercially available).
(2) in sodium alginate soln, add the hydrogen peroxide that mass concentration is 10%, hydrogen peroxide consumption is 10% of sodium alginate soln cumulative volume, is heated to 45 DEG C, (ultrasonic power 150W) insulation reaction 5h under ultrasound condition.
(3) in the sodium alginate soln after step (2) process, gac is added, activated carbon dosage is 3% of the sodium alginate soln weight after step (2) process, stir 1h, cross filtering gac, filtrate adds mass concentration 95% ethanol of 6 times of volumes, alcohol precipitation 8h, obtains alcohol hypostasis after suction filtration.
(4) by water-soluble for the alcohol hypostasis alcohol hypostasis solution making mass concentration 10%, and regulate pH to 6.0, according to the proportioning of volume ratio=1:1, alcohol hypostasis solution is mixed with the liquor zinci chloridi of mass concentration 30%, be heated to 55 DEG C, insulation reaction 18h under agitation condition, centrifugal, supernatant liquor obtains modified sodium alginate after vacuum concentration, lyophilize.
Embodiment 2:
Reduce a heavy metal deactivator for Cadmium in Soil biological effectiveness, be mixed by the component of following weight percent meter: charcoal 90%, modified sodium alginate 10%.
Charcoal uses after dilute alkaline soln process, and dilute alkaline soln process is specially: charcoal is placed in the sodium hydroxide solution that concentration is 0.7mol/L, is heated to 40 DEG C, heat-insulation soaking 5h, clean with distilled water flushing after taking-up, dries.
Charcoal is mixed according to the weight ratio of 3:2:1 by bamboo charcoal, pecan shell charcoal and Pericarppium arachidis hypogaeae charcoal.The preparation method of described bamboo charcoal is: by bamboo in oxygen-free environment, cracking 90min at 700 DEG C and obtaining; The preparation method of described pecan shell charcoal is: by pecan shell in oxygen-free environment, cracking 90min at 600 DEG C and obtaining; The preparation method of described Pericarppium arachidis hypogaeae charcoal is: by Pericarppium arachidis hypogaeae in oxygen-free environment, cracking 90min at 500 DEG C and obtaining.
Preparation method's step of described modified sodium alginate is as follows:
(1) by the sodium alginate soln making mass concentration 10% soluble in water for sodium alginate (commercially available).
(2) in sodium alginate soln, add the hydrogen peroxide that mass concentration is 20%, hydrogen peroxide consumption is 8% of sodium alginate soln cumulative volume, is heated to 50 DEG C, insulation reaction 3h under ultrasound condition.
(3) in the sodium alginate soln after step (2) process, gac is added, activated carbon dosage is 5% of the sodium alginate soln weight after step (2) process, stir 3h, cross filtering gac, filtrate adds mass concentration 95% ethanol of 8 times of volumes, alcohol precipitation 10h, obtains alcohol hypostasis after suction filtration.
(4) by water-soluble for the alcohol hypostasis alcohol hypostasis solution making mass concentration 15%, and regulate pH to 6.5, according to the proportioning of volume ratio=1:0.5, alcohol hypostasis solution is mixed with the liquor zinci chloridi of mass concentration 50%, be heated to 65 DEG C, insulation reaction 15h under agitation condition, centrifugal, supernatant liquor obtains modified sodium alginate after vacuum concentration, lyophilize.
Embodiment 3:
Reduce a heavy metal deactivator for Cadmium in Soil biological effectiveness, be mixed by the component of following weight percent meter: charcoal 80%, modified sodium alginate 20%.
Charcoal uses after dilute alkaline soln process, and dilute alkaline soln process is specially: charcoal is placed in the sodium hydroxide solution that concentration is 0.5mol/L, is heated to 35 DEG C, heat-insulation soaking 6h, clean with distilled water flushing after taking-up, dries.
Charcoal is mixed according to the weight ratio of 3:2:1 by bamboo charcoal, pecan shell charcoal and Pericarppium arachidis hypogaeae charcoal.The preparation method of described bamboo charcoal is: by bamboo in oxygen-free environment, cracking 100min at 600 DEG C and obtaining; The preparation method of described pecan shell charcoal is: by pecan shell in oxygen-free environment, cracking 100min at 550 DEG C and obtaining; The preparation method of described Pericarppium arachidis hypogaeae charcoal is: by Pericarppium arachidis hypogaeae in oxygen-free environment, cracking 100min at 400 DEG C and obtaining.
Preparation method's step of described modified sodium alginate is as follows:
(1) by the sodium alginate soln making mass concentration 8% soluble in water for sodium alginate (commercially available).
(2) in sodium alginate soln, add the hydrogen peroxide that mass concentration is 15%, hydrogen peroxide consumption is 9% of sodium alginate soln cumulative volume, is heated to 50 DEG C, insulation reaction 4h under ultrasound condition.
(3) in the sodium alginate soln after step (2) process, gac is added, activated carbon dosage is 4% of the sodium alginate soln weight after step (2) process, stir 2h, cross filtering gac, filtrate adds mass concentration 95% ethanol of 7 times of volumes, alcohol precipitation 9h, obtains alcohol hypostasis after suction filtration.
(4) by water-soluble for the alcohol hypostasis alcohol hypostasis solution making mass concentration 12%, and regulate pH to 6.0, according to the proportioning of volume ratio=1:0.8, alcohol hypostasis solution is mixed with the liquor zinci chloridi of mass concentration 40%, be heated to 60 DEG C, insulation reaction 16h under agitation condition, centrifugal, supernatant liquor obtains modified sodium alginate after vacuum concentration, lyophilize.
Heavy metal deactivator of the present invention is utilized to carry out pot experiment
5 process are established in test.Get heavy metal deactivator of the present invention, 0.5% (T1), 1.0% (T2), 2.5% (T3), 5.0% (T4) four Pitch-based sphere are set respectively, with gather in advance and cross the topsoil gong Homogeneous phase mixing that 2mm sieves, load engagement.2.0kg loaded by every basin.Supplying to study thing is Xiaoqinling Nature Reserve.Transplanting having planted the identical Xiaoqinling Nature Reserve of growing way in advance respectively in experiment basin, starting test.Wherein Cd concentration adopts CdCl
2solution external source is allocated, and unified allocation of resources is to the initial cadmium concentration 50mg/kg of soil.Conventional fertilizer application is according to N:P
2o
5: K
2o=2:1:1.2 implements, and the sowing amount of N presses 180kg/hm
2, wherein azophoska is provided by urea, normal superphosphate and Repone K respectively.Establish pure soil contrast (representing with CK) of not adding heavy metal deactivator simultaneously.Each process repetition 4 times.Water with deionized water, gather pedotheque in experiment basin after 3 months, results Xiaoqinling Nature Reserve carries out drying and processing, analytic sample cadmium concentration.The results are shown in Table 1, as shown in Table 1, after adding heavy metal deactivator of the present invention, soil available cadmium relative concentration obviously reduces in control group, and the total Cd relative concentration of Xiaoqinling Nature Reserve also significantly reduces in control group.
Table 1 different treatment soil available cadmium concentration and the total cadmium concentration of Xiaoqinling Nature Reserve
| Process | Soil available cadmium concentration (mg/kg) | The total Cd concentration (mg/kg) of Xiaoqinling Nature Reserve |
| CK | 20.5±0.99 | 47.8±3.22 |
| T1 | 18.7±1.16 | 32.1±1.54 |
| T 2 | 17.5±0.81 | 29.4±3.76 |
| T 3 | 16.2±1.23 | 25.9±2.23 |
| T 4 | 15.6±1.60 | 21.7±4.17 |
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (8)
1. reduce a heavy metal deactivator for Cadmium in Soil biological effectiveness, it is characterized in that, be mixed by the component of following weight percent meter: charcoal 70-90%, modified sodium alginate 10-30%.
2. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 1, is characterized in that: described charcoal is mixed according to the weight ratio of 3:2:1 by bamboo charcoal, pecan shell charcoal and Pericarppium arachidis hypogaeae charcoal.
3. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 1 and 2, is characterized in that: described charcoal uses after dilute alkaline soln process.
4. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 3, it is characterized in that: dilute alkaline soln process is specially: charcoal is placed in the sodium hydroxide solution that concentration is 0.3-0.7mol/L, be heated to 30-40 DEG C, heat-insulation soaking 5-8h, clean with distilled water flushing after taking-up, dry.
5. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 1 and 2, is characterized in that, the preparation method of described bamboo charcoal is: by bamboo in oxygen-free environment, cracking 90-120min at 500-700 DEG C and obtaining; The preparation method of described pecan shell charcoal is: by pecan shell in oxygen-free environment, cracking 90-120min at 500-600 DEG C and obtaining; The preparation method of described Pericarppium arachidis hypogaeae charcoal is: by Pericarppium arachidis hypogaeae in oxygen-free environment, cracking 90-120min at 350-500 DEG C and obtaining.
6. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 1, is characterized in that, preparation method's step of described modified sodium alginate is as follows:
(1) by the sodium alginate soln making mass concentration 5-10% soluble in water for sodium alginate;
(2) in sodium alginate soln, add hydrogen peroxide, be heated to 45-50 DEG C, insulation reaction 3-5h under ultrasound condition;
(3) in the sodium alginate soln after step (2) process, gac is added, activated carbon dosage is the 3-5% of the sodium alginate soln weight after step (2) process, stir 1-3h, cross filtering gac, filtrate adds mass concentration 95% ethanol of 6-8 times of volume, alcohol precipitation 8-10h, obtains alcohol hypostasis after suction filtration;
(4) by water-soluble for the alcohol hypostasis alcohol hypostasis solution making mass concentration 10-15%, and regulate pH to 6.0-6.5, alcohol hypostasis solution is mixed with the liquor zinci chloridi of mass concentration 30-50%, be heated to 55-65 DEG C, insulation reaction 15-18h under agitation condition, centrifugal, supernatant liquor obtains modified sodium alginate after vacuum concentration, lyophilize.
7. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 6, is characterized in that: in step (2), hydrogen peroxide consumption is the 8-10% of sodium alginate soln cumulative volume, and hydrogen peroxide mass concentration is 10-20%.
8. a kind of heavy metal deactivator reducing Cadmium in Soil biological effectiveness according to claim 6, is characterized in that: the volume ratio=1:0.5-1 of alcohol hypostasis solution and liquor zinci chloridi in step (4).
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| CN107824612A (en) * | 2017-11-04 | 2018-03-23 | 江西夏氏春秋环境股份有限公司 | A kind of Fe3O4The preparation method of base charcoal soil passivator |
| CN107824612B (en) * | 2017-11-04 | 2018-09-28 | 江西夏氏春秋环境股份有限公司 | A kind of Fe3O4The preparation method of base charcoal soil passivator |
| CN107955615A (en) * | 2017-11-20 | 2018-04-24 | 湖南农业大学 | A kind of biology drop cadmium agent |
| US11124461B2 (en) | 2019-07-04 | 2021-09-21 | Incitec Pivot Limited | Fertilizer |
| US11691929B2 (en) | 2019-07-04 | 2023-07-04 | Incitec Fertilizers Pty Limited | Fertiliser |
| CN113773849A (en) * | 2021-09-23 | 2021-12-10 | 湖南国重环境科技有限责任公司 | Slow-release heavy metal fixing agent, preparation method thereof and application thereof in remediation of heavy metal contaminated farmland soil |
| CN114181323A (en) * | 2021-12-14 | 2022-03-15 | 舟山市食品药品检验检测研究院 | Method for enriching and purifying heavy metals in seawater |
| CN114181323B (en) * | 2021-12-14 | 2022-07-26 | 舟山市食品药品检验检测研究院 | Method for enriching and purifying heavy metals in seawater |
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