CN105295938B - The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil - Google Patents

The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil Download PDF

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CN105295938B
CN105295938B CN201510645721.2A CN201510645721A CN105295938B CN 105295938 B CN105295938 B CN 105295938B CN 201510645721 A CN201510645721 A CN 201510645721A CN 105295938 B CN105295938 B CN 105295938B
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charcoal
sodium alginate
soil
heavy metal
cadmium
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CN105295938A (en
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刘玉学
汪玉瑛
吕豪豪
杨生茂
钟哲科
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Zhejiang Academy of Agricultural Sciences
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Zhejiang Academy of Agricultural Sciences
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Abstract

The invention discloses a kind of heavy metal deactivators of bioavailability of cadmium in reduction soil, are mixed by the component of following weight percent meter:Charcoal 70-90%, modified sodium alginate 10-30%.The present invention not only has the function of in-situ passivation heavy metal-polluted soil, but also can also improve soil texture, increase soil porosity, greatly improves soil pH value, has both the function of repairing acidified soil.

Description

The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil
Technical field
The present invention relates to a kind of heavy metal deactivator, more particularly to a kind of heavy metal reducing bioavailability of cadmium in soil Passivator.
Background technology
Due to industrializing the accelerated development with urbanization, China part agricultural land soil various degrees cadmium (Cd) pollution Risk.It is reported that in China's topsoil soils Cd average input rate be annual 0.004mg/kg, be high risk heavy metal element it One.Harmful heavy metal accumulation to a certain extent, not only results in soil degradation, crop yield and quality decline in soil, and And directly poisonous plant or human health may be endangered by food chain approach.
Have many reports to the research of heavy metal pollution of soil recovery technique at present, various countries researcher successively explores Deep ploughing, casting method, heavy metal pollution of soil, thermal desorption method, heat treating process, electrochemical process and chemical flush method, chemical in situ deactivation method etc. Various physical/chemical restorative procedures.There is certain limitation in view of the above method, ideal reclamation activities could not be become, It is not widely applied.Such as casting method and heavy metal pollution of soil, because soil is up to 150,000 kg per acre, freight volume is huge, and cost is too Height, and it is mishandling can cause secondary pollution, consider from economy and method angle, it is impossible to become mainstream recovery technique.It is existing It is the in-situ passivation method of heavy metal-polluted soil in most common physical/chemical restorative procedure, and has preliminarily formed clay mineral, phosphate fertilizer The alkalinity such as substance, iron and manganese oxides, silicon element substance, trace-element fertilizer, iron and manganese oxides substance, organic materials and multiple Close the other soil heavy metal passivants of eight major class such as passivator.This method is that passivator is added in contaminated soil, passes through change Heavy metal effective concentration in the soil or redox state, to reduce the effective concentration of heavy metal in the soil, drop The low toxicity to organism.In-situ passivation recovery technique is a kind of controlling area-source pollution technology of economical and efficient, due to operation side Just quick with effect, so that it is had not replaceable effect in contaminated soil governance process, meets China's sustainable agriculture hair The needs of exhibition, by the more and more extensive concern of soil, environmentalist.For example, utilizing industrial waste and agriculture waste in recent years Object (such as red mud, rape stalk, maize straw) reduces the biological effectiveness of Cd in soil, Jin Erfang as in-situ passivation agent Only its research shifted into food chain has been reported.Its principle is by changing the existence of heavy metal in the soil, making It is changed into stable state by activated state, to reduce its toxic action.Charcoal be biomass in the case where limiting Oxygen Condition through heat A kind of highly stable solid matter that solution charing generates.The raw material sources for preparing charcoal are extensive, such as agricultural wastes, bamboo wood Forest, shell etc..As a kind of novel absorption material, molecule is fine and closely woven porous, and surface area is huge, has superpower adsorption energy Power is widely used in fields such as environmental protection, soil geology and atmospheric science.It is usually used in purification of water quality, sky in daily life Gas deodorization, damping be fresh-keeping and room health care etc..
Invention content
The purpose of the present invention is to provide a kind of heavy metal deactivators of bioavailability of cadmium in reduction soil, not only have The function of in-situ passivation heavy metal-polluted soil, and soil texture can also be improved, increase soil porosity, greatly improve soil Earth pH value has both the function of repairing acidified soil.
The technical solution adopted by the present invention to solve the technical problems is:
The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil is mixed by the component of following weight percent meter It is made:Charcoal 70-90%, modified sodium alginate 10-30%.
The present invention gives full play to the good characteristic of charcoal, uses it to prepare heavy metal deactivator, by proper ratio by its It is applied to soil with the mixing of common chemical nitrogen fertilizer, the effect for inhibiting fertilizer nitrogen volatilization, realizing nitrogen sustained release can be played, to slow Solving agricultural non-point source pollution has highly important scientific meaning.
The present invention is compounded using charcoal and modified sodium alginate, and charcoal can be passivated absorption heavy metal, modified alginic acid Sodium more can directly be reacted with heavy metal adsorption, so as to reduce the bio-available Zn concentration of cadmium in soil, to reduce plant to cadmium Uptake.
Preferably, the charcoal by bamboo charcoal, pecan shell charcoal and peanut shell charcoal according to 3:2:1 weight ratio mixing and At.
Inventor is combined with particular kind of charcoal by the discovery that studies for a long period of time, especially selects pecan shell The charcoal of the waste processing of this Hangzhou local characteristic of charcoal, the combination of these three charcoals is comprehensive to work, in the hole of the charcoal of formation Gap, specific surface area etc. can preferably be passivated, adsorbing heavy metal cadmium.
Preferably, the charcoal uses after dilute alkaline soln is handled.
Preferably, dilute alkaline soln processing is specially:Charcoal is placed in the sodium hydroxide of a concentration of 0.3-0.7mol/L In solution, it is heated to 30-40 DEG C, heat-insulation soaking 5-8h, clean with distilled water flushing after taking-up, drying.The present invention will be by that will give birth to Object charcoal passes through specific dilute alkaline soln treatment process, concentration, processing time and the temperature of alkali is controlled, to change the table of charcoal Face functional group, improve charcoal passivation, adsorbing heavy metal cadmium ability.
Preferably, the preparation method of the bamboo charcoal is:By bamboo in oxygen-free environment, 90- is cracked at 500-700 DEG C 120min and obtain;The preparation method of the pecan shell charcoal is:By pecan shell in oxygen-free environment, cracked at 500-600 DEG C 90-120min and obtain;The preparation method of the peanut shell charcoal is:By peanut shell in oxygen-free environment, cracked at 350-500 DEG C 90-120min and obtain.For the different charcoal of the present invention using different specific temperature cracking production, the charcoal of formation can be more preferable Ground passivation, adsorbing heavy metal cadmium.
Preferably, steps are as follows for the preparation method of the modified sodium alginate:
(1) by the sodium alginate sodium alginate soln soluble in water that mass concentration 5-10% is made;
(2) hydrogen peroxide is added into sodium alginate soln, is heated to 45-50 DEG C, insulation reaction 3-5h under ultrasound condition;
(3) activated carbon is added into step (2) treated sodium alginate soln, activated carbon dosage is step (2) processing The 3-5% of sodium alginate soln weight afterwards stirs 1-3h, crosses and filters out activated carbon, and the mass concentration of 6-8 times of volume is added in filtrate 95% ethyl alcohol, alcohol precipitation 8-10h, after suction filtration alcohol hypostasis;Activated carbon processing can remove partial impurities.
(4) alcohol hypostasis is dissolved in water and the alcohol hypostasis solution of mass concentration 10-15% is made, and adjust pH to 6.0-6.5, it will Alcohol hypostasis solution is uniformly mixed with the liquor zinci chloridi of mass concentration 30-50%, is heated to 55-65 DEG C, is kept the temperature under stirring condition 15-18h, centrifugation are reacted, supernatant obtains modified sodium alginate after being concentrated in vacuo, being freeze-dried.Alcohol hypostasis (oligosaccharides) and metal Salt (zinc chloride) chelatropic reaction, obtains oligosaccharides-metal complex, that is, modified sodium alginate, and removing heavy metal cadmium effect is good.
The present invention (45-50 DEG C) degradation under hydrogen peroxide, specific temperature by sodium alginate, while being aided with supersound process, have Helping the fracture degradation of macromolecular sodium alginate, auxiliary sodium alginate is degraded to oligosaccharides, is ready for next step degradation reaction, The oligosaccharides degree of polymerization prepared is better, and conducive to the oligosaccharides-metal complex prepared below, removing heavy metal cadmium effect is more preferable.
Preferably, dioxygen water consumption is the 8-10% of sodium alginate soln total volume in step (2), dioxygen water quality is dense Degree is 10-20%.
Preferably, in step (4) alcohol hypostasis solution and liquor zinci chloridi volume ratio=1:0.5-1.
The beneficial effects of the invention are as follows:
1, not only have the function of in-situ passivation heavy metal-polluted soil, but also soil texture can also be improved, increase soil aperture Degree, greatly improves soil pH value, has both the function of repairing acidified soil, is suitable for the rice of various soil parent materials development Soil is a kind of multifunctional broad-spectrum type environment-friendly products.
2, raw material sources of the present invention are extensive, and preparation method is simple, easy to spread using convenience, have significant ring Border benefit and economic benefit.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art. Method in following embodiments is unless otherwise instructed the conventional method of this field.
Embodiment 1:
The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil is mixed by the component of following weight percent meter It is made:Charcoal 70%, modified sodium alginate 30%.
Charcoal uses after dilute alkaline soln is handled, and dilute alkaline soln processing is specially:Charcoal is placed in a concentration of In the sodium hydroxide solution of 0.3mol/L, 30 DEG C, heat-insulation soaking 8h are heated to, clean with distilled water flushing after taking-up, drying.
Charcoal is by bamboo charcoal, pecan shell charcoal and peanut shell charcoal according to 3:2:1 weight ratio mixes.The bamboo charcoal Preparation method is:By bamboo in oxygen-free environment, cracks 120min at 500 DEG C and obtain;The preparation method of the pecan shell charcoal For:By pecan shell in oxygen-free environment, cracks 120min at 500 DEG C and obtain;The preparation method of the peanut shell charcoal is:It will spend Raw shell cracks 120min at 350 DEG C and obtains in oxygen-free environment.
Steps are as follows for the preparation method of the modified sodium alginate:
(1) by sodium alginate (commercially available) sodium alginate soln soluble in water that mass concentration 5% is made.
(2) hydrogen peroxide that mass concentration is 10% is added into sodium alginate soln, dioxygen water consumption is that sodium alginate is molten The 10% of liquid total volume is heated to 45 DEG C, (ultrasonic power 150W) insulation reaction 5h under ultrasound condition.
(3) activated carbon is added into step (2) treated sodium alginate soln, activated carbon dosage is step (2) processing The 3% of sodium alginate soln weight afterwards stirs 1h, crosses and filters out activated carbon, and 95% second of mass concentration of 6 times of volumes is added in filtrate Alcohol, alcohol precipitation 8h, after suction filtration alcohol hypostasis.
(4) alcohol hypostasis is dissolved in water and the alcohol hypostasis solution of mass concentration 10% is made, and adjust pH to 6.0, according to volume Than=1:Alcohol hypostasis solution is uniformly mixed by 1 proportioning with the liquor zinci chloridi of mass concentration 30%, is heated to 55 DEG C, stirring bar Insulation reaction 18h under part, centrifugation, supernatant obtain modified sodium alginate after being concentrated in vacuo, being freeze-dried.
Embodiment 2:
The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil is mixed by the component of following weight percent meter It is made:Charcoal 90%, modified sodium alginate 10%.
Charcoal uses after dilute alkaline soln is handled, and dilute alkaline soln processing is specially:Charcoal is placed in a concentration of In the sodium hydroxide solution of 0.7mol/L, 40 DEG C, heat-insulation soaking 5h are heated to, clean with distilled water flushing after taking-up, drying.
Charcoal is by bamboo charcoal, pecan shell charcoal and peanut shell charcoal according to 3:2:1 weight ratio mixes.The bamboo charcoal Preparation method is:By bamboo in oxygen-free environment, cracks 90min at 700 DEG C and obtain;The preparation method of the pecan shell charcoal For:By pecan shell in oxygen-free environment, cracks 90min at 600 DEG C and obtain;The preparation method of the peanut shell charcoal is:It will spend Raw shell cracks 90min at 500 DEG C and obtains in oxygen-free environment.
Steps are as follows for the preparation method of the modified sodium alginate:
(1) by sodium alginate (commercially available) sodium alginate soln soluble in water that mass concentration 10% is made.
(2) hydrogen peroxide that mass concentration is 20% is added into sodium alginate soln, dioxygen water consumption is that sodium alginate is molten The 8% of liquid total volume is heated to 50 DEG C, insulation reaction 3h under ultrasound condition.
(3) activated carbon is added into step (2) treated sodium alginate soln, activated carbon dosage is step (2) processing The 5% of sodium alginate soln weight afterwards stirs 3h, crosses and filters out activated carbon, and 95% second of mass concentration of 8 times of volumes is added in filtrate Alcohol, alcohol precipitation 10h, after suction filtration alcohol hypostasis.
(4) alcohol hypostasis is dissolved in water and the alcohol hypostasis solution of mass concentration 15% is made, and adjust pH to 6.5, according to volume Than=1:Alcohol hypostasis solution is uniformly mixed by 0.5 proportioning with the liquor zinci chloridi of mass concentration 50%, is heated to 65 DEG C, stirring Under the conditions of insulation reaction 15h, centrifugation, supernatant after being concentrated in vacuo, being freeze-dried modified sodium alginate.
Embodiment 3:
The heavy metal deactivator of bioavailability of cadmium in a kind of reduction soil is mixed by the component of following weight percent meter It is made:Charcoal 80%, modified sodium alginate 20%.
Charcoal uses after dilute alkaline soln is handled, and dilute alkaline soln processing is specially:Charcoal is placed in a concentration of In the sodium hydroxide solution of 0.5mol/L, 35 DEG C, heat-insulation soaking 6h are heated to, clean with distilled water flushing after taking-up, drying.
Charcoal is by bamboo charcoal, pecan shell charcoal and peanut shell charcoal according to 3:2:1 weight ratio mixes.The bamboo charcoal Preparation method is:By bamboo in oxygen-free environment, cracks 100min at 600 DEG C and obtain;The preparation method of the pecan shell charcoal For:By pecan shell in oxygen-free environment, cracks 100min at 550 DEG C and obtain;The preparation method of the peanut shell charcoal is:It will spend Raw shell cracks 100min at 400 DEG C and obtains in oxygen-free environment.
Steps are as follows for the preparation method of the modified sodium alginate:
(1) by sodium alginate (commercially available) the sodium alginate soln soluble in water that mass concentration 8% is made
(2) hydrogen peroxide that mass concentration is 15% is added into sodium alginate soln, dioxygen water consumption is that sodium alginate is molten The 9% of liquid total volume is heated to 50 DEG C, insulation reaction 4h under ultrasound condition.
(3) activated carbon is added into step (2) treated sodium alginate soln, activated carbon dosage is step (2) processing The 4% of sodium alginate soln weight afterwards stirs 2h, crosses and filters out activated carbon, and 95% second of mass concentration of 7 times of volumes is added in filtrate Alcohol, alcohol precipitation 9h, after suction filtration alcohol hypostasis.
(4) alcohol hypostasis is dissolved in water and the alcohol hypostasis solution of mass concentration 12% is made, and adjust pH to 6.0, according to volume Than=1:Alcohol hypostasis solution is uniformly mixed by 0.8 proportioning with the liquor zinci chloridi of mass concentration 40%, is heated to 60 DEG C, stirring Under the conditions of insulation reaction 16h, centrifugation, supernatant after being concentrated in vacuo, being freeze-dried modified sodium alginate.
Pot experiment is carried out using the heavy metal deactivator of the present invention
Experiment sets 5 processing.Take the present invention heavy metal deactivator, be respectively set 0.5% (T1), 1.0% (T2), 2.5% (T3), 5.0% (T4) four pitch-based spheres are uniformly mixed with the advance topsoil for acquiring and crossing 2mm sieves, are loaded Enter basin.2.0kg is loaded per basin.It is Xiaoqinling Nature Reserve for studying object.The identical Xiaoqinling Nature Reserve of growing way will have been planted in advance to be transplanted respectively to reality It tests in basin, starts to test.Wherein Cd concentration uses CdCl2Solution external source is allocated, unified allocation of resources to the initial cadmium concentration 50mg/ of soil kg.Conventional fertilizer application is according to N:P2O5:K2O=2:1:1.2 implement, and the sowing amount of N presses 180kg/hm2, wherein nitrogen, phosphorus and potassium fertilizer respectively by Urea, normal superphosphate and potassium chloride provide.The pure soil control (being indicated with CK) for not adding heavy metal deactivator is set simultaneously.Often A processing is repeated 4 times.It is poured with deionized water, pedotheque, harvest Xiaoqinling Nature Reserve are dried in acquisition experiment basin after 3 months Sample cadmium concentration is analyzed in dry-cure.1 is the results are shown in Table, as shown in Table 1, soil is effective after adding the heavy metal deactivator of the present invention State Cd concentration is substantially reduced relative to control group, and the total Cd concentration of Xiaoqinling Nature Reserve is significantly reduced relative to control group.
1 different disposal soil available cadmium concentration of table and the total cadmium concentration of Xiaoqinling Nature Reserve
Processing 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-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.

Claims (4)

1. a kind of heavy metal deactivator reducing bioavailability of cadmium in soil, which is characterized in that by following weight percent meter Component be mixed:Charcoal 70-90%, modified sodium alginate 10-30%;
The charcoal is mixed by bamboo charcoal, pecan shell charcoal and peanut shell charcoal according to 3: 2: 1 weight ratio;Charcoal is through dilute It is used after alkaline solution treatment:Charcoal is placed in the sodium hydroxide solution of a concentration of 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, drying;
Steps are as follows for the preparation method of the modified sodium alginate:
(1) by the sodium alginate sodium alginate soln soluble in water that mass concentration 5-10% is made;
(2) hydrogen peroxide is added into sodium alginate soln, is heated to 45-50 DEG C, insulation reaction 3-5h under ultrasound condition;
(3) activated carbon is added into step (2) treated sodium alginate soln, activated carbon dosage is that treated for step (2) The 3-5% of sodium alginate soln weight stirs 1-3h, crosses and filters out activated carbon, and the mass concentration 95% of 6-8 times of volume is added in filtrate Ethyl alcohol, alcohol precipitation 8-10h, after suction filtration alcohol hypostasis;
(4) alcohol hypostasis is dissolved in water and the alcohol hypostasis solution of mass concentration 10-15% is made, and adjust pH to 6.0-6.5, by alcohol precipitation Object solution is uniformly mixed with the liquor zinci chloridi of mass concentration 30-50%, is heated to 55-65 DEG C, insulation reaction under stirring condition 15-18h, centrifugation, supernatant obtain modified sodium alginate after being concentrated in vacuo, being freeze-dried.
2. a kind of heavy metal deactivator reducing bioavailability of cadmium in soil according to claim 1, which is characterized in that The preparation method of the bamboo charcoal is:By bamboo in oxygen-free environment, cracks 90-120min at 500-700 DEG C and obtain;The mountain core The preparation method of peach shell charcoal is:By pecan shell in oxygen-free environment, cracks 90-120min at 500-600 DEG C and obtain;The flower The preparation method of raw shell charcoal is:By peanut shell in oxygen-free environment, cracks 90-120min at 350-500 DEG C and obtain.
3. a kind of heavy metal deactivator reducing bioavailability of cadmium in soil according to claim 1, it is characterised in that: Dioxygen water consumption is the 8-10% of sodium alginate soln total volume in step (2), and hydrogen peroxide mass concentration is 10-20%.
4. a kind of heavy metal deactivator reducing bioavailability of cadmium in soil according to claim 3, it is characterised in that: Volume ratio=1 of alcohol hypostasis solution and liquor zinci chloridi in step (4): 0.5-1.
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