CN105061114B - A kind of heavy metal polluted soil of farmland composite modifying agent and preparation method thereof and method of administration - Google Patents
A kind of heavy metal polluted soil of farmland composite modifying agent and preparation method thereof and method of administration Download PDFInfo
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Abstract
The present invention relates to a kind of heavy metal polluted soil of farmland composite modifying agent and preparation method thereof and method of administration, it is to comprise the following raw materials by weight percent：Activate weathered coal 20%~40%, charcoal 15%~25%, sepiolite 10%~25%, calcium magnesium phosphate 10%~20%, Diammonium phosphate (DAP) 10%~20%；Wherein activation weathered coal is the gained after ammonium hydrogen carbonate and ultrasonic activation.Sepiolite is through 600 800 DEG C of pyrolysis gained.The composite modifying agent of the present invention is of low cost, formula is simple, is mainly used for being passivated Cd, Cu, Pb, Zn heavy metal in soil, heavy-metal contaminated soil effectively can be repaired, it can ensure the sustainable production capacity of soil again, realize the sustainable use of soil.
Description
Technical field
The present invention relates to a kind of heavy metal polluted soil of farmland composite modifying agent and preparation method thereof and method of administration, belong to
Technical field of soil remediation.
Background technology
In recent years, China's heavy metal pollution shows aggravation situation, and heavy metal pollution of soil is to ecological environment, food security
It constitutes a serious threat with health.The whole nation by heavy metal pollution arable land there are about 10,000,000 hectares, account for about total cultivated area
More than 10%, every year by up to 12,000,000 tons of the grain of heavy metal pollution, grain drop in production is caused to be up to due to heavy metal pollution
More than 1000 ten thousand tons, add up at least 20,000,000,000 yuan of economic loss.Further, since heavy metal pollution of soil has complexity, the length formed
The cumulative bad of phase, the concealment occurred, the slow of toxicity, the particularity of diagnosis and the chronicity of recovery, cause heavy metal-polluted
Dye has become " the stealthy killer " of health.
At present, domestic and international scientific research personnel has carried out extensive research to heavy metal polluted soil of farmland reparation.According to improvement
The difference of technique and principle, contaminated soil Treatment process can be divided into：Naturally reparation, physical engineering reparation, chemical remediation, biology are repaiied
Multiple, joint reparation etc..Wherein, chemical remediation is directed to add modifying agent in soil to change the physics of soil, chemical property, logical
Absorption, precipitation or the co-precipitation to heavy metal are crossed, changes the existing forms of heavy metal in the soil, so as to reduce its life
Object validity and migration.The features such as chemical remediation technology is of low cost, simple, quick, efficient, it is light to be highly suitable for large area
The agricultural land soil of moderate heavy metal pollution.
Chemical improvement agent type currently used for restoration of soil polluted by heavy metal is more, and common modifying agent includes inorganic change
Good dose and organic amendment.Inorganic amendment mainly includes the alkaline matters such as lime, flyash, hydroxyapatite, ground phosphate rock etc.
The minerals such as phosphate and zeolite, sepiolite, bentonite；Organic amendment mainly includes farm manure, green manure, biological carbon etc.
Organic materials.It has been reported that heavy metal modifying agent have it is as follows：Chinese patent CN103484125A discloses a kind of solid bamboo shoot shell base
Charcoal heavy metal-polluted soil lead modifying agent；Chinese patent CN103468269A discloses a kind of soil using modified straw as raw material
Heavy metal renovation agent；Chinese patent CN103589435A discloses a kind of soil weight using tea waste and humic acid potassium as raw material
Metal-regulatory agent；It is raw material that Chinese patent CN102174325A, which discloses a kind of utilization plant slag, sepiolite powder and quick lime,
Farmland soil heavy metals passivator；Chinese patent CN103936530A discloses one kind with calcium magnesium phosphate, charcoal base manure and lime stone
Cadmium pollution soil passivator agent for primary raw material；Chinese patent CN101722183A discloses a kind of with whole soil, addition improvement
The modification method of agent and earthing for the heavy-metal contaminated soil of main flow；Chinese patent CN102807872A discloses a kind of profit
With the soil heavy metal passivant that charcoal, medical stone powder, diatomite in powder, flyash and lignite are raw material.
Although there is respective advantage in terms of above-mentioned modifying agent heavy-metal contaminated soil reparation, but still there are the following problems：(1)
Contain heavy metal in the raw material of part heavy metal modifying agent, secondary pollution can be generated；(2) modifying agent kind is more single and uses
Amount is big, and permanence operation can produce bigger effect soil quality.Therefore, research one kind can be heavy metal-passivated but also be improved
The modifying agent of soil quality, and a cheap and effective soil remediation measure is made, in actual production will
It is extremely important.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of heavy metal polluted soil of farmland composite modifying agent, the soil
Composite modifying agent not only can effectively repair heavy-metal contaminated soil, but also can ensure the sustainable production capacity of soil,
For being passivated heavy metal-polluted soil and improving soil quality, solve soil influences asking for its sustainable use due to heavy metal pollution
Topic.
The present invention also provides a kind of preparation methods of heavy metal polluted soil of farmland composite modifying agent.
The present invention also provides a kind of method of administration of heavy metal polluted soil of farmland composite modifying agent.
Term explanation：
Due to mankind's activity, the content of minor metallic element in the soil in soil is more than background value, excess deposition and
Caused too high levels, are referred to as heavy metal pollution of soil.Evaluate the general foundation of soil environment quality《Soil environment quality mark
It is accurate》(GB15618-1955) standard limited value in, using synthetic temperature difference, calculation formula is：
P in formulaiMass fraction for i pollution factors；CiMeasured concentration for i pollution factors；SiFor commenting for i pollution factors
Price card is accurate, usually selects the i-th pollutant load (mg/kg) in background value sample.
Slight heavy-metal contaminated soil：Refer to 1 ＜ P ＜ 2, be slight heavy-metal contaminated soil.
Between slight and moderate heavy-metal contaminated soil：Refer to 2 ＜ P ＜ 3, be between slight and moderate heavy metal-polluted
Contaminate soil.
The heavy-metal contaminated soil of moderate：Refer to 3 ＜ P ＜ 4, be the heavy-metal contaminated soil of moderate.
Technical scheme is as follows：
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Activate weathered coal 20%~40%, charcoal 15%~25%, sepiolite 10%~25%, calcium magnesium phosphate 10%
~20%, Diammonium phosphate (DAP) 10%~20%；
The activation weathered coal is by weathered coal and ammonium hydrogen carbonate in mass ratio 1：After the mass ratio mixing of (1-5), in
50-70 DEG C of temperature is once activated, and re-activation is then carried out under ultrasound condition is made, soak time 1-2 days, and two
The ultrasonic power of secondary activation is 100-300W, and ultrasonic time is 10-30 minutes；
The sum of above each raw material weight percentage is 100%.
Currently preferred, activation weathered coal is obtained by the following method：Weathered coal is crushed, crosses 80-120 mesh sieve, wind
Change coal and ammonium hydrogen carbonate in mass ratio 1：The mass ratio mixing of (1-5) is subsequently placed in 50-70 DEG C and carries out primary activation 1-3 days, obtains
Weathered coal after primary activation；It once adds in distilled water in weathered coal after activation to stir evenly, the addition of distilled water is lived with primary
The mass ratio of weathered coal is (7-9) after change:1,10-30 points of re-activation is then carried out in ultrasound of the power for 100-300W
Activation weathered coal is made in clock, forced air drying.
It is further preferred that weathered coal is 1 in mass ratio with ammonium hydrogen carbonate:1.
It is currently preferred, a kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent be by with
The raw material composition of lower weight percent：Activation weathered coal 32%~38%, charcoal 16%~18%, sepiolite 12%~
20%, calcium magnesium phosphate 12%~16%, Diammonium phosphate (DAP) 12%~16%.
Currently preferred, the activation weathered coal grain size is 80-120 mesh, and charcoal grain size is 20-40 mesh, sepiolite
Grain size is 80-100 mesh, in sepiolite dioxide-containing silica between 54~60%, content of magnesia is between 21~25%；Calcium
Magnesium-phosphorus fertilizer and Diammonium phosphate (DAP) grain size are 60-80 mesh；
The content of humic acid that dissociates in the activation weathered coal of the present invention can improve 6-8 times compared with weathered coal raw material.Charcoal master
If the solid product that agricultural wastes in anoxic or anoxybiotic environment, generate after low temperature thermal cracking, ingredient are contained based on carbon
Amount is related with raw material.
Above-mentioned a kind of preparation method of heavy metal polluted soil of farmland composite modifying agent provided by the present invention, step is such as
Under：
(1) by sepiolite raw ore mechanical crushing to 80-100 mesh powders, at 100-105 DEG C freeze-day with constant temperature to constant weight,
600-800 DEG C is then heated to, is heated 0.5-2 hours；
(2) will through step (1) treated sepiolite is cooled to 40-50 DEG C, it is small to add in activation weathered coal heat preservation 0.5-2
When, it is cooled to room temperature, obtains preliminary mixture；
(3) charcoal, calcium magnesium phosphate, Diammonium phosphate (DAP) are added in into preliminary mixture by proportioning, with 100-200 revs/min
Speed of agitator be mixed 5-10 minutes to get heavy metal polluted soil of farmland composite modifying agent.
Currently preferred, in above-mentioned steps (1), warming temperature is 750-780 DEG C, heating time 0.5-1 hour.
Above-mentioned a kind of method of administration of heavy metal polluted soil of farmland composite modifying agent provided by the present invention, using as follows
A kind of method carries out：
1. for slight heavy-metal contaminated soil, composite modifying agent is applied into contaminated soil surface, then rotary tillage 2-3 times,
Rotary tillage depth is 15-20cm, is placed 10-15 days after rotary tillage, the amount of application of composite modifying agent be 70-90kg/ per acre；Further promote
It is fully reacted with heavy metal into modifying agent；
2. for the heavy-metal contaminated soil between slight and moderate, composite modifying agent is applied into contaminated soil surface, first
It is ploughed deeply, ploughs deeply thickness as 25-30cm, then rotary tillage 1-2 times, rotary tillage depth is 15-20cm, is placed 10-15 days after rotary tillage,
The amount of application of composite modifying agent for 110-130kg/ per acre；Further modifying agent is promoted fully to be reacted with heavy metal；
3. contaminating soil for moderate dirt heavy metal, composite modifying agent is applied into contaminated soil surface, rotary tillage 1-2 times, rotary tillage
Depth is 15-20cm, is ploughed deeply after rotary tillage, ploughs deeply thickness as 25-30cm, rotary tillage 1-2 times is carried out to soil again after ploughing deeply,
Placed 10-15 days after rotary tillage, the amount of application of composite modifying agent for 150-170kg/ per acre；Further promote modifying agent and heavy metal
Fully reaction.
Currently preferred, for slight heavy-metal contaminated soil, the amount of application 80kg/ of composite modifying agent is per acre.
Currently preferred, for the heavy-metal contaminated soil between slight and moderate, the amount of application of composite modifying agent is
120kg/ is per acre.
It is currently preferred, for moderate heavy-metal contaminated soil, the amount of application of composite modifying agent for 160kg/ per acre.
The present invention also provides a kind of heavy metal polluted soil of farmland composite modifying agent in the application of passivation heavy metal-polluted soil, use
In being passivated Cd, Cu, Pb, Zn heavy metal in soil.
Containing a large amount of humic acid in weathered coal, humic acid contains phenol as larger molecular organics matter on molecular structure
The various actives such as hydroxyl, hydroxyl and alcoholic extract hydroxyl group functional group, because it has very high reactivity, therefore can be sent out with metal ion
Raw complex reaction, ion exchange etc., humic acid has very strong absorption property.But its activity is relatively low, the present invention uses
Weathered coal after activation improves its free humic acid content.In addition, the weathered coal after ultrasonication, humic acid activity
6-8 times can be improved, so as to improve the absorption to heavy metal.
Charcoal mainly includes following aspect to the improvement mechanism of heavy metal：Heavy metal and charcoal surface oxygen functional group
Between surface complexing；Form the precipitations such as carbonate or the phosphate of heavy metal；In addition, charcoal has larger ratio
Surface area and higher surface energy can carry out adsorption to heavy metal ion.Sepiolite is a kind of tool layer chain structure
The clay mineral of magnesium silicate containing Shuifu County is a kind of environmentally friendly mineral material, due to huge specific surface area and special
Layer structure has very strong adsorption capacity to the heavy metal element in soil.
Calcium magnesium phosphate can increase soil pH value, and heavy metal ion is promoted to precipitate, and have so as to reduce heavy metal in soil
Imitate state content.In addition, the adsorbable divalent class heavy metal in insoluble phosphate surface in calcium magnesium phosphate, and form the low difficulty of solubility
Molten mineral, while the Mg in calcium magnesium phosphate2+、Ca2+Etc. can be with heavy metal (Cd2+、Pb2+Deng) antagonism occurs, alleviate a huge sum of money
The toxic action of category, so as to reduce absorption of the plant to heavy metal.Diammonium phosphate (DAP) mechanism of action, which is mainly based upon phosphate radical, to be changed
Become soil surface charge, increase the absorption of soil/Mineral pairs heavy metal, so as to reduce the validity of heavy metal.
The preparation method of the present invention uses natural sepiolite directly to steep natural sea by the method for heat modification for raw material
Stone carries out reaming, and partial activation weathered coal is made to enter in sepiolite lattice system, original mineral composition by recombinating and reacting,
Make its metal ion that complex reaction, ion exchange enhancing occur, strengthen sepiolite and weathered coal absorption, complex copper, lead,
The effect of zinc, cadmium.
The reaction mechanism of the heavy metal composite modifying agent processing contaminated soil of the present invention is as follows：
The composite modifying agent of the present invention is of low cost, and formula is simple, is mainly used for being passivated Cd, Cu, Pb, Zn huge sum of money in soil
Belong to, heavy-metal contaminated soil can effectively be repaired, and can ensure the sustainable production capacity of soil, for being passivated soil
Earth heavy metal and improvement soil quality, the weathered coal after charcoal, sepiolite and activation can improve the quality of soil agreegate, water
Stable aggregate content and Cation Exchange Capacity in Soils, calcium magnesium phosphate and Diammonium phosphate (DAP) can increase soil fertility.In addition, rotary tillage
Purpose is to be sufficiently mixed modifying agent and heavy metal in soil, reduces bioavailability of heavy metals；The main function mechanism ploughed deeply
It is to be diluted contaminated soil, reduces the concentration of heavy metal in the soil.
Specific embodiment
With reference to embodiment, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Activate weathered coal 20%%, charcoal 20%, sepiolite 20%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
The activation weathered coal is obtained by the following method：Weathered coal is crushed, is sieved with 100 mesh sieve, weathered coal and carbonic acid
Hydrogen ammonium in mass ratio 1:1 mass ratio mixing is placed in 60 DEG C and carries out primary activation 2 days, then will be after an ammonium hydrogen carbonate activation
Weathered coal presses water：The mass ratio of weathered coal and ammonium hydrogen carbonate is 8:1 adds in distilled water, after stirring evenly, in power be 200W
Re-activation is carried out in ultrasound 20 minutes, activation weathered coal is made in forced air drying.
Preparation process is as follows：
(1) by sepiolite raw ore mechanical crushing to 100 mesh powders, at 105 DEG C then freeze-day with constant temperature heats up to constant weight
To 780 DEG C, heat 1 hour；
(2) will through step (1) treated sepiolite is cooled to 40 DEG C, add in activation weathered coal and keep the temperature 1 hour, be cooled to
Room temperature obtains preliminary mixture：
(3) charcoal, calcium magnesium phosphate, Diammonium phosphate (DAP) are added in into preliminary mixture by proportioning, with 200 revs/min stir
Mix rotating speed is mixed 8 minutes to get heavy metal polluted soil of farmland composite modifying agent.
The method that slight heavy-metal contaminated soil is purified using above-mentioned heavy metal modifying agent, is included the following steps：It is clear first
Except upper soll layer sundries, keep upper soll layer smooth, by above-mentioned heavy metal modifying agent uniform broadcasting to contaminated soil surface, a huge sum of money
The additive for belonging to modifying agent is 80kg per acre, and after having broadcasted sowing heavy metal modifying agent, rotary tillage is carried out to topsoil using rotary cultivator,
Rotary tillage 3 times, rotary tillage depth are 18cm, are placed 12 days after rotary tillage, to ensure that modifying agent is uniformly mixed with soil, are further promoted
Modifying agent is reacted with heavy metal.
Embodiment 2
A kind of heavy metal polluted soil of farmland composite modifying agent, with embodiment 1, the difference lies in：
The soil composite modifying agent is to comprise the following raw materials by weight percent：Activate weathered coal 30%, charcoal
15%, sepiolite 15%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Using the purification of above-mentioned heavy metal modifying agent between the method for slight and moderate heavy-metal contaminated soil, including as follows
Step：Upper soll layer sundries is removed first, keeps upper soll layer smooth, by above-mentioned heavy metal modifying agent uniform broadcasting to Polluted Soil
Earth surface, the additive amount of heavy metal modifying agent is 120kg per acre, and after having broadcasted sowing heavy metal modifying agent, soil is ploughed deeply, deep
Thickness is turned over as 26cm, rotary tillage later 2 times, rotary tillage depth is 18cm to ensure that modifying agent is uniformly mixed with soil.Then farmland
It places 10-15 days, further modifying agent is promoted to be reacted with heavy metal.
Embodiment 3
A kind of heavy metal polluted soil of farmland composite modifying agent, with embodiment 1, the difference lies in：
The soil composite modifying agent is to comprise the following raw materials by weight percent：Weathered coal 35%, charcoal 15%, sea
Afrodite proportion is 10%, and calcium magnesium phosphate proportion is 20%, and Diammonium phosphate (DAP) proportion is 20%.
Using the method for the heavy-metal contaminated soil of above-mentioned heavy metal modifying agent purification moderate, include the following steps：First
Upper soll layer sundries is removed, keeps upper soll layer smooth, by above-mentioned heavy metal modifying agent uniform broadcasting to contaminated soil surface, weight
The additive amount of metal modifying agent is 160kg per acre, after having broadcasted sowing heavy metal modifying agent, using rotary cultivator to topsoil rotary tillage 1
Time, rotary tillage depth is 18cm, is ploughed deeply (purpose is to dilute heavy metal) later, ploughs deeply thickness as 26cm, after ploughing deeply again
Rotary tillage 1 time is carried out to soil, to ensure that modifying agent is uniformly mixed with soil.The farmland for adding passivator is placed 15 later
My god, further modifying agent is promoted to be reacted with heavy metal.
Comparative example 1
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Activate weathered coal 60%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Comparative example 2
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Charcoal 60%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Comparative example 3
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Sepiolite 60%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Comparative example 4
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Weathered coal 30%, charcoal 30%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Comparative example 5
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Charcoal 30%, sepiolite 30%, calcium magnesium phosphate 20%, Diammonium phosphate (DAP) 20%.
Comparative example 6
A kind of heavy metal polluted soil of farmland composite modifying agent, the soil composite modifying agent are by following weight percent
Raw material forms：Weathered coal 40%, charcoal 30%, sepiolite 30%.
Experimental example：Application of the composite modifying agent of the present invention in heavy metal-polluted soil passivation
1st, profile test
1.1st, test site：Greenhouse is tested by Shandong Academy of Agricultural Sciences, is cinnamon soil for examination soil, for trying the basic physics and chemistry of soil
Character is shown in Table 1.Experimental planting crop：Green vegetables.
Table 1, for try the basic physicochemical character of soil
1.2nd, experiment setting：Potting is taken in experiment, sets 10 different processing, and each processing is repeated 4 times, and is planted per basin
10 seeds of program request.May 25 was sowed, and of the right age seedling stage carries out thinning, final singling 4.Test process is shown in (table 2).Below processing 2,
The method of administration of modifying agent of the present invention described in processing 3 and processing 4 is manured into soil by the modifying agent of the present invention, remaining
The method of administration of processing is according to a conventional method.
Table 2, soil conditioner effect test setting (10 processing, 40 basins)
1.3rd, test method：Shandong Province's farmland pollution soil (content of beary metal and soil second mass mark are chosen in experiment
Standard is compared), it air-dries and crushed 2mm hole sizers, 2 kilograms of the dress soil per basin soil, while according to test process (table 2) by modifying agent
It uniformly mixes, the 80% of soil conservation field capacity, is kept for 15 days, it is therefore an objective to ensure modifying agent and heavy metal-polluted soil with soil
Fully reaction, carries out sowing pre-treatment, program request is carried out after green vegetables vernalization later, and pakchoi and soil are carried out after green vegetables harvest
Sampling analysis.1.4th, project and method are measured：Organic matter uses potassium bichromate titrimetric method；Full nitrogen uses Kjeldahl's method；Full phosphorus
Using molybdenum antimony resistance colorimetric method；Full potassium uses flare photometer；Soil pH is by Tu Shui than 1:2.5 electrode method；Copper, lead, zinc, cadmium are adopted
Use HF-HNO3-HClO4Digestion, Available Cu, lead, zinc, cadmium are extracted with DTPA methods, and atomic absorption spectrophotometer measures.
2nd, result and analysis
2.1st, composite modifying agent is to green vegetables growth and the influence of yield
Although being polluted for examination soil by heavy metal copper, lead, zinc, cadmium, after planting emergence is normal, and after seedling stage,
The green vegetables plant strain growth of part processing shows apparent growth restriction, shows as the symptoms such as growth and development is slow, and plant is short and small.
Green vegetables are measured its character and yield, the results are shown in Table 3 after the growth of 40 days.
The plant height of green vegetables and determination of yield under the conditions of 3 different disposal of table
| Processing | Average plant height (cm) | Average product (g/ plants) |
| 1 | 11 | 13.1 |
| 2 | 23 | 77.3 |
| 3 | 21 | 75.2 |
| 4 | 22 | 74.7 |
| 5 | 19 | 55.2 |
| 6 | 19 | 54.6 |
| 7 | 20 | 50.0 |
| 8 | 21 | 66.0 |
| 9 | 20 | 59.5 |
| 10 | 14 | 25.6 |
2.1.1 there is apparent difference in the plant height and yield, respectively handled, is not added with the green vegetables of the processing 1 (CK) of modifying agent
Average product is minimum (table 3).It adds the green vegetables plant height of the processing 10 of part modifying agent and yield is higher than processing 1, but less than processing
2-9。
2.1.2, plant height and yield performance most preferably use the processing 2-4 of modifying agent of the present invention, and green vegetables grow fine, table
Reveal repairing effect (table 3) of the composite modifying agent to contaminated soil.
Although 2.1.3, less than processing 2-4, its yield is higher than 10 (tables 3) of processing for the green vegetables plant height of processing 5-9 and yield,
This aspect illustrates that the effect of heavy metal composite modifying agent is better than single modifying agent using effect, on the other hand also illustrates to improve
Agent has also played the effect of its fertilizer efficiency in green vegetables growth course.
2.2nd, influence of the composite modifying agent to content of beary metal in green vegetables
2.2.1, in all processing, being not added with green vegetables content of beary metal in the processing 1 (control) of any modifying agent is
Highest, applying green vegetables content of beary metal in the processing 2-10 of modifying agent has different degrees of decline, shows modifying agent certain
Absorption of the green vegetables to heavy metal can be reduced in degree, reduces influence of the heavy metal to quality of agricultural product.
2.2.2, in the processing of addition modifying agent, green vegetables in processing 5-9 will be less than by handling green vegetables content of beary metal in 2-4
Content of beary metal, this illustrates that composite modifying agent is better than the improved effect of heavy-metal contaminated soil single or less than two kinds objects
Expect the modifying agent of composition.
2.2.3, in the processing of addition modifying agent, green vegetables content of beary metal is higher than green vegetables in processing 2-4 in processing 10
Content of beary metal, this may be because being added to calcium magnesium phosphate and Diammonium phosphate (DAP) in composite modifying agent, contain in both substances
Certain nutrient, and nutrient can reduce absorption of the green vegetables to heavy metal with weathered coal, biological carbon and sepiolite synergistic effect.
The use of modifying agent of the present invention described above can effectively reduce absorption of the green vegetables to copper, lead, zinc, cadmium in soil.
The measurement result of green vegetables content of beary metal under the conditions of 4 different disposal of table
2.3rd, influence of the composite modifying agent to soil available content of beary metal
After heavy-metal contaminated soil addition modifying agent, it is mainly manifested in the variation of soil available content of beary metal.And have
The biological effectiveness of effect state content of beary metal and heavy metal has substantial connection, is the principal element for influencing plant absorption heavy metal.
Table 5 is the situation of change of soil available content of beary metal before and after plantation green vegetables.As can be seen from Table 5, the soil of all processing
Available heavy metal content is below the content before experiment, having in processing 2, processing 3 and the processing 4 of modifying agent of the present invention in earth
Effect state copper, lead, cadmium content decline 22.6%, 11.3% and 20.2% respectively than control (processing 1) highest, and zinc is not shown significantly
Variation, highest only decline 2.4%, this is primarily due to bring a part of zinc in modifying agent into, counteract the part of modifying agent passivation
Zinc.In addition, the Available Cu, lead, zinc, cadmium content in the processing 2-4 of modifying agent of the present invention contain less than heavy metal in processing 5-9
Amount, but higher than content of beary metal in processing 10, this is mainly due to be higher than in processing 10 for heavy metal-passivated material ratio
Handle 2-4.
Table 5 tests front and rear soil available content of beary metal variation
Claims (6)
1. a kind of heavy metal polluted soil of farmland composite modifying agent, which is by the original of following weight percent
Material composition：Activation weathered coal 20%~40%, charcoal 15%~25%, sepiolite 10%~25%, calcium magnesium phosphate 10%~
20%, Diammonium phosphate (DAP) 10%~20%；
The activation weathered coal is obtained by the following method：Weathered coal is crushed, crosses 80-120 mesh sieve, weathered coal and bicarbonate
Ammonium in mass ratio 1：The mass ratio mixing of (1-5) is placed in 50-70 DEG C and carries out primary activation 1-3 days, then an ammonium hydrogen carbonate is lived
Weathered coal after change presses water：The mass ratio of weathered coal and ammonium hydrogen carbonate is (7-9):1 adds in distilled water, after stirring evenly, Yu Gong
Re-activation is carried out in the ultrasound that rate is 100-300W 10-30 minutes, and activation weathered coal is made in forced air drying；
It is 80-120 mesh to activate weathered coal grain size, and charcoal grain size is 20-40 mesh, and sepiolite grain size is 80-100 mesh, sepiolite
Middle dioxide-containing silica is between 54~60%, content of magnesia is between 21~25%；Calcium magnesium phosphate and Diammonium phosphate (DAP) grain size
For 60-80 mesh；
The sum of above each raw material weight percentage is 100%；
Preparation method, step are as follows：
(1) by sepiolite raw ore mechanical crushing to 80-100 mesh powders, freeze-day with constant temperature is to constant weight at 100-105 DEG C, then
600-800 DEG C is warming up to, is heated 0.5-2 hours；
(2) will through step (1) treated sepiolite is cooled to 40-50 DEG C, add in activation weathered coal and keep the temperature 0.5-2 hours, it is cold
But to room temperature, preliminary mixture is obtained：
(3) charcoal, calcium magnesium phosphate, Diammonium phosphate (DAP) are added in into preliminary mixture by proportioning, with 100-200 revs/min stir
Mix rotating speed is mixed 5-10 minutes to get heavy metal polluted soil of farmland composite modifying agent.
2. heavy metal polluted soil of farmland composite modifying agent according to claim 1, which is characterized in that activating weathered coal is
It is made by the following method：Weathered coal is 1 in mass ratio with ammonium hydrogen carbonate:1.
3. heavy metal polluted soil of farmland composite modifying agent according to claim 1, which is characterized in that the soil is compound to be changed
Good dose is to comprise the following raw materials by weight percent：Activate weathered coal 32%~38%, charcoal 16%~18%, sepiolite
12%~16%, calcium magnesium phosphate 12%~16%, Diammonium phosphate (DAP) 12%~16%.
4. heavy metal polluted soil of farmland composite modifying agent according to claim 1, which is characterized in that in step (1), rise
Temperature is 750-780 DEG C, heating time 0.5-1 hour.
5. a kind of method of administration of heavy metal polluted soil of farmland composite modifying agent described in claim 1, using a kind of following side
Method carries out：
1. for slight heavy-metal contaminated soil, composite modifying agent is applied into contaminated soil surface, then rotary tillage 2-3 times, rotary tillage
Depth is 15-20cm, is placed 10-15 days after rotary tillage, the amount of application of composite modifying agent for 70-90kg/ per acre；Further promote to change
Good dose is fully reacted with heavy metal；
2. for the heavy-metal contaminated soil between slight and moderate, composite modifying agent is applied into contaminated soil surface, is first carried out
It ploughs deeply, ploughs deeply thickness as 25-30cm, then rotary tillage 1-2 times, rotary tillage depth is 15-20cm, is placed 10-15 days after rotary tillage, compound
The amount of application of modifying agent for 110-130kg/ per acre；Further modifying agent is promoted fully to be reacted with heavy metal；
3. contaminating soil for moderate dirt heavy metal, composite modifying agent is applied into contaminated soil surface, rotary tillage 1~2 time, rotary tillage depth
It for 15-20cm, is ploughed deeply after rotary tillage, ploughs deeply thickness as 25-30cm, carry out rotary tillage 1~2 time, rotation after ploughing deeply to soil again
Is placed 10-15 days after ploughing, the amount of application of composite modifying agent be 150-170kg/ per acre；Further modifying agent is promoted to be filled with heavy metal
Divide reaction.
6. the method for administration of the 1 heavy metal polluted soil of farmland composite modifying agent, feature are required according to claims
It is, for slight heavy-metal contaminated soil, the amount of application 80kg/ of composite modifying agent is per acre；For between slight and moderate
Heavy-metal contaminated soil, the amount of application of composite modifying agent for 120kg/ per acre；For moderate heavy-metal contaminated soil, compound improvement
The amount of application of agent for 160kg/ per acre.
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