CN107502357A - A kind of heavy metal-polluted soil renovation agent and preparation method thereof - Google Patents
A kind of heavy metal-polluted soil renovation agent and preparation method thereof Download PDFInfo
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- CN107502357A CN107502357A CN201710598811.XA CN201710598811A CN107502357A CN 107502357 A CN107502357 A CN 107502357A CN 201710598811 A CN201710598811 A CN 201710598811A CN 107502357 A CN107502357 A CN 107502357A
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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
- C09K17/06—Calcium compounds, e.g. lime
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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
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
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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
- C09K2101/00—Agricultural use
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention discloses a kind of heavy metal-polluted soil renovation agent and preparation method thereof, is to carry out overlay film to carrier using the modified biomass charcoal impregnated of rich calcium constituent and iron and manganese oxides as carrier, and using nano-scale magnetic material；The particle diameter of product is in 0.25 5mm, and the Fe contents of product are 2 5%, Mn contents are 5 10%, Ca contents are 10 15%.The renovation agent all has certain repair to the single and combined pollution of the cadmium under different pH backgrounds, chromium, arsenic, lead and mercury, so as to which the reparation to contaminated soil and food security all have certain contribution function.The renovation agent prepared using the present invention, can substantially effectively have the repair materials of special passivation using heavy metal, realize the purpose that spectrum reparation is carried out to heavy metal pollution of soil.
Description
Technical field
The invention belongs to soil restoring technology, will be specifically to be related to a kind of rich calcium, iron, the manganese of magnetic Nano material overlay film
Multielement composite biomass charcoal heavy metal-polluted soil renovation agent and preparation method thereof.
Technical background
As global pollution problem, the heavy metal pollution problem of soil receives the concern of related researcher, weight
Metallic pollution mainly includes the heavy metal pollutions such as cadmium, lead, chromium, mercury and arsenic.Increasing industrial activity and municipal refuse are not
Appropriate processing, also makes heavy metal pollution of soil problem increasingly sharpen.Because heavy metal pollution of soil has certain disguise, no
The features such as degradability, the heavy metal pollution of soil is caused to show the features such as concentration is high, species is more (Cheng, 2003).And weigh
Metal is migrated by food chain transmission, and caused toxicity amplification is that heavy metal is main to caused by human health in vivo
Threaten (Bernard, 2008；Dudka and Miller,1999；Horiguchi etc., 2013；2003；Singh
Deng 2010).Therefore, how using efficient, reliable control measures the migration of heavy metal in soil and biologically effective to be reduced
Property, it is the key issue for alleviating current heavy metal pollution of soil.
As a kind of stability material of rich charcoal, biomass carbon is due to higher pore structure, active functional group
And higher pH and CEC, obtained in terms of heavy metal pollution of soil is administered relatively broad application (Beesley etc., 2011；
Zhang etc., 2013；Joseph etc., 2013).Reduction of the bright biomass carbon of short-term table of field test results to rice grain cadmium
Amplitude may be up to 90% (Bian etc., 2013).However, larger otherness be present in the regulation effect of biomass carbon heavy metal,
This is due to that the difference of the preparation conditions such as raw materials for production, carburizing temperature can produce considerable influence to the property of biomass carbon.It is same
Under carburizing temperature, from the biomass carbon of shell, wood chip etc., although with higher specific surface area, abundant functional group with
And more oxygen-containing functional group, but its ash content and cation exchange capacity (CEC) are all than relatively low (Yuan Jinhua etc., 2011)；And stalk is biological
Preferably suppress to make although functional group and the heavy metal such as higher content of ashes, silicon, iron, manganese of the matter with compared with horn of plenty have
The content of beneficial element is relatively low.And identical material, due to the difference of carburizing temperature, property also has larger difference,
Pyrocarbon has higher content of ashes, but functional group content declines, and then on the contrary, therefore, biomass carbon is to a huge sum of money during low temperature
The regulation effect of category can have larger floatability due to the difference of preparation condition.Secondly, it is raw when heavy metal concentration is higher
The passivation effect of material charcoal heavy metal can be by larger suppression (Ma etc., 2014).
In recent years, modification of the researcher to biomass carbon improves controlling for biomass carbon heavy metal to a certain extent
Manage effect.Due to the effects such as biomass carbon mainly adsorbed by hole, functional groups, liming effect and Electrostatic Absorption come pair
Heavy metal produces certain absorption and passivation.Therefore, the modification to biomass carbon at present mainly by steam activation,
Heating, sour modification, alkali modification etc. increase the porosity of biomass carbon and functional group etc., so as to by improving biomass carbon
Physicochemical property strengthen the regulation effect of its heavy metal.In addition, by infusion process, metal salt and oxide or magnetic are utilized
The processing such as modified increases the hot research that the adsorption site of biomass carbon heavy metal is also current biomass carbon modification
Direction (Ahmed etc., 2016).
Iron and manganese oxides are composite oxides relatively conventional in environment, are had relative to single oxide higher
Adsorption capacity (Goh etc., 2008).Although iron and manganese oxides are not the key components of soil solid portion, due to compared with
High specific surface area, and higher surface charge density and control heavy metal-polluted soil migration and biological effectiveness in terms of have
More important effect (McKenzie 1980；Contin etc., 2007；Manceau etc., 2007；Stipp etc., 2002).Research
Show, iron and manganese oxides to arsenic, mercury, lead and all have preferable suction-operated (Lu etc., 2014；Wang and Mulligan,
2008；Fabisch etc., 2013；Ainsworth etc., 1994).The adsorption effect of iron and manganese oxides heavy metal is in many degree
It is upper depending on iron and manganese oxides grade size (Buj ň á kov á etc., 2013；Yean etc., 2005), however, under natural conditions
Iron and manganese oxides are easy to be gathered into the large particulate matters such as iron-manganese concretion, so as to reduce the adsorption effect of its heavy metal.
Migration and bioavailability of the pH value of soil to heavy metal-polluted soil have decisive role, pass through oxytropism soil
Heavy metal-polluted soil can be passivated to a certain extent to improve soil pH by applying the basic matterials such as lime in earth, and can be passed through
Base exchange process reduces the biological accessibility of heavy metal-polluted soil (Guo etc., 2006).Research shows, by into soil
The utilizability of soil calcium, magnesium can be improved to a certain extent by applying lime, so as to improve soil nutrient and interchangeability sun
Ion concentration, meanwhile, iron oxide precipitation can also increase (J.Derome 2000) with the enhancing of liming effect.As conventional
One of control measures, by into soil liming shown the drawbacks of certain, soil hardening to administer heavy metal
It is exactly more distinct issues, and the heavy metal being passivated by liming effect is also present by the work of the soil acidification such as acid rain process
Change, therefore, single application lime can only cure the symptoms, not the disease to administer heavy metal pollution of soil.
In recent years, the correlative study of nano level Fe/Ca/CaO composites appears in heavy metal pollution of soil and administers neck
Domain, this advanced composite material (ACM) is to the clearance of arsenic, cadmium, chromium and lead up to 65-80% (Srinivasa etc., 2013).But this
Requirement of the class material to soil moisture is higher.The application of nano-scale magnetic iron oxide is new in Environment control heavy metal pollution field
Research direction, the magnetic modification of biomass carbon can improve biomass carbon by forming the oxide of iron on biomass carbon surface
To the adsorption efficiency of cadmium, chromium and copper (Mohan etc., 2014；Reddy and Lee, 2014；Wang etc., 2014), and in water body
In environment, the biomass carbon that magnetic is modified has certain recyclable potentiality (Zhou etc., 2014).However, magnetic modified biomass charcoal
It is higher to biomass carbon structural requirement, it is necessary to there is preferable pore structure, and the suction-operated of its heavy metal mainly by
The suction-operated of surface magnetism ferriferous oxide and exchangeable cation content is increased by magnetic action, and then improve life
The action effect of material charcoal heavy metal.Have studies have shown that its only the relatively good heavy metal of the mobility such as cadmium is shown compared with
Effect well (Deng 2016).Therefore, single magnetic modification is carried out to biomass carbon to limit to a certain extent
The passivation of biomass carbon heavy metal.
In summary, biomass carbon, Fe-Mn oxidation, lime and magnetic modified biomass charcoal are administered in heavy metal pollution of soil
Aspect all has certain practical application and theoretical research foundation, and all shows preferable application potential and effect.However,
Biomass carbon and lime have preferable regulation effect to acid soil heavy metal pollution, and iron and manganese oxides have grain less
Certain regulation effect can be just shown under level, and the application effect of single magnetic material is easily by the shadow of edaphic condition
Ring.Therefore, in the natural soils of combined pollution, any of the above-described control measures of single utilization are all unable to reach ideal control
Manage effect.
The content of the invention
It is that providing a kind of heavy metal-polluted soil repaiies to solve the shortcomings that prior art and weak point, purpose of the invention
Multiple agent, using the modified biomass charcoal impregnated of rich calcium constituent and iron and manganese oxides as carrier, and utilize nano-scale magnetic material
Overlay film is carried out to carrier.Magnetic material overlay film can at utmost enriching heavy metal, the calcium constituent being rich in and iron and manganese oxides
Heavy metal is further exchanged, adsorbed, and so as to preferably fixed heavy metal, the mobility and biology for reducing heavy metal can
And property.Therefore, to the good passivation effect of various heavy, can be to acid and basic soil under the conditions of, Compound Heavy Metals soil
Earth carries out various heavy, as being passivated while cadmium, lead, arsenic, chromium and mercury, realizes effective improvement of heavy metals in farmland pollution, protects
Agricultural product security is demonstrate,proved, is effectively improved China's heavy metals in farmland pollution situation.
Another purpose of the present invention is to provide a kind of preparation method of heavy metal-polluted soil renovation agent, first, by iron
In salt, manganese salt and alkaline calcareous material dipping stalk and wood chip the like waste, high temperature limit oxygen thermal cracking obtains modified biomass
Carbon so that calcium constituent and iron and manganese oxides enter the structure hole of modified biomass carbon biomass carbon and are mounted to its surface；
Then, impregnation is carried out to modified biomass carbon with nanoscale magnetic iron ore suspension, obtains magnetic Nano material overlay film
Rich calcium constituent and iron and manganese oxides composite biomass charcoal heavy metal-polluted soil renovation agent.
The foregoing invention purpose of the present invention, is achieved through the following technical solutions：
A kind of heavy metal-polluted soil renovation agent, load is used as using the modified biomass charcoal impregnated of rich calcium constituent and iron and manganese oxides
Body, and overlay film is carried out to carrier using nano-scale magnetic material；Particle diameter contains in 0.25-5mm, the Fe contents of product for 2-5%, Mn
It is 10-15% to measure as 5-10%, Ca content.
The raw material of biomass carbon is selected from straw or wood chip, and particle diameter is in 0.25-1mm.
The straw is at least one in rice straw, peanut straw, rape stalk, maize straw and wheat stalk
Kind or mixture；
Described wood chip is gardening forest tree castoff, building at least one of wood chip discarded object and shuck or mixing
Thing.
A kind of preparation method of heavy metal-polluted soil renovation agent, comprises the following steps：
Step 1: prepared by rich calcium constituent and the biomass carbon of iron and manganese oxides：
Biomass is impregnated with the maceration extract containing molysite, alkaline calcareous material and manganese salt, after biomass is drained, in anaerobic
Under the conditions of, 550 DEG C -600 DEG C are warming up to 20 DEG C -30 DEG C per minute of heating rate, is incubated 1-4h, then keeps isolation air
Under be cooled to room temperature, obtain rich in iron, manganese, the biomass carbon of calcium constituent.
Dipping process, preferably substep are carried out, i.e., first biomass are immersed in iron salt solutions, after impregnating 24h, then are being impregnated
Alkaline calcareous material and manganese salt are added in liquid, impregnates 24h.
Biomass carbon presses 1 with iron salt solutions:2-7:10 (W/V) ratio mixing；The concentration of iron salt solutions is 0.2mol/L；
It is 24h that the dip time of molysite, alkaline calcareous material and manganese salt, which is,.
Molysite is ferric nitrate or iron chloride；
Described alkaline calcareous material is at least one of quick lime or white lime, and addition is made a living material mass
19%-25%, preferably 20%-22%；
Described manganese salt is at least one of manganese chloride, manganese sulfate and potassium permanganate, and the mass ratio with biomass is 1:
28-1:20, preferably 1:25-1:20.
Step 2：The preparation of nano-scale magnetic material：
The aqueous solution of iron sulfate heptahydrate is prepared, pH about 12.0 is adjusted, filtering, is positioned over after filtrate is diluted into 1-2 times micro-
In ripple stove, 10-15min is heated under maximum fire, washs and to suspended pH liquid weakly acidic pH, is obtained containing non-metering nanoscale magnetic repeatedly
Iron ore suspension, grade 25-100nm；
Described iron sulfate heptahydrate and the mixed proportion of water are 1:50-1:100, preferably 1:60-1:80.
Step 3: nano material overlay film modified biomass charcoal：
The biomass carbon and the magnetic iron ore suspension of step 2 that step 1 is obtained press 1:2-1:4 (W/V) ratio mixing
Uniformly, dried at a temperature of less than 60 DEG C, obtain the rich calcium, iron, manganese multielement complex biological of magnetic Nano material overlay film
Matter charcoal heavy metal-polluted soil renovation agent, particle diameter is in 0.25-5mm, and pH is between 8-11, and cation exchange capacity (CEC) is in 280-410mmol/
kg。
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) heavy metal soil-repairing agent prepared by the present invention contains calcium constituent, iron and manganese oxides, nano-scale magnetic iron oxide
And the active ingredient such as biomass carbon, be a kind of multielement synergy soil-repairing agent, to such as cadmium of the heavy metal in soil,
Chromium, lead, arsenic and mercury etc. all have passivation；Reparation available for the Heavy metals single pollution or combined pollution of a variety of soil
Administer.
(2) soil-repairing agent of the invention does carrier using biomass carbon, make use of the pore structure that biomass carbon is good,
Magnetic modification is carried out to it using nanoscale magnetic iron ore, effectively combines the double dominant of calcium constituent and iron and manganese oxides, magnetic is modified
The accumulation ability of biomass carbon heavy metal is improved, can be to the acid and neutral meta-alkalescence soil table of Compound Heavy Metals
Reveal preferable repairing effect.
(3) materials are extensive, raw material is cheap and easy to get；Concise production process environmental protection, large-scale industrialized can be produced.
Brief description of the drawings
Fig. 1 be rice straw charcoal of the gained of embodiment 1 rich in iron and manganese oxides and calcium constituent before modified after contrast Electronic Speculum
Figure；
Fig. 2 be embodiment 5 potted plant experiment in soil-repairing agent processing of the invention to rice grain heavy metal Cd, Pb,
The influence of As, Cr content.Compared with the control, different disposal (T1-T5) all reduces the content of Cd and Pb in rice grain.Its
In, reduction amplitude of the renovation agent to Cd in rice grain and Pb in embodiment 2 is maximum, respectively reaches 38.7% and 61.1%.
And the renovation agent in embodiment 1 and embodiment 3 can also reach certain suppression effect to the Cd in rice grain and Pb content
Fruit, amplitude is reduced respectively up to 19.4% and 25.8% (Cd) and 42.6% and 38.9% (Pb).And ordinary student is administered alone
Material charcoal and lime are respectively 6.5% and 0% to the reduction amplitude of Cd in rice grain, and the reduction amplitude to Pb is respectively
9.3% and 3.7%.And to the reducing effect of arsenic, then the renovation agent only in embodiment 1 to embodiment 3 is in rice grain
Arsenic there is obvious reduction to act on, wherein embodiment 2 is up to 55.2% to the reduction amplitude of arsenic in rice grain；And common biology
Matter charcoal and lime all promote absorption of the rice grain to arsenic to a certain extent.Based on the above results as can be seen that by pair
Common biomass carbon enters modification, can significantly improve biomass carbon and absorb heavy metal Cd, Pb and As to rice grain
Inhibition.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1：
(1) will grind sieving, particle diameter the iron nitrate solution that 0.25-1mm rice straw and concentration are 0.2mol/L with
3:5 (W/V) ratio mixing, after stirring 24h at room temperature, continue to add 20% life stone of rice straw quality into soak
Ash, meanwhile, it is 1 by with rice straw mass ratio:25 ratio adds manganese chloride, at room temperature intermittent stirring, will after placing 24h
After rice straw after immersion treatment drains, dried at 80 DEG C, 25 DEG C per minute of liter is pressed under the oxygen free condition of nitrogen protection
Warm speed is warming up to 550 DEG C, and keeps 3h, then proceedes to keep to be cooled to room temperature under isolation air conditionses, that is, obtains being rich in iron
The rice straw charcoal of Mn oxide and calcium constituent.
(2) iron sulfate heptahydrate and water are pressed 1:70 ratio wiring solution-forming, and the potassium hydroxide for being slowly added to 1M will be molten
The pH of liquid is adjusted to 12, is positioned over after filtrate is diluted into 2 times after filtering in micro-wave oven, heats 10min under maximum fire, will obtain
Material rinsed repeatedly to neutrality with ultra-pure water after and with above-mentioned rice straw charcoal by 1:3 (W/V) ratio is mixed, mixing
Rice straw charcoal is dried under the temperature conditionss less than 60 DEG C to 48h to absolutely dry after uniformly, obtained rice straw charcoal ferro element contains
Amount is 2.5%, and manganese element content is 5.4%, and calcium element content is in 10%, pH 8.45, cation exchange capacity (CEC) 283mmol/
Kg, particle diameter is in 1-4mm.
Embodiment 2：
Will grinding sieving, particle diameter is 0.2mol/L ferric chloride solution with 1 in 0.25-1mm maize straw and concentration:2
(W/V) ratio mixing, after stirring 24h at room temperature, continue to add 22% quick lime of rice straw quality into soak,
Meanwhile by with rice straw mass ratio be 1:20 ratio adds manganese sulfate, at room temperature intermittent stirring, after placing 24h, will soak
After rice straw after processing drains, dried at 80 DEG C, it is fast by 30 DEG C per minute of heating under the oxygen free condition of nitrogen protection
Degree is warming up to 600 DEG C, and keeps 2h, then proceedes to keep to be cooled to room temperature under isolation air conditionses, that is, obtains being rich in ferrimanganic oxygen
The rice straw charcoal of compound and calcium constituent.
Iron sulfate heptahydrate and water are pressed 1:80 ratio wiring solution-forming, and the pH of solution is by the KOH for being slowly added to 1M
12, it is positioned over after filtrate is diluted into 2 times after filtering in micro-wave oven, 15min is heated under maximum fire, by obtained material with ultrapure
Water is rinsed to neutrality repeatedly, and above-mentioned rice straw charcoal and nano-scale magnetic iron oxide suspension are pressed into 1:3 (W/V) ratio is carried out
Mixing, rice straw charcoal is dried under the temperature conditionss less than 60 DEG C to 48h to composite that is absolutely dry, obtaining after well mixed,
Iron content is 4.5%, and manganese element content is 9.8%, and calcium element content is in 12.5%, pH 11.01, cation exchange capacity (CEC)
For 410mmol/kg, particle diameter is in 0.25-3mm.
Embodiment 3：
It is 0.2mol/L iron nitrate solution with 7 that sieving, particle diameter, which will be ground, in 0.25-1mm wood chip and concentration:10(W/
V ratio mixing), after stirring 24h at room temperature, continue to add 25% quick lime of rice straw quality into soak, together
When, it is 1 by with rice straw mass ratio:26 ratio adds potassium permanganate, at room temperature intermittent stirring, after placing 24h, will soak
After rice straw after processing drains, dried at 80 DEG C, it is fast by 30 DEG C per minute of heating under the oxygen free condition of nitrogen protection
Degree is warming up to 600 DEG C, and keeps 2h, then proceedes to keep to be cooled to room temperature under isolation air conditionses, that is, obtains being rich in ferrimanganic oxygen
The rice straw charcoal of compound and calcium constituent.
Iron sulfate heptahydrate and water are pressed 1:60 ratio wiring solution-forming, and 1M KOH solution is slowly added to by solution
PH is adjusted to 12, is positioned over after filtrate is diluted into 2 times after filtering in micro-wave oven, heats 12min under maximum fire, the thing that will be obtained
Matter is rinsed to neutrality repeatedly with ultra-pure water.
Above-mentioned rice straw charcoal and nano-scale magnetic iron oxide suspension are pressed 1:4 (W/V) ratio is mixed, mixing
Rice straw charcoal is dried under the temperature conditionss less than 60 DEG C to 48h to absolutely dry after uniformly, in obtained composite treating agent, iron content
2.1%, manganese element content is 6%, and calcium element content is in 14.6%, pH 11.02, cation exchange capacity (CEC) 290mmol/
Kg, particle diameter is in 2-5mm.
Embodiment 4：
It is 0.2mol/L iron nitrate solution with 7 that sieving, particle diameter, which will be ground, in 0.25-1mm peanut straw and concentration:10
(W/V) ratio mixing, after stirring 24h at room temperature, continue to add 19% white lime of rice straw quality into soak,
Meanwhile by with rice straw mass ratio be 1:28 ratio adds potassium permanganate, at room temperature intermittent stirring, after placing 24h, will soak
After rice straw after bubble processing drains, dried at 80 DEG C, 20 DEG C per minute of heating is pressed under the oxygen free condition of nitrogen protection
Speed is warming up to 580 DEG C, and keeps 4h, then proceedes to keep to be cooled to room temperature under isolation air conditionses, that is, obtains being rich in ferrimanganic
The rice straw charcoal of oxide and calcium constituent.
Iron sulfate heptahydrate and water are pressed 1:50 ratio wiring solution-forming, and 1M KOH solution is slowly added to by solution
PH is adjusted to 12, is positioned over after filtrate is diluted into 2 times after filtering in micro-wave oven, heats 12min under maximum fire, the thing that will be obtained
Matter is rinsed to neutrality repeatedly with ultra-pure water.
Above-mentioned rice straw charcoal and nano-scale magnetic iron oxide suspension are pressed 1:2 (W/V) ratio is mixed, mixing
Rice straw charcoal is dried under the temperature conditionss less than 60 DEG C to 48h to absolutely dry after uniformly, in obtained composite treating agent, iron content
3.1%, manganese element content is 8.3%, and calcium element content is in 12.8%, pH 9.6, cation exchange capacity (CEC) 360mmol/
Kg, particle diameter is in 0.5-4mm.
Embodiment 5：
Pot experiment of the soil-repairing agent to acid paddy soil Compound Heavy Metals passivation effect：Soil collection is from lake
Soil of the southern Changsha Xiangyin County one by the farmland top layer 0-20cm for irrigating water pollution；Soil crosses 2mm sieves, soil after natural air drying
Earth basic physical and chemical is as shown in table 1.
The pot experiment of table 1 is for examination soil labile organic matter
| Test index | Content |
| pH | 5.52 |
| Total Pb (mgkg-1) | 197 |
| Total Cd (mgkg-1) | 1.32 |
| Total As (mgkg-1) | 13 |
| Cation exchange capacity (CEC) (cmolkg-1) | 15.6 |
| SOC(g·kg-1) | 51 |
Weigh after 8kg soil is put into Plastic Drum (diameter 35cm, high 40cm), be handled as follows per basin：
T1：Renovation agent prepared by 8 kilograms of soil+80g embodiments 1；
T2：Renovation agent prepared by 8 kilograms of soil+80g embodiments 2；
T3：Renovation agent prepared by 8 kilograms of soil+80g embodiments 3；
T4：8 kilograms of common biomass carbons of soil+80g；
T5：8 kilograms of soil+10g lime；
Not add any renovation agent as control (CK).
Each 3 repetitions of processing, are positioned in glasshouse.Apply the latter week plantation water of renovation agent of each treatment group
Rice, rice sample measure Cd, Pb and As content is collected in the rice harves phase, as shown in Figure 1.
Embodiment 6：
Pot experiment of the soil-repairing agent to alkaline dryland soil Compound Heavy Metals passivation effect：Soil collection is from river
One contaminated farmland top layer 0-20cm of Nan Sheng Jiyuan Cities Jia Zhuan villages；Soil crosses 2mm sieves, the basic physics and chemistry of soil after natural air drying
Matter such as table 2.
Table 2 is potted plant for examination physiochemical properties of soil
| Test index | Content |
| pH | 8.07 |
| Total Pb (mgkg-1) | 220 |
| Total Cd (mgkg-1) | 3.76 |
| Total As (mgkg-1) | 20 |
| Cation exchange capacity (CEC) (cmolkg-1) | 13.2 |
| SOC(g·kg-1) | 12 |
Weigh after 8kg soil is put into Plastic Drum (diameter 35cm, high 40cm), be handled as follows per basin：
T1：Renovation agent prepared by 8 kilograms of soil+80g embodiments 1；
T2：Renovation agent prepared by 8 kilograms of soil+80g embodiments 2；
T3：Renovation agent prepared by 8 kilograms of soil+80g embodiments 3；
T4：8 kilograms of common biomass carbons of soil+80g；
T5：8 kilograms of soil+10g lime；
Not add any renovation agent as control (CK).
Each 3 repetitions of processing, are positioned in glasshouse.Apply the latter week plantation wheat of each renovation agent, in small wheat harvest
Obtain the phase and collect wheat samples measure Cd, Pb and As content, the results are shown in Table 3：
Cd, Pb and As content in the wheat seed of table 3
As shown in table 3, in the dryland soil of alkalescence, compared with the control, different disposal (T1-T5) can reduce wheat
Cd and Pb content in seed.Wherein, reduction amplitude of the renovation agent in embodiment 2 to Cd in rice grain and Pb is maximum, point
36.4% and 53.2% are not reached.And the renovation agent in embodiment 1 and embodiment 3 is to the Cd and Pb content in rice grain
There is inhibition, reduce amplitude respectively up to 12.1% and 38.7% (Cd) and 15.1% and 45.2% (Pb).And individually apply
It is respectively 9.1% and 3.0% to the reduction amplitude of Cd in rice grain with common biomass carbon and lime, the reduction to Pb
Amplitude is respectively 27.4% and 17.7%.And to the reducing effect of arsenic, then the renovation agent only in embodiment 1 to embodiment 3
There is obvious reduction to act on to the arsenic in rice grain, wherein embodiment 2 is up to the reduction amplitude of arsenic in rice grain
48.4%；And common biomass carbon and lime all promote absorption of the wheat seed to arsenic to a certain extent.In summary tie
Fruit can be seen that the heavy metal pollution of soil renovation agent for preparing of the present invention, wheat seed can be absorbed heavy metal Cd, Pb and
As has preferable inhibition.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of heavy metal-polluted soil renovation agent, it is characterised in that be with the modification biological impregnated of rich calcium constituent and iron and manganese oxides
Matter charcoal carries out overlay film as carrier, and using nano-scale magnetic material to carrier；The particle diameter of product is in 0.25-5mm, the Fe of product
Content is that 2-5%, Mn content are that 5-10%, Ca content are 10-15%.
2. the heavy metal-polluted soil renovation agent described in claim 1, it is characterised in that the raw material of biomass carbon be selected from straw or
Person's wood chip, particle diameter is in 0.25-1mm.
3. the heavy metal-polluted soil renovation agent described in claim 2, it is characterised in that the straw is rice straw, peanut stems
At least one of stalk, rape stalk, maize straw and wheat stalk or mixture；Described wood chip is that gardening forest discards
Thing, building at least one of wood chip discarded object and shuck or mixture.
4. the preparation method of the heavy metal-polluted soil renovation agent described in claim 1, it is characterised in that comprise the following steps：
Step 1: prepared by rich calcium constituent and the biomass carbon of iron and manganese oxides：
Biomass is impregnated with the maceration extract containing molysite, alkaline calcareous material and manganese salt, after biomass is drained, in oxygen free condition
Under, 550 DEG C -600 DEG C are warming up to 20 DEG C -30 DEG C per minute of heating rate, is incubated 1-4h, then keeps cold under isolation air
But to room temperature, rich calcium constituent and the biomass carbon of iron and manganese oxides are obtained；
Step 2：The preparation of nano-scale magnetic material：
The aqueous solution of iron sulfate heptahydrate is prepared, pH 12.0 or so is adjusted, filtering, microwave is positioned over after filtrate is diluted into 1-2 times
In stove, big fire heating 10-15min, it is neutrality to wash to suspension, is obtained containing non-metering nanoscale magnetic iron ore suspension, grain
Level 25-100nm；
Step 3: nano material overlay film modified biomass charcoal：
The rich calcium constituent and the biomass carbon of iron and manganese oxides and the magnetic iron ore suspension of step 2 that step 1 is obtained press 1:2-
1:4 mass volume ratio is well mixed, and is dried at a temperature of less than 60 DEG C, obtain the rich calcium of magnetic Nano material overlay film, iron,
Manganese multielement complex biological matter charcoal heavy metal-polluted soil renovation agent.
5. the preparation method of the heavy metal-polluted soil renovation agent described in claim 4, it is characterised in that in step 1, dipping process
Substep is carried out, and first biomass is immersed in iron salt solutions, after steeped overnight, then add in maceration extract alkaline calcareous material and
Manganese salt, steeped overnight；
Biomass carbon presses 1 with iron salt solutions:2-7:10 mass volume ratio mixing；The concentration of iron salt solutions is 0.2mol/L；
Described molysite is ferric nitrate or iron chloride；
Described alkaline calcareous material is at least one of quick lime or white lime, and addition is made a living the 19%- of material mass
25%；
Described manganese salt is at least one of manganese chloride, manganese sulfate and potassium permanganate, and the mass ratio with biomass is 1:28-1:
20。
6. the preparation method of the heavy metal-polluted soil renovation agent described in claim 4, it is characterised in that the alkalescence described in step 1
Calcareous material addition is made a living the 20%-22% of material mass；Described manganese salt be manganese chloride, manganese sulfate and potassium permanganate in extremely
Few one kind, the mass ratio with biomass are 1:25-1:20.
7. the preparation method of the heavy metal-polluted soil renovation agent described in claim 4, it is characterised in that in step 2, described seven
The mixed proportion of ferric sulfate hydrate and water is 1:50-1:100.
8. the preparation method of the heavy metal-polluted soil renovation agent described in claim 4, it is characterised in that in step 2, described seven
The mixed proportion of ferric sulfate hydrate and water is 1:60-1:80.
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