CN109628099A - A kind of passivation stabilizer for agricultural land soil cadmium pollution reparation and preparation method thereof and application method - Google Patents
A kind of passivation stabilizer for agricultural land soil cadmium pollution reparation and preparation method thereof and application method Download PDFInfo
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- CN109628099A CN109628099A CN201811060375.1A CN201811060375A CN109628099A CN 109628099 A CN109628099 A CN 109628099A CN 201811060375 A CN201811060375 A CN 201811060375A CN 109628099 A CN109628099 A CN 109628099A
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The present invention relates to farmland cadmium pollution soils to administer field, more particularly to a kind of passivation stabilizer for agricultural land soil cadmium pollution reparation and preparation method thereof and application method, the passivation stabilizer includes calcium dihydrogen phosphate, charcoal, bio-bacterial manure, according to weight fraction meter: calcium dihydrogen phosphate 35-45%, charcoal 10-20%, bio-bacterial manure 35-45%.Passivation agent material provided by the present invention for Cd-polluted farmland soil is to combine various passivating materials, calcium dihydrogen phosphate is by generating precipitating with cadmium, and charcoal has big gap, cadmium is fixed by suction-operated, and bio-bacterial manure passes through the method for ionic adsorption and ion exchange, to reduce the bio-available Zn concentration of cadmium in soil, while soil organic matter content can be provided.In addition, having adjusted soil pH value, re-dissolving for pollutant is reduced.The present invention is by synergistic effect, requirement that be well positioned to meet that heavy-metal contaminated soil reparation is strong to stability, without secondary pollution, effect is lasting stable.
Description
Technical field
The present invention relates to farmland cadmium pollution soils to administer field, more particularly to a kind of for agricultural land soil cadmium pollution reparation
Passivation stabilizer and preparation method thereof and application method.
Background technique
Soil is paid close attention to by people always as one of valuable source for the survival of mankind, safety, but in recent years,
Due to industrial boom, " three wastes " discharge increase and municipal pollution aggravation, result in heavy metal pollution of soil problem day
It is beneficial severe.
The main reason for causing the cadmium pollution of China farmland is that rural sewage is irrigated, and pollution sources mostly come from factory, smelting
Exhaust gas, the waste water of the discharges such as refinery, enterprise.Remediation of heavy metal-contaminated soil mainly has peripheral doses, chemical remediation, life
Object reparation etc., wherein in-situ passivation recovery technique because it is low in cost, simple and easy the advantages that and receive significant attention, the party
The farmland of the applicable heavy metal pollution of method selects efficient passivation stabilizer that heavy metal validity can be effectively reduced and can improve soil
Earth fertility is the key that in-situ immobilization.
Phosphate is a kind of passivation stabilizer for being widely used in heavy metal pollution of soil, the form of heavy metal in soil,
Phosphatic dissolubility is the effect of Diffluent phosphorus hydrochlorate passivation an important factor for influencing phosphate heavy metal-passivated contaminated soil
Fruit is better than insoluble phosphate, but application Diffluent phosphorus hydrochlorate is possible to generate and causes surface water water body rich in the soil
The risk of nutrient laden.Charcoal possesses biggish specific surface area, stronger suction-operated by it, becomes heavy metal pollution
Renovation agent.Charcoal can reduce the mobility of heavy metal ion in the soil by the pH value in soil, to heavy metal
Fixed function is played, and is had by ion exchange, co-precipitation, physical absorption, surface complexing etc. to reduce in soil
Imitate state cadmium.After soil using organic materials repairing heavy metal pollution, the pH value of soil is significantly improved, and in soil sun from
Subsubstitution amount also occurs significantly to increase, and organic materials can be complexed with the heavy metal in the soil by heavy metal pollution at big
The validity of the heavy metal in soil can be significantly reduced in molecule organic complex.
Summary of the invention
In order to make up it is different passivation stabiliser materials be used alone rehabilitating soils during deficiencies, improve remediation efficiency,
Three kinds of calcium dihydrogen phosphate, charcoal, bio-fertilizer repair materials are carried out compounding passivation Cd-polluted farmland soil by the present invention.
It is an object of the present invention to provide a kind of passivation stabilizer for agricultural land soil cadmium pollution reparation, the passivation
Stabilizer can effectively be passivated restoring cadmium polluted agricultural land soil, and cadmium bio-available Zn concentration in agricultural land soil, passivation effect is effectively reduced
Long-acting stabilization, it is a further object to provide the above-mentioned passivation for the reparation of farmland soil heavy metals combined pollution is steady
Determine the method for preparation and use of agent.
In order to achieve the above-mentioned object of the invention, the technical scheme adopted by the invention is as follows: one kind be used for agricultural land soil cadmium pollution
The passivation stabilizer of reparation, which is characterized in that the passivation stabilizer includes calcium dihydrogen phosphate, charcoal, bio-bacterial manure, is pressed
According to weight fraction meter: calcium dihydrogen phosphate 35-45%, charcoal 10-20%, bio-bacterial manure 35-45%.
It is highly preferred that according to weight fraction meter: calcium dihydrogen phosphate 40-45%, charcoal 10-20%, bio-bacterial manure 40-
45%.
Calcium dihydrogen phosphate be colourless three inclined tab shape, granular or crystalline powder；Charcoal is by stalk in closed container
High temperature is fired；Bio-bacterial manure is bacillus amyloliquefaciens BZ6-1 bio-bacterial manure, and solution starch gemma is mainly contained in bacterial manure
Bacillus BZ6-1, it is living which can generate Surfactin, Feng Yuansu (fengycin) and iturin (iturin) etc.
Property substance, utilize bacterial strain application patent: application of the BZ6-1 bacterial strain in preparation treatment plant bacterial wilt of peanut drug, specially
Benefit number: 2010102415773.
Passivator of the invention is suitable for the agricultural land soil of cadmium pollution, by above-mentioned a variety of differences with certain content
The porous adsorbent and passivation of material form, and have complementary advantages between each other, in conjunction with the principles such as absorption and stabilisation, pass through
Ion exchange, complexing, chelating and adsorption method effectively enhance the combining form of heavy metal, are translated into more stable
Strong organically combine state and residual form, are effectively reduced heavy metal bio-available Zn concentration in agricultural land soil, the long-acting stabilization of passivation effect is right
There is great repair in the agricultural land soil of cadmium pollution.
A kind of preparation method of the passivation stabilizer for agricultural land soil cadmium pollution reparation, includes the following steps:
One, calcium dihydrogen phosphate, the charcoal, bio-bacterial manure of corrresponding quality score are weighed；
Two, by the broken mixing of component described in step 1, removal partial size is greater than 50 μm -150 μm of particle,
Obtain passivation stabilizer.
In step 1, charcoal preparation process are as follows: stalk is placed in closed container, is burnt under 300-600 degrees celsius
Charcoal is made.300-600 degrees Celsius is charcoal carbonization temperature.
A kind of application method of the passivation stabilizer for agricultural land soil cadmium pollution reparation, includes the following steps:
Dry field is turned over, by aggravation of soil fragmentation, adds the passivation stabilizer；
After having broadcasted sowing passivation stabilizer, rotary tillage processing, in length and breadth rotary tillage 3 times are carried out to dry ground, rotary tillage depth is 15-20cm,
Ensure it is horizontal and vertical be uniformly mixed, placed 10-20 days after rotary tillage；
After rotary tillage, the water surface is added water to higher than soil surface 10-12cm, soil is aged, with rotation during ageing
The machine of ploughing carries out rotary tillage process to soil；
After the farmland of addition passivation stabilizer is placed 12-15 days, dry field.
As restriction, according to cadmium pollution degree, lower than 1mg/kg, passivator amount of application is agricultural land soil cadmium content per acre
400-800kg；Agricultural land soil cadmium content is higher than 1mg/kg, and passivator amount of application is 1000-1500kg per acre.
Compared with prior art, the present invention acquired technological progress is:
Passivation agent material provided by the present invention for Cd-polluted farmland soil is to combine various passivating materials, passivation effect
Fruit is better than single passivating material, and calcium dihydrogen phosphate is by generating precipitating with cadmium, and charcoal has big gap, passes through absorption
Cadmium is fixed in effect, and bio-bacterial manure is by the method for ionic adsorption and ion exchange, to reduce having for cadmium in soil
Imitate state content.In addition, having adjusted soil pH value, re-dissolving for pollutant is reduced.The present invention passes through synergistic effect,
It is well positioned to meet that heavy-metal contaminated soil reparation is strong to stability, without secondary pollution, effect is lasting and stablizes, low cost is wanted
It asks.The passivation agent material is largely that trade waste and agricultural wastes are from a wealth of sources, and preparation and application is simple, repairs
It is multiple at low cost, turn waste into wealth, realizes industrial solid castoff and agricultural wastes resource utilization.
The preparation method of passivator provided by the invention is simple, has industrialized production and broad application prospect.
Passivator of the present invention belongs to in-situ immobilization agricultural land soil cadmium pollution, does not influence agricultural production, will not destroy soil
Earth structure, and can be improved soil fertility.
The present invention is suitable for repairing farmland cadmium pollution soil.
Detailed description of the invention
Fig. 1 difference is passivated influence of the combination of stabilizers to the effective cadmium content of soil；
Fig. 2 difference, which is passivated stabilizer, influences soil pH；
Fig. 3 difference, which is passivated stabilizer, influences the soil organism；
Wherein, 1:10% calcium dihydrogen phosphate, 30% charcoal, 60% bio-fertilizer are handled；Handle 2:15% biphosphate
Calcium, 10% charcoal, 75% bio-fertilizer；Handle 3:40% calcium dihydrogen phosphate, 20% charcoal, 40% bio-fertilizer；Processing 4:
40% calcium dihydrogen phosphate, 15% charcoal, 45% bio-fertilizer；Handle 5:45% calcium dihydrogen phosphate, 10% charcoal, 45% life
Object fertilizer；Handle 6:65% calcium dihydrogen phosphate, 5% charcoal, 30% bio-fertilizer；Handle 7:70% calcium dihydrogen phosphate, 15% biology
Charcoal, 15% bio-fertilizer；Handle 8:75% calcium dihydrogen phosphate, 10% charcoal, 15% bio-fertilizer.
Specific embodiment
In order to illustrate technical solution of the present invention and technical purpose, with reference to the accompanying drawing explanation and specific embodiment pair
The present invention is described further.
1 materials and methods
1.1 experimental design
This test sets 8 processing altogether, is shown in Table 1.It is each processing in triplicate, specific experiment step: will passivation stabilizer with
Cd-polluted farmland soil is sufficiently mixed, and weight method keeps the water content of soil 60%, is sampled after cultivating 1 month under room temperature environment,
It is spare that 100 mesh are crossed after natural air drying is levigate.The pitch-based sphere for being passivated stabilizer is the 1% of Cd contaminated soil weight.Cd pollution
Initially effective cadmium content is 7.8mg/kg to soil.
Table 1 is passivated stabilizer composition
1.2 measurements and analysis method
1.2.1 in soil DTPA extract state cadmium content measurement
The measurement of the effective cadmium content of soil uses DTPA extraction-atomic absorption spectrophotometry.Accurately weigh air-dried soil sample
2.50g is placed in 100ml plastic jar, and DTPA5ml is added, is put into vibrating machine and vibrates 2h, is filtered after standing 30min, quasi-
Filtrate 1ml is really pipetted, DTPA4ml is added, measures cadmium content with AAS method after shaking up.The production method of graticule when measurement: accurate
It measures 1ml1000 μ g/ml cadmium standard solution to move in 10 ml volumetric flasks, DTPA dilution is added to get to 100 μ g/ml cadmium standards
Solution repeats aforesaid operations once to get to the cadmium standard solution of 10 μ g/ml.Accurately pipette the cadmium standard solution of 10 μ g/ml
5,10,15,20,25,50ml is placed in the volumetric flask of 100ml, be added DTPA constant volume to get to 0.5,1,1.5,2,2.5,
The cadmium standard solution of 5 μ g/ml.
1.2.2 the measurement of soil pH value
It accurately weighs air-dried soil sample 10g to be placed in centrifuge tube, pure water 25ml is added, is put into vibrating machine and vibrates 1h, take out
It after standing 30min, is kept completely separate to supernatant liquor and soil sample to be measured, takes out supernatant liquor, pH meter is inserted, wait read
PH value is recorded after stabilization.
2 results and analysis
Influence of the 2.1 addition passivation stabilizers to effective cadmium content of soil
The calcium dihydrogen phosphate, charcoal, influence of the bio-fertilizer to soil available Cd content of different proportion are added as schemed
1.The effective cadmium content of original soil sample is 7.80mg/kg.As shown in Figure 1, applying different passivation stabilizers can make in soil effectively
State cadmium content reduces, and reduces between 36%-72% respectively.The validity passivation effect for handling 3,4,5 pairs of cadmiums is best, respectively
Reach 72%, 69%, 71%.
Influence of the 2.2 addition passivation stabilizers to soil pH value
The pH value of soil is important one of the basic physical and chemical of soil, significant to the heavy metal in soil.Generally
For, the pH value of soil is relatively high, and the eco-toxicity of the heavy metal in soil is lower, and biological effectiveness is smaller；The pH of soil
It is worth lower, the eco-toxicity of the heavy metal in soil is higher, and biological effectiveness is bigger.And the pH value of soil is to influence a huge sum of money
Belong to one of the principal element of absorption, precipitating, dissolution, thus by regulation soil pH value to reduce heavy metal-polluted soil validity,
Transfer ability etc. plays a significant role.
The following Fig. 2 of influence of calcium dihydrogen phosphate, charcoal and the bio-fertilizer of different proportion to the pH value of soil is applied,
Middle initial (before the untreated) pH value for trying soil is 7.15.As seen from the figure, addition passivation stabilizer can make the pH value of soil
It increases.Processing 3,4,5 three kind of processing influence soil pH value maximum, and pH respectively reaches 8.13,7.82 and 7.99.And to processing 1
Minimum is influenced with processing 2, only 7.36 and 7.52.Influence of the 2.3 addition passivation stabilizers to the soil organism
The calcium dihydrogen phosphate, charcoal, influence of the bio-fertilizer to soil available Cd content of different proportion are added as schemed
3.The original soil sample content of organic matter is 6.85g/kg.The addition of different passivator can all improve soil organic matter content, improve soil
Nutrient content.Compare between different disposal as can be seen that charcoal and bio-fertilizer are affected to soil organic matter content, it is special
It is not bio-fertilizer, bio-fertilizer content ratio is bigger in passivator, and soil organic matter content is higher, such as processing 1 and 2, and soil is organic
Matter content reaches 20g/kg and 15g/kg.
2.4 correlation analysis
The content of soil available cadmium and the correlation of pH value, charcoal, bio-fertilizer, calcium dihydrogen phosphate are as shown in table 3.
The correlation of available Cd content and pH in soil reaches extremely significant negative correlation, shows soil pH by correlation analysis
Rising can promote Cadmium in Soil to change from using state to difficulty using state, reduce its biological effectiveness and toxicity, repair to reach
The purpose of earth backing earth.Simultaneously it can be found that calcium dihydrogen phosphate is significantly negatively correlated with pH, show that calcium dihydrogen phosphate is by improving soil
Earth pH is to make the validity of Cadmium in Soil reduce.It is also seen that charcoal and effective cadmium content of soil are also pole from table
It is significant negatively correlated, show that effective cadmium content in soil can be significantly reduced in charcoal, the researchs such as Singh indicate, apply charcoal
Afterwards, the cadmium in soil can reduction-state and bound residue reduce, and oxidable state and residual form increase.The application of charcoal
Amount and administration time can influence the content of available Cd, with the increase of charcoal applicating ratio and the increasing of administration time
Long, the pH value of soil increases, and the cadmium conversion in soil is promoted to utilize state cadmium to be difficult.
2 correlation analysis of table
Note: * indicates significant correlation, and * * indicates extremely significant correlation.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, this
A little changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by the attached claims
Book and its equivalent thereof.
Claims (7)
1. a kind of passivation stabilizer for agricultural land soil cadmium pollution reparation, which is characterized in that the passivation stabilizer includes phosphorus
Acid dihydride calcium, charcoal, bio-bacterial manure, according to weight fraction meter: calcium dihydrogen phosphate 35-45%, charcoal 10-20%, biological bacteria
Fertile 35-45%.
2. a kind of passivation stabilizer for agricultural land soil cadmium pollution reparation according to claim 1, which is characterized in that press
According to weight fraction meter: calcium dihydrogen phosphate 40-45%, charcoal 10-20%, bio-bacterial manure 40-45%.
3. a kind of passivation stabilizer for agricultural land soil cadmium pollution reparation according to claim 1, which is characterized in that phosphorus
Acid dihydride calcium be colourless three inclined tab shape, granular or crystalline powder；Charcoal by stalk closed container high temperature fire and
At；Bio-bacterial manure is bacillus amyloliquefaciens BZ6-1, generates Surfactin, Feng Yuansu (fengycin) and iturin
(iturin).
4. a kind of preparation side of the passivation stabilizer for agricultural land soil cadmium pollution reparation described in claim 1-3 any one
Method, which comprises the steps of:
Weigh calcium dihydrogen phosphate, the charcoal, bio-bacterial manure of corrresponding quality score；
By the broken mixing of component described in step 1, removal partial size is greater than 50 μm -150 μm of particle to get passivation stabilizer is arrived.
5. a kind of preparation method of passivation stabilizer for agricultural land soil cadmium pollution reparation according to claim 4,
It is characterized in that, in step 1, charcoal preparation process are as follows: stalk is placed in closed container, under 300-600 degrees celsius
It is fired into charcoal.
6. a kind of user of the passivation stabilizer for agricultural land soil cadmium pollution reparation described in claim 1-3 any one
Method, which comprises the steps of:
Dry field is turned over, by aggravation of soil fragmentation, adds the passivation stabilizer；
After having broadcasted sowing passivation stabilizer, rotary tillage processing, in length and breadth rotary tillage 3 times are carried out to dry ground, rotary tillage depth is 15-20cm, it is ensured that
It is horizontal and vertical to be uniformly mixed, it is placed 10-20 days after rotary tillage；
After rotary tillage, the water surface is added water to higher than soil surface 10-12cm, soil is aged, rotary cultivator is used during ageing
Rotary tillage process is carried out to soil；
After the farmland of addition passivation stabilizer is placed 12-15 days, dry field.
7. the application method of the passivation stabilizer according to claim 6 for agricultural land soil cadmium pollution reparation, feature
It is, when agricultural land soil cadmium content is lower than 1mg/kg, being passivated stabilizer amount of application per acre is 400-800kg；When agricultural land soil cadmium
Content is higher than 1mg/kg, and being passivated stabilizer amount of application per acre is 1000-1500kg.
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| CN112920803A (en) * | 2021-01-21 | 2021-06-08 | 中国科学院南京土壤研究所 | Application of monocalcium phosphate as repairing material in reducing bioavailability of alkalescent soil Cd |
| CN113133396A (en) * | 2021-04-21 | 2021-07-20 | 扬州大学 | Method for reducing cadmium content in rice |
| CN113604225A (en) * | 2021-08-10 | 2021-11-05 | 广东石油化工学院 | Soil pollution-control and yield-increase bidirectional regulation material and preparation method thereof |
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