CN108517215B - Acid soil heavy metal lead-cadmium in-situ passivator and preparation method and application thereof - Google Patents
Acid soil heavy metal lead-cadmium in-situ passivator and preparation method and application thereof Download PDFInfo
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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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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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
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- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Pest Control & Pesticides (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Fertilizers (AREA)
Abstract
The acid soil heavy metal lead-cadmium in-situ passivator as well as the preparation method and the application thereof comprise the following raw materials in parts by weight: 30-80 parts of biomass ash, 3-50 parts of steel slag, 3-30 parts of ammonium lignosulfonate and 5-30 parts of ferrous sulfate. According to the invention, the heavy metal Cd and Pb in-situ passivator is researched and developed by the synergistic effect of multiple components such as biomass ash, steel slag, ammonium lignosulfonate and ferrous sulfate, the pH value of soil is increased, meanwhile, rich medium and trace elements are provided for the soil, and the yield and quality of crops are increased. The problems of stacking of biomass ash, dust emission, high pH value and other environmental pollution caused by biomass power plants are solved, and comprehensive utilization of waste resources such as biomass ash, steel slag and the like is realized.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to an acid soil heavy metal lead-cadmium in-situ passivator, and a preparation method and application thereof.
Background
At present, heavy metal pollution in soil in China is serious and tends to rise year by year due to the influence of factors such as planting mode, large application of inorganic fertilizer, discharge of industrial waste, abuse of pesticide, climate and the like. Once entering the soil, heavy metals are accumulated in the soil in large quantities, so that the heavy metal pollution of the soil becomes an irreversible process. Heavy metals Cd and Pb have strong activity in soil, are easily absorbed by plants to pollute food chains and seriously harm human health, reportedly, the farmland area polluted by cadmium, lead, arsenic, chromium and other heavy metals in 2014 reaches 2600 hectares, more seriously, the cadmium content of the farmland is still increased by 0.004mg/kg per year, if the farmland cadmium concentration is increased continuously according to the range, the farmland cadmium concentration is doubled after 50 years, and the pollution problem of the farmland cadmium, lead and chromium becomes more prominent and severe.
The acidic soil in China is far more than 3 hundred million mu, the soil in the south of Yangtze river is acidic, and particularly, the soil in the south of Hunan is acidified, so that heavy metal pollution is serious. Most acid soils have a pH of less than 5.5, and some even less than 4.5. Soil acidification presents the following hazards: (1) the Cation Exchange Capacity (CEC) and salt saturation decrease, resulting in a decrease in soil fertility; (2) the fixation of other nutrient elements (such as phosphorus) is promoted, and the effective utilization rate of the phosphorus element is greatly reduced; (3) promoting the release, activation and dissolution of certain toxic elements (such as heavy metal, aluminum ions and the like), polluting soil and water environment and even threatening human health; (4) inhibiting the growth of beneficial microorganisms in soil, and influencing the decomposition of organic matters in the soil and the circulation of C, N, P and S in the soil; meanwhile, with the increasing aggravation of non-renewable energy crisis, the biomass power generation technology is rapidly developed in China, 665 biomass power plants in the whole country produce more than 2660 million tons of biomass ash every year at present, and the treatment mode is only simple landfill or land renting stacking at present, so that the environmental atmosphere, soil and water are seriously polluted.
The method for treating heavy metal pollution in soil mainly comprises the following steps: a soil agrochemical conditioning control method, an engineering physical chemical method and a biological remediation method, wherein the engineering physical chemical method is suitable for treating the soil pollution of a factory and has high treatment cost. The bioremediation method does not fundamentally change the treatment from soil and is not a long-term treatment method. The soil agrochemical conditioning control method changes the water solubility of heavy metals in soil by adjusting factors such as the pH value of soil, organic matters, CEC, soil moisture and the like, improves the bioavailability, reduces the harm of heavy metal pollution, has low cost and is suitable for farmland heavy metal treatment. But the key is how to find the raw materials with large quantity and stable quality.
The domestic product for adjusting the pH of the soil is mainly quicklime which is a natural mineral fired by using calces, consumes a large amount of energy in the production process, is applied for a long time, can cause soil hardening by supplementing a large amount of simple substance Ca, is seriously acidified if being discontinuously used, and simultaneously solves the problem of uniform and stable content of heavy metals in the national quicklime.
Chinese invention CN 105670636A passivation material for repairing cadmium-copper polluted acid soil, preparation method and application thereof, passivationThe pH value of the material is 10-13, the raw materials are biomass power plant ash, lime and phosphate rock, the materials are formed into balls under the condition that no adhesive is added, and heavy metal cadmium and copper in acid soil are passivated; the invention CN 106010542A of China is a sludge biochar for heavy metal contaminated soil remediation and a preparation method thereof, the sludge-based biochar is prepared by mixing and gasifying municipal sludge and palygorskite, and is used as a heavy metal contaminated soil remediation agent, and the activity of heavy metals is reduced only by utilizing the adsorption of carbon; the invention provides a restoring conditioner for copper and cadmium polluted acid soil and a preparation method thereof, which are disclosed by CN 103242849A in China, and the restoring conditioner for restoring copper and cadmium polluted acid soil is prepared by utilizing an organic fertilizer, quicklime and nano hydroxyapatite. The materials and the principle used by the invention are different from those of the invention, the pH value of the soil is improved by using the medium trace elements in the biomass ash, the physical and chemical properties of the soil are improved, and conditions are created for passivating heavy metals; CaO and active SiO contained in steel slag2Adsorbing and passivating Cd and Pb; FeSO4Form slightly water-soluble PbSO with Pb ions4Can passivate crops and can lead Cr to be6+Reduction to Cr3+The activity and toxicity of heavy metal Cr are reduced, the pH value of the passivation material is 10-13, the passivation material has multiple principles and can be used for compounding and cooperatively passivating soil heavy metal, and the effect is better.
The biomass ash is waste generated by a biomass power plant, the pH value is 10-13, the main components are metal oxides such as k, Si, Ca, Mg, Fe, Cu, Zn, Mn, B and the like, the elements are medium and trace elements which are necessary for plant growth and are lacking in soil, and the content proportion of the elements is basically consistent with that of the elements required by plants; when the fertilizer is applied to soil, the pH value of the soil can be improved, and simultaneously metal cation elements in the soil are recovered, so that the fertilizer has long-term and stable effect on passivating the activity of heavy metal ions; meanwhile, the active SiO in the biomass ash2After being absorbed by plants, the plant cell passivator and plant cells form silicified cells, so that the strength of plant cell walls is improved, the cell membrane permeability is reduced, the absorption of plants to heavy metals such as Cd, Pb and Cr is inhibited, and the passivation effect is achieved.
The steel slag mainly contains SiO236%, CaO 42%, MgO 6%, etc., active SiO2Absorbed by plant, forming silicified cells with plant cells, increasing plant cell wallStrength, reducing cell membrane permeability, inhibiting the absorption of heavy metals Cd, Pb, Cr and the like by plants, and playing a role in passivation.
The ammonium lignosulfonate is an aromatic macromolecular compound, has complexing and chelating effects, and can be used for complexing heavy metals Pb and Cd, so that the activity is reduced, and the passivation effect is achieved; meanwhile, the complex is complexed with metal cations such as Ca, Mg, Fe, Cu, Zn, Mn and the like in the biomass ash, so that the loss with water is reduced, and the utilization rate of medium and trace elements is improved.
Ferrous sulfate (FeSO)4) The functions of (1): (a) fe2+Adsorbing the heavy metal ions in the soil by plant roots to form an iron film so as to prevent the heavy metal ions from contacting the plant roots; (b) fe2+Make Cr6+Reduction to Cr3+The activity and toxicity of heavy metal Cr are reduced; (c) SO (SO)4 2-With Pb2+Formation of slightly water-soluble PbSO4Plays a role in passivation; (d) supplementing iron element to soil and promoting chlorophyll formation.
The research and development of the in-situ composite passivator product of heavy metals Pb and Cd in soil are initiated at home by utilizing the synergistic effect of biomass ash, steel slag, ammonium lignosulfonate, ferrous sulfate and the like.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides an in-situ passivant for heavy metal lead and cadmium in acid soil, and a preparation method and application thereof. According to the invention, the heavy metal Cd and Pb in-situ passivator is researched and developed by the synergistic effect of multiple components such as biomass ash, steel slag, ammonium lignosulfonate and ferrous sulfate, the pH value of soil is increased, meanwhile, rich medium and trace elements are provided for the soil, and the yield and quality of crops are increased. The problems of stacking of biomass ash, dust emission, high pH value and other environmental pollution caused by biomass power plants are solved, and comprehensive utilization of waste resources such as biomass ash, steel slag and the like is realized.
The technical scheme is as follows: the acid soil heavy metal lead-cadmium in-situ passivator comprises the following raw materials in parts by weight: 30-80 parts of biomass ash, 3-50 parts of steel slag, 3-30 parts of ammonium lignosulfonate and 5-30 parts of ferrous sulfate.
Preferably, the feed additive comprises the following raw materials in parts by weight: 50 parts of biomass ash, 25 parts of steel slag, 10 parts of ammonium lignosulfonate and 15 parts of ferrous sulfate.
The preparation method of the acid soil heavy metal lead-cadmium in-situ passivator comprises the following steps: (1) mixing and stirring the biomass ash, the steel slag, the ammonium lignosulfonate and the ferrous sulfate for later use; (2) removing iron from the mixture obtained in the step (1) through an iron remover, and conveying the mixture to a granulator; (3) and drying and cooling the granulated semi-finished product, screening and subpackaging to obtain the finished product.
The acid soil heavy metal lead-cadmium in-situ passivator is applied to preparing a conditioner for corn or wheat planting.
Has the advantages that: (1) the biomass ash is waste of a biomass power plant, the pH value is 10-13, the main components are metal oxides such as Si, Ca, Mg, Fe, Cu, Zn, Mn and B, the elements are medium and trace elements which are necessary for plant growth and are lacked in soil, the content proportion of the elements is basically consistent with that required by plants, and the alkalinity and the pb form insoluble pb (OH)2Is a high-quality raw material for passivating heavy metals Pb and Cd; active SiO in biomass ash2Absorbed by plants, forms silicified cells with plant cells, improves the strength of plant cell walls, reduces the permeability of cell membranes, inhibits the absorption of heavy metals Cd and Pb by the plants, and plays a role in passivation. (2) The steel slag mainly contains SiO236%, CaO 42%, MgO 6%, etc., active SiO2Absorbed by plant root system, forms silicified cell with plant cell, improves plant cell wall strength, reduces cell membrane permeability, inhibits plant absorption of heavy metals Cd, Pb, Cr, etc., and has passivation effect. (3) The ammonium lignosulphonate is a macromolecular aromatic compound, has complexing and chelating effects, is complexed with heavy metals Pb and Cd, and reduces the activity of Pb and Cd; meanwhile, the complex is complexed with cations of Ca, Mg, Fe, Cu, Zn, Mn and other elements in the biomass ash, so that the absorption of plants is promoted, the loss is reduced, and the utilization rate of medium and trace elements is improved. (4) Ferrous sulfate (FeSO)4) The functions of (1): (a) fe2+Adsorbing the heavy metal ions in the soil by plant roots to form an iron film so as to prevent the heavy metal ions from contacting the plant roots; (b) fe2+Make Cr6+Reduction to Cr3+The activity and toxicity of heavy metal Cr are reduced; (c) SO (SO)4 2-With Pb2+Formation of slightly water-soluble PbSO4To play bluntActing; (d) supplementing iron element to soil and promoting chlorophyll formation.
Drawings
FIG. 1: a trend graph of the concentration change of heavy metals Cd and Pb in the corn planting soil;
FIG. 2: a trend graph of the concentration change of heavy metals Cd and Pb in the wheat planting soil;
FIG. 3: the yield change trend chart of the crops corn and wheat.
Detailed Description
The following examples are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Example 1
The preparation method comprises the following steps: 50 parts of biomass ash, 25 parts of steel slag, 10 parts of ammonium lignosulfonate and 15 parts of ferrous sulfate.
(1) Mixing and stirring the biomass ash, the steel slag, the ammonium lignosulfonate and the ferrous sulfate for later use;
(2) removing iron from the mixture obtained in the step (1) through an iron remover, and conveying the mixture to a granulator;
(3) and drying, cooling, screening, subpackaging and warehousing the granulated semi-finished product.
Purpose of the test
In order to verify the field use effect of passivators with different formulas, the applicant selects to test on urban corn and wheat crops in Biquan county of Anhui province, verifies the effect and the economic benefit, performs in-situ passivator tests on heavy metals Pb and Cd from multiple aspects of the formula and the dosage, and provides scientific basis for large-area popularization and application.
2 general description of the test
2.1 test site and soil conditions
The test site is selected from towns in Linquan county, the soil is clay, and the current situation of the soil is shown in the following table 1.
TABLE 1 analysis of soil nutrient in plots before test
2.2 test article
Two crop trials, corn, huawan 267; wheat, wan wheat 38.
2.3 test fertilizers and passivating agents
45% of Anhuihongternary compound fertilizer (28:6:6), 40% of Anhuihongternary compound fertilizer (25:12:8) and 45% of Anhuihongternary compound fertilizer, and different heavy metal passivators are applied.
2.4 test formulation design
The experiment was run in 5 treatments, each treatment was repeated 3 times, and randomized block wise. Test area of each treatment was 100m2。
The test plot is rectangular, small plastic film ridges are formed among all the cells of the corn, single irrigation and single row are formed, water and fertilizer serial exchange among different treatment rooms is prevented, and the treatment settings are as follows:
TABLE 2 passivator, Fertilizer formula and dosage table
The test is corn and wheat, and is carried out from corn, and the two crops are treated identically.
The test dosage of each treatment of the passivator is 150 kg/mu, the seedlings are basically the same, other agricultural measures of each treatment are consistent, and single difference is kept.
2.5 corn test
Fertilizing and passivating the corns in 2015 for 6 months and 1 day, wherein the fertilizer and passivating agent dosage is carried out according to the table; sowing 6 days in 6 months and harvesting 16 days in 10 months
TABLE 3 statistical table of physical and chemical properties and yield of soil under different formula treatment conditions of corn
As can be seen from table 3, there is a very significant difference between control 1 and treatment 5 in the heavy metals Pb, Cd in the soil:
(1) passivating Cd: compared with the comparison 1, the treatment 2 to the treatment 5 have passivation effect on heavy metal Cd, and from the passivation effect analysis, the passivation effect is improved along with the synergistic effect of the multi-component complexing agent, the passivation effect of the complexing agent of the treatment 5 is the best, and the effective state is reduced by 82.68%;
(2) passivating Cr: compared with the comparison 1, the treatment 2 to the treatment 5 have passivation effect on heavy metal Pb, from the passivation effect analysis, the passivation effect is more and more excellent along with the synergistic effect of the multi-component complexing agent, the treatment 5 has the best passivation effect, and the effective state is reduced to 88.72%;
(3) pH of treatment 2 to treatment 5 compared with control 1, the pH of the acid soil was increased, and the best effect was treatment 2, which was increased by 0.7, and treatment 5, which was increased by 0.3.
(4) Yield: compared with the control 1, the yield of the treatments 2 to 5 is increased, the yield of the treatment 4 is increased by 24.79 percent, the yield of the treatment 5 is increased by 32.20 percent, and the effects are ideal.
And (3) corn test: the composite passivator with the formula of biomass ash, steel slag, ammonium lignosulfonate and ferrous sulfate has the best passivation effect on heavy metals Pb and Cd in soil, and the corn yield is increased by over 32.20%.
2.6 wheat test procedure
Applying fertilizer and passivator to the wheat in 2015, 10 months and 20 days according to the table 1; wheat was sown 10 and 25 days 2015, and harvested 6 and 2 days 2016.
TABLE 4 statistical table of soil biological properties and yield under different formula treatment conditions of wheat
As can be seen from table 4, the heavy metals Pb, Cd in the soil are very significantly different between control 1 and treatment 5:
(1) passivating Cd: compared with the control 1, the treatment 2 to the treatment 5 have passivation effect on heavy metal Cd, from the passivation effect analysis, the passivation effect is more and more obvious along with the synergistic effect of the multi-component complexing agent, the treatment 5 has the best composite passivator effect, and the effective state is reduced to 76.76%;
(2) passivating Pb: compared with the comparison 1, the treatment 2 to the treatment 5 have passivation effect on heavy metal Pb, and from the passivation effect analysis, the passivation effect is more and more obvious along with the synergistic effect of the multi-component complexing agent, the treatment 5 has the best passivation effect, and the effective state is reduced to 88.88%;
(3) pH of treatment 2 to treatment 5 compared with control 1, the pH of the acid soil was increased, and the best effect was treatment 2, with a pH increase of 0.7 and treatment 5, with a pH increase of 0.4.
(3) Yield: compared with the control 1, the yield of the treatments 2 to 5 is increased, the yield of the treatment 4 is increased by 24.30%, the yield of the treatment 5 is increased by 23.87%, and the effects are ideal.
Wheat test: the formula is a multi-component synergistic composite passivator of biomass ash, steel slag, ammonium lignosulfonate and ferrous sulfate, the passivating effect on heavy metals Pb and Cd in soil is optimal, and the yield of wheat is increased by 23.87%.
3 conclusion
The test uses a plurality of heavy metal passivators with different formulas, and the analysis results are shown in tables 3 and 4 and figures 1, 2 and 3: in tests of corn and wheat, all the formulas have passivation effects, the yield is increased, but the synergistic compound effect of the 5-component treatment is optimal, the pH value of soil is improved by using medium and trace elements in biomass ash, conditions are created for passivating heavy metals, and the combined action of carbon, a complexing agent, a reducing agent and the like is compounded; the effective state of heavy metal Cd on corn is reduced by 82.68%, the effective state of Pb is reduced by 88.72%, the pH of soil is increased by 0.3, and the yield is increased by 32.20%. The effective state of heavy metal Cd on wheat in soil is reduced by 76.76%, the effective state of pb is reduced by 88.88%, the pH of soil is increased by 0.3, and the yield is increased by 23.87%.
According to the formula, the multi-component synergistic compound acidic soil heavy metal passivator such as biomass ash, steel slag, ammonium lignosulfonate and ferrous sulfate provides medium and trace elements for soil, has obvious effects on improvement of physical and chemical properties of soil, improvement of pH value of acidic soil, passivation of heavy metals Pb and Cd and improvement of yield, and has popularization and application prospects.
Claims (1)
1. The application of the acid soil heavy metal lead-cadmium in-situ passivator in preparing the conditioner for planting corn or wheat comprises the following steps: (1) the components by weight portion are as follows: mixing and stirring 50 parts of biomass ash, 25 parts of steel slag, 10 parts of ammonium lignosulfonate and 15 parts of ferrous sulfate for later use; (2) removing iron from the mixture obtained in the step (1) through an iron remover, and conveying the mixture to a granulator; (3) and drying and cooling the granulated semi-finished product, screening and subpackaging to obtain the finished product.
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