CN102220136B - Soil heavy metal composite passivator with humic acid minerals and preparation method thereof - Google Patents
Soil heavy metal composite passivator with humic acid minerals and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a soil heavy metal composite passivator with humic acid minerals and a preparation method thereof. The soil heavy metal composite passivator is prepared by humic acid mineral powder, fused calcium magnesium phosphate and quick lime according to a certain proportion. The preparation method comprises the following steps: A, preparing the humic acid mineral powder: taking humic acid raw ore, carrying out ball-milling to the humic acid raw ore, and sieving the humic acid raw ore by a 110-140-mesh sieve for standby; and B, uniformly mixing the raw material prepared in the step A, fused calcium magnesium phosphate and quick lime, adjusting the water content of the mixture to be 10% counting by H2O, and stacking the mixture for five-seven days to obtain the soil heavy metal composite passivator with the humic acid minerals, so that the operation is simple and the method is easy to implement. By the invention, the available cadmium content of red sand mud soil with the full-cadmium content of 10mg/kg (by exogenous adding) is reduced by 0.36-2.25mg/kg within ninety-day culture time, the reduction amplitude reaches up to 4.7-25.7%, the efficiency of the soil heavy metal composite passivator with the humic acid minerals under a water condition of 45% WHC (Water-holding Capacity) is better than that under a flooded condition, and the soil heavy metal composite passivator with the humic acid minerals also has the functions of passivating heavy metal in soil, soil fertility and the like and has significant popularization and application values in vast heavy metal pollution regions.
Description
Technical field
The invention belongs to agricultural environment child care and recovery technique field, what more specifically relate to is a kind of soil heavy metal combined passivator that contains humic acid minerals, also relate to simultaneously a kind of preparation method who contains the soil heavy metal combined passivator of humic acid minerals, be applicable to various contaminated by heavy metals soil, especially dryland soils.
Background technology
Along with the fast development of industry and the continuous increase of agricultural input intensity, the pollutents such as plurality of heavy metal enter edatope, thereby have caused Heavy metal pollution of soil, and become one by the global problem of extensive concern.Heavy metal in the soil can enter food chain by plant absorbing, and then HUMAN HEALTH is constituted a serious threat.It is reported that China is subjected to the cultivated area of the heavy metal contaminations such as cadmium, lead, mercury, arsenic, nickel to break through 2,000 ten thousand hm
2, account for 20% of national total cultivated area, had a strong impact on the stable of modern agricultural development and society.The toxic heavy metal elements such as cadmium mainly are subjected to the impact of the factors such as potential of hydrogen (pH), redox potential (Eh), organic content and cation exchange capacity (CEC) of soil on the validity of plant.Studies show that in a large number humic acids can change the form that exists of the toxic heavy metal elements such as Cadmium in Soil, thereby affects it to the validity of plant.But this impact has multiplicity, and the fulvic acid of molecular weight etc. can promote the desorb of the heavy metal elements such as Cadmium in Soil, strengthen it to the validity of plant; The rotten acid of the ash that molecular weight is larger and ulmic acid etc. are the activity of the heavy metal element such as passivation Cadmium in Soil effectively, thereby reduces it to the validity of plant.Yet the extraction cost of the rotten acid of ash and ulmic acid is higher, and the difficulty of large scale application is very large.The humic acids breeze is directly made through ball milling by its raw ore, it is a kind of baroque natural polymer organic polymer, contain a large amount of carboxyls, quinonyl and phenolic hydroxyl group isoreactivity group, have wetting ability, adsorptivity, ion exchangeable, complexing, oxidation-reduction quality and biological activity.In a single day the humic acids breeze applies in the soil, can with soil in the various reactions such as heavy metal ion generation ion-exchange, redox, absorption and complexing of the plant availability such as water-soluble attitude, ADSORPTION STATE, make heavy metal ion fixing by complexing, chelating or absorption, thereby reduce it to the validity of plant, and the Manufacture and application cost is relatively cheap, has larger application potential aspect the heavy-metal contaminated soil improvement.Simultaneously, fused(calcium magnesium)phosphate also is the soil heavy metal passivant of at present the most frequently used a kind of phosphorus element class material.
Summary of the invention
The objective of the invention is to be to provide a kind of soil heavy metal combined passivator that contains humic acid minerals, it is by the humic acids breeze, three kinds of raw materials of fused(calcium magnesium)phosphate and unslaked lime are made by a certain percentage, making full cadmium content is the red husky mud of 10mg/kg (adding by external source), saturated field capacity (WHC) 110% is the 0.36-1.43mg/kg that descended of the effective cadmium content of soil under the flooding condition, decrease by 4.7-18.0%, effective cadmium content of soil under 45% saturated field capacity (WHC) condition has reduced 0.87-2.25mg/kg, decrease by 9.9-25.7%, and effect significantly strengthens along with the increasing of using product amount of the present invention, has huge application value in vast heavy metal contamination area.
Another object of the present invention is to be to provide a kind of preparation method who contains the soil heavy metal combined passivator of humic acid minerals, and is simple to operate, easy to implement the method.
In order to realize above-mentioned Destination and task, the present invention has adopted following technical measures:
A kind of soil heavy metal combined passivator that contains humic acid minerals, it is made by the massfraction of following three kinds of raw materials:
A kind of soil heavy metal combined passivator that contains humic acid minerals, it makes (preferable range) by the massfraction of following three kinds of raw materials:
A kind of preferred plan that contains the soil heavy metal combined passivator of humic acid minerals is:
Described humic acids breeze, directly sieved through ball milling by its raw ore and to make (reaching the requirement of 110-140 order), it is a kind of baroque natural polymer organic polymer, contain a large amount of carboxyls, quinonyl and phenolic hydroxyl group isoreactivity group, has wetting ability, adsorptivity, ion exchangeable, complexing, the characteristic such as oxidation-reduction quality and biological activity, after applying in the soil by with soil in water-soluble attitude, the heavy metal ion generation ion-exchange of the plant availabilities such as ADSORPTION STATE, redox, the various reactions such as absorption and complexing, make heavy metal ion by complexing, chelating or absorption are fixing, thereby reduce the plant availability of heavy metal in soil ion, its organic carbon content is generally between 25-40%, also be a kind of colory organic mineral fertilizer, it has the dual-use function of passivation heavy metal-polluted soil and Study on Fertilizing soil fertility in the present invention concurrently.But because humic acids breeze itself belongs to weakly acidic material (pH value＜6), need to regulate its potential of hydrogen to neutral (the pH value is about 7) by alkaline matter, use the problems such as soil acidification of initiation to prevent disposable deposit.
Described fused(calcium magnesium)phosphate is the stronger phosphate fertilizer commonly used of a kind of alkalescence, also is the soil heavy metal passivant of at present the most frequently used a kind of phosphorus element class material, and its alkali divides (in CaO), soluble silicon (with SiO
2Meter) and effectively the content of magnesium (in MgO) is respectively 45%, 20% and 12%, and it has the passivation heavy metal-polluted soil in the present invention concurrently, regulate the normally multi-functionals such as the plain nutrition of phosphorus of production of the pH value of humic acids breeze and supply crop.
Described unslaked lime, it is a kind of strong alkaline substance of being produced through operations such as acidolysis, adding reaction of sodium bicarbonate and calcinings by calcium carbonate, main component is calcium oxide, the content of its CaO generally reaches 90-99%, it is the soil heavy metal passivant of the most frequently used a kind of alkaline matter, its major function in the present invention is the pH value of regulating the humic acids breeze, and improves rapidly in the short period of time the pH value of soil, consolidates and strengthen the effect of passivation heavy metal-polluted soil.
A kind of preparation method who contains the soil heavy metal combined passivator of humic acid minerals the steps include:
A. humic acids breeze preparation: select the humic acids raw ore, cross the 110-140 mesh sieve through ball milling, for subsequent use.Described humic acids raw ore, its organic carbon content (take C) is 25-40%, heavy metal cadmium content (in Cd)≤1mg/kg, content of heavy metal lead (in Pb)≤20mg/kg, moisture content is (with H
2The O meter)≤10%.
B. with the prepared raw material of step (A), mix with fused(calcium magnesium)phosphate, unslaked lime, and by spray pattern with the moisture content of mixture (with H
2O meter) transfer to 10% after, macerated again heap 5-7 days, be a kind of soil heavy metal combined passivator that contains humic acid minerals.Described fused(calcium magnesium)phosphate, its quality need meet the standard of GB 20412-2006 premium grads; Described unslaked lime, its CaO content is 90-99%, heavy metal cadmium and lead amount (in Cd, Pb)≤5mg/kg, moisture content is (with H
2The O meter)≤1.5%.
Product after making can be widely used in various contaminated by heavy metals soil, especially dryland soils.
The present invention compared with prior art has the following advantages and effect:
A. principal character of the present invention has been reasonable disposition to cadmium, plumbous, copper, zinc, chromium, the heavy metal elements such as nickel have humic acids breeze and the stronger fused(calcium magnesium)phosphate of alkalescence of extremely strong adsorptive power, three kinds of materials of unslaked lime, and given full play to the multi-functional of various materials, making full cadmium content is the red husky mud of 10mg/kg (adding by external source), saturated field capacity (WHC) 110% is the 0.36-1.43mg/kg that descended of the effective cadmium content of soil under the flooding condition, decrease by 4.7-18.0%, effective cadmium content of soil under 45% saturated field capacity (WHC) condition has reduced 0.87-2.25mg/kg, decrease by 9.9-25.7%, and effect significantly strengthens along with the increasing of using product amount of the present invention, has huge application value in vast heavy metal contamination area.
B. the present invention not only has the function of in-situ passivation heavy metal-polluted soil, and can also improve greatly organic content and the cation exchange capacity of soil, have the function of fertilizing soil etc. concurrently, be applicable to the soil that various soil parent materials are grown, especially dryland soil is a kind of broad spectrum type, multi-functional environmentfriendly products.
C. raw material sources of the present invention are extensive, simple, the easy row of preparation method, and easy to use, popularizing application prospect is wide.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but is not to be limitation of the present invention, all any this areas of doing according to the disclosure of invention be equal to replacement, all belong to protection scope of the present invention.
Embodiment 1:
A kind of soil heavy metal combined passivator that contains humic acid minerals, it is made by the massfraction of following three kinds of raw materials:
A kind of preparation method who contains the soil heavy metal combined passivator of humic acid minerals the steps include:
A. humic acids breeze preparation: select the humic acids raw ore, cross 110 orders through ball milling, or 120 orders, or 130 orders, or 140 mesh sieves, for subsequent use.Described humic acids raw ore, its organic carbon content (take C) is 25-40%, heavy metal cadmium content (in Cd)≤1mg/kg, content of heavy metal lead (in Pb)≤20mg/kg, moisture content is (with H
2The O meter)≤10%.
B. with the prepared raw material of step (A), mix with fused(calcium magnesium)phosphate, unslaked lime, and by spray pattern with the moisture content of mixture (with H
2O meter) transfer to 10% after, macerated again heap 5 or 6 or 7 days, be a kind of soil heavy metal combined passivator that contains humic acid minerals.Described fused(calcium magnesium)phosphate, its quality need meet the standard of GB 20412-2006 premium grads; Described unslaked lime, its CaO content is 90-99%, heavy metal cadmium and lead amount (in Cd, Pb)≤5mg/kg, moisture content is (with H
2The O meter)≤1.5%.
Product after making can be widely used in various contaminated by heavy metals soil, especially dryland soils.
Embodiment 2-example 15:
A kind of soil heavy metal combined passivator that contains humic acid minerals, it is made by the massfraction of following raw material:
| Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| The humic acids breeze | 97.0 | 96.0 | 95.0 | 94.0 | 93.0 | 92.0 | 91.0 | 89.0 | 88.0 | 87.0 | 86.0 | 85.0 | 84.0 | 83.0 |
| Fused(calcium magnesium)phosphate | 2.5 | 3.0 | 3.5 | 4.0 | 4.5 | 5.0 | 5.5 | 6.5 | 7.0 | 7.5 | 8.0 | 8.5 | 9.0 | 9.5 |
| Unslaked lime | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 | 3.5 | 4.5 | 5.0 | 5.5 | 6.0 | 6.5 | 7.0 | 7.5 |
Its preparation process is identical with embodiment 1.Product after making can be widely used in various contaminated by heavy metals soil, especially dryland soils.
A kind of pot experiment of the soil heavy metal combined passivator that contains humic acid minerals is as described below:
For trying material: supplying examination soil is the red husky mud of 0-20cm topsoil, picks up from Fauna of Taoyuan, Nw Hunan, and its essential property sees attached list 1; Originate from Pingxiang Jiangxi for examination humic acids breeze, its essential property sees attached list 2.
Soil pretreatment: natural air drying, grind, cross the 2mm nylon mesh, with 1.00g/LCdCl
2The solution form of (in Cd) is added external source Cd, and addition is 10mgCd/kg
Soil, stablize 2 weeks of ageing after, the air-dry 2mm nylon mesh of crossing is for subsequent use again.
Process to arrange: the fertilizing standards that 2 soil water contents (45%WHC and 110%WHC), 3 composite passivants are set (uses respectively 0,15 and 30g/kg by the product of embodiment 1
SoilComposite passivant), totally 6 processing, each is processed three times and repeats.Described WHC is the abbreviation of saturated field capacity.
Culture experiment: with the plastic cup of 18 750ml, load onto each 600g of air-dry soil that states preparation, under the air humidity conditions of 25 ± 1 ℃ room temperatures and 100%, cultivated 90 days.Gathered respectively pedotheque, and measured the available Cd (Cd of its soil in the the the the the 2nd, the 5th, the 10th, the 20th, the 30th, the 60th and the 90th day after on-test
DTPA) content, and the 2nd day cadmium form with the 90th day be analyzed.
Sample determination: the available Cd content in the soil is measured with DTPA digestion agent (pH=7.3) extraction-atomic absorption spectrophotometer (GBC Australia) method, and the cadmium form is measured with Tessier continuous extraction extraction-atomic absorption spectrophotometer (GBC Australia) method.
Main result: result of study shows (subordinate list 3), in 90 days incubation period, use product of the present invention, make the effective cadmium content of soil of red husky mud under the 110%WHC flooding condition descended 0.36-1.43mg/kg, decrease by 4.7-18.0%, then be respectively 0.87-2.25mg/kg and 9.9-25.7% under the 45%WHC moisture content condition, and effect strengthens significantly along with the increasing of using product amount of the present invention.
Compared with the control (subordinate list 4) under the 110%WHC flooding condition, uses the content (range of decrease is 5.1-11.3%) that product of the present invention has significantly reduced exchangeable cadmium, and its effect strengthens with the prolongation of incubation time and the increase of addition; Significantly increased the content of carbonate combined (amplification is 3.1-105.2%) and iron and manganese oxides combined (amplification is 11.3-29.3%) cadmium, its effect all strengthens with the addition of humic acids, but the prolongation with incubation time, the amplification of carbonate combined cadmium reduces gradually, and the amplification of iron and manganese oxides combined cadmium increases gradually; The variation that organically combines attitude cadmium and residual form cadmium is less.Under the moisture condition of 45%WHC (subordinate list 5), use the content (range of decrease is 3.7-17.7%) that product of the present invention has significantly reduced exchangeable cadmium, its variation tendency is consistent with 110%WHC's, but rangeability is larger; Carbonate combined cadmium (amplification is 8.4-145.3%) and iron and manganese oxides combined cadmium (amplification is 18.4-65.2%) have significantly been increased, its effect all strengthens with addition, but the prolongation with incubation time, the amplification of iron and manganese oxides combined cadmium reduces gradually and the amplification of carbonate combined cadmium increases gradually, and this overall variation trend with 110%WHC is just in time opposite; Organically combining attitude cadmium and residual form cadmium changes less.
Subordinate list 1 is for the essential property of examination soil
Subordinate list 2 is for the essential property of examination humic acids breeze
Use the content of the soil available cadmium of product of the present invention under the subordinate list 3 different in moisture conditions
Subordinate list 4Tessier cadmium classification (110%WHC)
Subordinate list 5Tessier cadmium classification (45%WHC)
Claims (9)
1. soil heavy metal combined passivator that contains humic acid minerals, it is made by the massfraction of following raw material:
Raw material %
Humic acids breeze 83.0-97.0
Fused(calcium magnesium)phosphate 2.5-9.5
Unslaked lime 0.5-7.5
Described humic acids breeze, being sieved through ball milling by its raw ore makes, and is a kind of natural polymer organic polymer, contains carboxyl, quinonyl and phenolic hydroxyl group active group, cadmium, lead, copper, zinc, chromium, nickel heavy metal ion are had adsorptive power, and its organic carbon content is between 25-40%;
Described unslaked lime is a kind of strong alkaline substance of being produced through acidolysis, adding reaction of sodium bicarbonate and calcination process by calcium carbonate, and its composition is calcium oxide, and chemical formula is CaO;
The described soil heavy metal combined passivator that contains humic acid minerals, its preparation process is:
A. humic acids breeze preparation: it is for subsequent use to select the humic acids raw ore to cross the 110-140 mesh sieve through ball milling; Described humic acids raw ore is take the organic carbon content of C as 25-40%, in heavy metal cadmium content≤1mg/kg of Cd, in content of heavy metal lead≤20mg/kg of Pb, with H
2The moisture content of O meter≤10%;
B. the raw material that step (A) is prepared and fused(calcium magnesium)phosphate, unslaked lime mix, and with its mixture with H
2Macerate again heap 5-7 days after the moisture content of O meter transfers to 10%, be a kind of soil heavy metal combined passivator that contains humic acid minerals;
Described unslaked lime, its CaO content is 90-99%, in heavy metal cadmium and the lead amount≤5mg/kg of Cd, Pb, moisture content is with H
2O meter≤1.5%.
2. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 87.0-93.0
Fused(calcium magnesium)phosphate 4.5-7.5
Unslaked lime 2.5-5.5.
3. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 90.0
Fused(calcium magnesium)phosphate 6.0
Unslaked lime 4.0.
4. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 97.0
Fused(calcium magnesium)phosphate 2.5
Unslaked lime 0.5.
5. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 95.0
Fused(calcium magnesium)phosphate 3.5
Unslaked lime 1.5.
6. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 92.0
Fused(calcium magnesium)phosphate 5.0
Unslaked lime 3.0.
7. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 88.0
Fused(calcium magnesium)phosphate 7.0
Unslaked lime 5.0.
8. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 85.0
Fused(calcium magnesium)phosphate 8.5
Unslaked lime 6.5.
9. a kind of soil heavy metal combined passivator that contains humic acid minerals according to claim 1 is characterized in that:
Raw material %
Humic acids breeze 83.0
Fused(calcium magnesium)phosphate 9.5
Unslaked lime 7.5.
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| CN101805617A (en) * | 2009-02-16 | 2010-08-18 | 中国科学院沈阳应用生态研究所 | Soil heavy metal passivant for facilities vegetable field and preparation method thereof |
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