CN112920805A - Heavy metal compound passivator - Google Patents
Heavy metal compound passivator Download PDFInfo
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- CN112920805A CN112920805A CN202110070286.0A CN202110070286A CN112920805A CN 112920805 A CN112920805 A CN 112920805A CN 202110070286 A CN202110070286 A CN 202110070286A CN 112920805 A CN112920805 A CN 112920805A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 145
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 36
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- 229920001661 Chitosan Polymers 0.000 claims abstract description 40
- 238000002161 passivation Methods 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010881 fly ash Substances 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
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- 235000019738 Limestone Nutrition 0.000 claims abstract description 15
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- 239000010949 copper Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 239000002689 soil Substances 0.000 claims description 52
- 239000013049 sediment Substances 0.000 claims description 43
- 239000010871 livestock manure Substances 0.000 claims description 28
- 210000003608 fece Anatomy 0.000 claims description 26
- 244000144972 livestock Species 0.000 claims description 26
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- 239000002361 compost Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
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- 238000009264 composting Methods 0.000 claims description 19
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- 238000002360 preparation method Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 29
- 230000007774 longterm Effects 0.000 abstract description 6
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- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 13
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- 239000010802 sludge Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 5
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- 230000001988 toxicity Effects 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
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Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention relates to the technical field of metal passivators, in particular to a heavy metal compound passivator which comprises the following raw materials in parts by mass: 20-40 parts of diatomite, 1-10 parts of fly ash and phosphorus-rich tailings, 20-30 parts of sepiolite, 10-30 parts of straw powder and 1-10 parts of chitosan, and adding limestone to adjust the pH value to 7-7.6; the invention changes the pollution of underground water caused by phosphate used by the prior passivator and also solves the problems that the traditional passivator has slow effect and can not directly carry out short-term passivation and long-term passivation on copper, zinc, cadmium and chromium in bottom mud and excrement.
Description
Technical Field
The invention relates to the technical field of metal passivators, and particularly relates to a heavy metal compound passivator.
Background
Dredged sediment is mainly used as a soil conditioner in agriculture, however, the sludge contains a certain amount of heavy metals and carcinogenic substances, and the untreated exposure can cause secondary pollution in nature.
The passivating agent is widely concerned about treating polluted dredged sediment due to the advantages of low cost, quick effect, simple operation, no influence on crop production and the like. Passivation techniques rely on passivating agents to reduce the mobility and bioavailability of heavy metals in the sediment, rendering them in a more stable form in the soil. The heavy metal in the bottom sediment and the passivating agent are subjected to physical and chemical reactions such as adsorption, complexation and coprecipitation to adjust and change the existing form of the heavy metal in the bottom sediment, so that the biological effectiveness of the heavy metal is mainly reduced, the toxicity of the heavy metal to biological receptors such as plants and human bodies is further reduced, and the purpose of repairing the polluted soil is achieved. Generally, the magnitude of the relationship between heavy metal morphology and bioavailability is expressed as exchangeable > carbonate bound > ferromanganese oxide bound > organic bound > sludge. The organic combination state and the residue state are almost ineffective for plants and are relatively stable existing forms.
Heavy metals such as Cu, Zn and Cd in traditional dredging sediment are subjected to combined pollution, the activity and the biological effectiveness of each heavy metal are different, the heavy metals with low activation degrees such as the combined state of Cu, Zn and Cd and the organic combined state are slowly and continuously released in a soil system along with the comprehensive action of temperature, humidity, microorganisms and the like, so that the activity and the biological effectiveness of the heavy metals are continuously existed in a specific period, the effectiveness and the timeliness of the passivator are relatively low, the conventional soil heavy metal passivator can not completely realize the due effect in the aspect of medium and long-term soil heavy metal pollution, in addition, the passivation effect of a chemical passivator is good, but the chemical passivator per se is always polluted to the environment, the research on the type and the passivation mechanism of the biological passivator is not enough, and further exploration and improvement are still.
Therefore, a mode is urgently needed to solve the problems that the traditional dredged sediment is high in water content and high in intercellular bound water, and the bound sludge and water are not easy to adsorb, so that heavy metals in the sludge are passivated.
China contains a large amount of sandy soil, contains a large amount of sand grains, has large inter-granular pores, good ventilation performance and loose soil texture, but water is easy to leak and is not easy to keep; the soil is easy to dry and not drought-resistant, the sandy soil contains less nutrients and has poor fertilizer absorption and retention capacity, and the applied nutrients are easy to run off along with water; the sandy soil has good air permeability, vigorous aerobic microorganism activity, fast nutrient conversion, insufficient after fertilization, lower organic matter content and nutrient content and inhibited enzyme activity, thereby influencing the life activity of microorganisms in the soil and being difficult to develop and utilize.
Patent CN202010652613.9, a heavy metal stabilizer for dredged sediment and a method for stabilizing dredged sediment heavy metal, which comprises mixing montmorillonite powder and carboxymethyl cellulose salt with sediment, stirring uniformly, and then standing and maintaining the mixed sediment in dark. The heavy metal stabilizer for dredged sediment has the effects of high efficiency, low cost and no secondary pollution. The problems of slow effect and short-term and long-term passivation of the traditional passivator are not solved.
The patent CN201510964820.7 discloses a heavy metal passivator and an application thereof, wherein the metal passivator is composed of straw, biochar and biological humic acid, has the effects of improving compost quality and improving soil, is used for passivating heavy metals in livestock and poultry manure in a composting process, and can further passivate the heavy metals in the soil after the passivated compost is applied to the soil. The problems of slow effect and short-term and long-term passivation of the traditional passivator are not solved.
The problem of removing heavy metals from dredged sediment and the problem of improving sandy soil at low cost.
Disclosure of Invention
The invention aims to provide a metal compound passivator, which changes the pollution of underground water caused by phosphate used by the existing passivator and also solves the problems that the traditional passivator is slow in effect and cannot directly carry out short-term passivation and long-term passivation on copper, zinc, cadmium and chromium in bottom mud and excrement.
In order to realize the purpose, the invention adopts the technical scheme that:
the heavy metal compound passivator comprises the following raw materials in parts by mass: 20-40 parts of diatomite, 1-10 parts of a mixture of fly ash and phosphorus-rich tailings, 20-30 parts of sepiolite, 10-30 parts of straw powder and 1-10 parts of chitosan, and adding limestone to adjust the pH value to 7-7.6.
Further, the mass ratio of the fly ash to the phosphorus-rich tailings is 1: 3 to 5.
Further, the particle size range of the phosphorus-rich tailings is 1-10 mm, the particle size range of the fly ash is 0.01-5 mm, and the particle size range of the straw powder is 1-10 mm.
Furthermore, the particle size range of the heavy metal compound passivator is 3-15 mm.
Furthermore, the water content of the straw powder is below 15%, and the water content of the heavy metal composite passivator is below 15%.
Further, the passivation efficiency of the heavy metal passivator on metal ions in the dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
A preparation method of a heavy metal compound passivator comprises the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to 7-7.6, and drying to obtain the heavy metal passivator.
A heavy metal compound passivator, and application thereof in passivating compost or passivating heavy metals in soil.
Further, the heavy metal passivator is used for passivating the heavy metals in the compost by the following steps:
applying the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting into soil, wherein the application amount of the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting is 1000 kg-3000 kg/mu of soil;
further, the mass water content of the livestock and poultry manure or the dredged sediment is 40-85%.
Further, the mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 3 to 8.
The invention has the beneficial effects that:
1. the invention takes chitosan and straw powder as raw materials to obtain a sticky mixture, and the chitosan is attached to the straw powder; diatomite, fly ash and phosphorus-rich tailings are used as raw materials, and are mixed with quick lime to react to prepare a prefabricated passivator, and then the prefabricated passivator is granulated and dried to prepare the long-acting heavy metal passivator; the fly ash and the phosphorus-rich tail of the invention are rich in silicon dioxide, the diatomite and the sepiolite have huge surface areas and extremely strong adsorptivity, and can fix heavy metal ions in soil through physical adsorption, while the quicklime gradually participates in the reaction to form silicate and phosphate, the silicate is hydrolyzed in the soil to release silicate ions, and then the silicate ions react with the metal ions in the soil to generate metal silicate with extremely low solubility; meanwhile, the quicklime can neutralize the acidity of the soil, the acidity and the alkalinity of the soil directly influence the dispersion degree of the heavy metal passivator, and in the neutral soil, the heavy metal passivator is strong in hydrophilicity, better in hydrophilicity, more uniform in dispersion and higher in passivation rate; with the increase of the dosage of the heavy metal compound passivator, the removal rate is finally kept stable but not up to 100%; multiple effects of passivating soil heavy metals, improving acid soil and promoting crop yield increase are realized, the passivator is endowed with an excellent passivation effect, and long-acting passivation is realized together.
2. The diatomite, the mixture of the fly ash and the phosphorus-rich tailings, the sepiolite, the straw powder and the chitosan are adopted, and the technical synergistic effect is the best through experimental demonstration. The problem that quantification is not realized on the passivator in the industry is solved, and if the technical defects that the quantification proportioning of each cost is not passed exist are as follows: under the condition that the proportion among the diatomite, the sepiolite and the chitosan is not accurate, the chitosan is easy to block the pores of the diatomite and the sepiolite, so that the internal surface area is reduced, the permeability among the pores is reduced, and the effect of the product is influenced. As shown in figure 1, the straw powder has the effect of combining with chitosan and then attaching to the surfaces of diatomite and sepiolite, and the pores of the diatomite and the sepiolite can be prevented from being blocked by the chitosan because the straw powder is not fixedly attached to the diatomite and the sepiolite.
3. The invention relates to a method for removing heavy metal in dredged sludge by using limestone, coal ash, chitosan and straw powder, which has comprehensive effects and is beneficial to further removing intercellular bound water of a heavy metal passivator when the heavy metal passivator is used for treating heavy metal in dredged sludge, so that the heavy metal in compact sludge particles can be conveniently removed, and the aim of uniformly removing the heavy metal is fulfilled.
4. After the heavy metal passivator disclosed by the invention is used for passivating heavy metal contaminated soil, the concentration of a heavy metal ion leaching solution of the passivated heavy metal contaminated soil is far lower than the standard limit value of 'hazardous waste identification standard leaching toxicity identification' (GB 5085.3-2007). The metal passivator is used for passivating the heavy metals in the livestock and poultry manure in the composting process, and the passivated compost is applied to soil to further passivate the heavy metals in the soil, so that the establishment of a fertilizer-soil heavy metal inhibition and control system is facilitated.
Drawings
FIG. 1 is a schematic diagram of adsorption of chitosan, straw powder, diatomite and sepiolite;
FIG. 2 is a microscopic cross-sectional view of the corn stalk powder at 100 times magnification.
Detailed Description
The present invention is described in detail below for the purpose of better understanding technical solutions of the present invention by those skilled in the art, and the description of the present invention is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
The heavy metal compound passivator comprises the following raw materials in parts by mass: 20-40 parts of diatomite, 1-10 parts of a mixture of fly ash and phosphorus-rich tailings, 20-30 parts of sepiolite, 10-30 parts of straw powder and 1-10 parts of chitosan, and adding limestone to adjust the pH value to 7-7.6.
Preferably, the mass ratio of the fly ash to the phosphorus-rich tailings is 1: 3 to 5.
Preferably, the particle size range of the phosphorus-rich tailings is 1 mm-10 mm, the particle size range of the fly ash is 0.01 mm-5 mm, the particle size range of the straw powder is 1-10 mm, the cross-sectional view of the straw powder is shown in fig. 2, and a is intercellular pores caused by vascular bundles.
Preferably, the particle size range of the heavy metal compound passivator is 3-15 mm.
Preferably, the water content of the straw powder is below 15%, and the water content of the heavy metal composite passivator is below 15%.
Preferably, the passivation efficiency of the heavy metal passivator on metal ions in the dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
A heavy metal compound passivator, and application thereof in passivating compost or passivating heavy metals in soil.
A preparation method of a heavy metal compound passivator comprises the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to 7-7.6, and drying to obtain the heavy metal passivator.
Preferably, the heavy metal passivator is used for passivating the heavy metals in the compost by the following steps: applying the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting into soil, wherein the application amount of the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting is 1000 kg-3000 kg/mu of soil;
preferably, the mass water content of the livestock and poultry manure or the dredged sediment is 40-85%.
Preferably, the mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 3 to 8.
As shown in fig. 1, sepiolite and diatomite are separately mixed with chitosan, and the pores and the surface of the diatomite and the sepiolite are blocked by the chitosan, so that the adsorption capacity of the sepiolite, the diatomite and the diatomite to heavy metals is reduced, as shown in a schematic diagram (1); the straw powder and chitosan are separately mixed, and the chitosan is dissolved in pores in the straw powder, as shown in a schematic diagram (2); the straw powder, the sepiolite, the diatomite and the chitosan are directly mixed, the chitosan is dissolved in pores in the straw powder, and meanwhile, the pores and the surfaces of the diatomite and the sepiolite are also mostly blocked by the chitosan, so that the adsorption capacity of the diatomite and the sepiolite is reduced, as shown in a schematic diagram (4); the holes of the straw powder, which are dissolved by the chitosan, are then mixed with the sepiolite and the diatomite, as shown in the schematic diagram (3), so that the chitosan is not easy to seep out, the holes of the diatomite and the sepiolite are blocked, and the binding capacity of 4 heavy metal ions is improved. The chitosan is dissolved in the straw powder, the straw powder is gradually decomposed in the composting process and the soil formation process, the chitosan is released, sterilization and heavy metal ion adsorption are carried out, and the chitosan is gradually adsorbed in the pores of the diatomite and the sepiolite after adsorption.
Example 1:
the heavy metal compound passivator comprises the following raw materials in parts by mass: 20 parts of diatomite, 1 part of a mixture of fly ash and phosphorus-rich tailings, 20 parts of sepiolite, 10 parts of straw powder and 1 part of chitosan, and then adding limestone to adjust the pH value to 7.6. A preparation method of a heavy metal compound passivator comprises the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to 7-7.6, and drying to obtain the heavy metal passivator.
The straw powder adopted in the embodiment is corn straw powder.
The mass ratio of the fly ash to the phosphorus-rich tailings is 1: 3. the particle size range of the phosphorus-rich tailings is 1mm, the particle size range of the fly ash is 0.01mm, and the particle size range of the straw powder is 1. The grain size range of the heavy metal compound passivator is 3 mm. The water content of the straw powder is below 15%, and the water content of the heavy metal composite passivator is below 15%. The passivation efficiency of the heavy metal passivator on metal ions in dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
The steps of the heavy metal passivator for passivating the heavy metals in the compost are as follows:
applying the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment mixed compost into soil, wherein the application amount of the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment mixed compost is 1000 kgg/mu of soil;
the mass water content of the livestock and poultry manure or the dredged sediment is 40 percent. The mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 3.
example 2
The heavy metal compound passivator comprises the following raw materials in parts by mass: 40 parts of diatomite, 10 parts of a mixture of fly ash and phosphorus-rich tailings, 30 parts of sepiolite, 30 parts of straw powder and 10 parts of chitosan, and then limestone is added to adjust the pH value to 7.3. The mass ratio of the fly ash to the phosphorus-rich tailings is 1: 5. a preparation method of a heavy metal compound passivator comprises the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to be 7.3, and drying to obtain the heavy metal passivator.
The particle size range of the phosphorus-rich tailings is 10mm, the particle size range of the fly ash is 5mm, and the particle size range of the straw powder is 10 mm. The grain size range of the heavy metal compound passivator is 15 mm. The water content of the straw powder is below 15%, and the water content of the heavy metal composite passivator is below 15%. The passivation efficiency of the heavy metal passivator on metal ions in dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
The steps of the heavy metal passivator for passivating the heavy metals in the compost are as follows: applying the product of the heavy metal passivator and livestock manure or dredged sediment mixed compost into soil, wherein the application amount of the product of the heavy metal passivator and livestock manure or dredged sediment mixed compost is 3000 kg/mu of soil;
the mass water content of the livestock and poultry manure or the dredged sediment is 85 percent. The mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 8.
example 3
The heavy metal compound passivator comprises the following raw materials in parts by mass: 30 parts of diatomite, 7 parts of a mixture of fly ash and phosphorus-rich tailings, 24 parts of sepiolite, 18 parts of straw powder and 7 parts of chitosan, and then adding limestone to adjust the pH value to 7.0. A preparation method of a heavy metal compound passivator comprises the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to 7.0, and drying to obtain the heavy metal passivator.
The mass ratio of the fly ash to the phosphorus-rich tailings is 1: 4. the particle size range of the phosphorus-rich tailings is 7mm, the particle size range of the fly ash is 3mm, and the particle size range of the straw powder is 6 mm.
The grain size range of the heavy metal compound passivator is 11 mm. The water content of the straw powder is below 15%, and the water content of the heavy metal composite passivator is below 15%.
The passivation efficiency of the heavy metal passivator on metal ions in dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
The steps of the heavy metal passivator for passivating the heavy metals in the compost are as follows:
applying the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment mixed compost into soil, wherein the application amount of the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment mixed compost is 1800 kg/mu of soil; the mass water content of the livestock and poultry manure or the dredged sediment is 65 percent.
The mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 5.
comparative example 1
In this comparative example, no fly ash and phosphorus-rich tailings were added, and the same amount of diatomaceous earth was used instead, as in example 3.
Comparative example 2
In this comparative example, no chitosan was added and the same amount of diatomaceous earth was used instead, as in example 3.
Comparative example 3
In the comparative example, a sticky mixture is not obtained by mixing chitosan and straw powder, but all raw materials of the heavy metal compound passivator are directly mixed, and the rest is the same as that in example 3.
Comparative example 4
All the raw materials of the heavy metal compound passivator in the comparative example comprise the following components in percentage by mass: 30 parts of diatomite, 7 parts of a mixture of fly ash and phosphorus-rich tailings, 24 parts of sepiolite, 18 parts of straw powder and 16 parts of chitosan, and then adding limestone to adjust the pH value to 7.0. The rest is the same as example 3.
Detection of passivation effect of heavy metals on soil containing livestock and poultry manure
The heavy metal passivation effect tests were performed on examples 1 to 3 of the present invention and comparative examples 1 and 2, respectively, and the test results are shown in table 1:
the detection method comprises the following steps: preparing a soil sample containing 0.2mg/kg of exchangeable heavy metal ions, mixing the passivators prepared in the embodiment and the comparative example with the soil sample applied with livestock and poultry manure according to the mass ratio of 1:60, standing and reacting for 1, 6 and 12 months, and measuring the reduction rate of the exchangeable heavy metal ions in the soil sample;
the reduction rate (%) of the exchangeable heavy metal ions is (exchangeable heavy metal ion content in the original soil sample-exchangeable heavy metal ion content in the soil sample after applying the soil passivator for one month)/exchangeable heavy metal ion content in the original soil sample;
the higher the reduction rate of the exchangeable heavy metal ions is, the better the passivation effect of the heavy metal ions in the soil is.
Table 1: and (5) performance detection results.
As can be seen from the detection data in the table above, the heavy metal passivation effect of comparative example 1 is deteriorated because no fly ash and phosphorus-rich tailings are added in comparative example 1, and meanwhile, no chitosan is added in comparative example 2, and the long-acting passivation effect cannot be maintained; in the comparative examples 3 and 4, the chitosan is not pretreated and is not quantitatively added, so that the sepiolite and the diatomite are blocked, and the passivation effect is reduced; therefore, the addition of the fly ash and the phosphorus-rich tailings not only improves the passivation effect of the passivator, but also improves the long-acting passivation capability of the passivator. Therefore, the addition of the fly ash, the phosphorus-rich tailings and the chitosan not only improves the passivation effect of the passivator, but also improves the short-term and long-acting passivation capability of the passivator.
Determination of the passivation Effect of Metal passivators
Respectively collecting compost samples before and after composting, respectively sampling at the middle part of the compost according to a high layer, a middle layer and a low layer, uniformly mixing the samples and naturally drying. The heavy metal forms were measured by BCR continuous extraction (as shown in Table 2) using ICP-OES (Optima5300DV, Perkin-Elmer).
TABLE 2 continuous extraction method for heavy metal form classification of compost
The concentration, the distribution rate and the distribution rate decrease of exchangeable Cu and exchangeable Cd in the Taihu lake dredging bottom mud before composting and in the compost obtained after composting are detected, the results are shown in Table 3, the heavy metal passivators in the examples are respectively added to the components of the examples to carry out the composting on the Taihu lake dredging bottom mud, and the comparative examples 1 and 2 show that the heavy metal passivators are not added in the composting process.
TABLE 3 reduction of exchangeable heavy metal concentration distribution in composting
As can be seen from the data in table 3, the comparative example group exhibited a tendency of activation in that the exchangeable state distribution ratio rose from 7.6% and 7.8% before composting to 7.89% and 8.03% after composting for the heavy metal Cu. Examples 1 to 3 were reduced in exchangeable state Cu distribution ratio, and passivation of exchangeable state Cu was achieved. For heavy metal Cd, the exchangeable state distribution rate of the comparative example group is reduced from the pre-composting stage to the post-composting stage. Compared with the comparative example group, the distribution rate reduction of exchangeable Cd in the examples 1 to 3 is large, and the long-term passivation effect of Cd in compost is improved.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (10)
1. The heavy metal compound passivator is characterized by comprising the following raw materials in parts by mass: 20-40 parts of diatomite, 1-10 parts of a mixture of fly ash and phosphorus-rich tailings, 20-30 parts of sepiolite, 10-30 parts of straw powder and 1-10 parts of chitosan, and adding limestone to adjust the pH value to 7-7.6.
2. The heavy metal compound passivator of claim 1, wherein the mass ratio of the fly ash to the phosphorus-rich tailings is 1: 3 to 5.
3. The heavy metal compound passivator of claim 1, wherein the particle size range of the phosphorus-rich tailings is 1 mm-10 mm, the particle size range of the fly ash is 0.01 mm-5 mm, and the particle size range of the straw powder is 1-10 mm.
4. The heavy metal compound passivator of claim 1, wherein the particle size range of the heavy metal compound passivator is 3-15 mm.
5. The heavy metal compound passivator of claim 1, wherein the moisture content of the straw powder is below 15%, and the moisture content of the heavy metal compound passivator is below 15%.
6. The heavy metal compound passivator of claim 1, wherein the passivation efficiency of the heavy metal passivator on metal ions in dredged sediment is as follows: the passivation efficiency of chromium and copper reaches more than 60 percent.
7. The preparation method of the heavy metal compound passivator is characterized by comprising the following steps of mixing chitosan and straw powder according to the proportion to obtain a sticky mixture; and step three, uniformly stirring the mixture prepared in the step one and the step two, adding limestone to adjust the pH value to 7-7.6, and drying to obtain the heavy metal passivator.
8. The application of the heavy metal compound passivator according to any one of claims 1-6, characterized in that the heavy metal compound passivator is applied to passivation of heavy metals in compost or soil.
9. Use according to claim 8, characterized in that: the steps of the heavy metal passivator for passivating the heavy metals in the compost are as follows:
applying the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting into soil, wherein the application amount of the product of the heavy metal passivator and the livestock and poultry manure or the dredged sediment after mixed composting is 1000 kg-3000 kg/mu of soil;
the mass water content of the livestock and poultry manure or the dredged sediment is 40-85%.
10. Use according to claim 8, characterized in that: the mass ratio of the heavy metal passivator to the livestock and poultry manure or the dredged sediment is 1: 3 to 8.
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| CN105623670A (en) * | 2015-12-21 | 2016-06-01 | 农业部规划设计研究院 | Heavy metal passivator and application thereof |
| US20180119008A1 (en) * | 2016-02-01 | 2018-05-03 | Guangdong Institute Of Eco-Environmental Science & Technology | Preparation and use of slow-release iron-based biochar soil heavy metal passivator |
| CN110184075A (en) * | 2019-07-12 | 2019-08-30 | 湖南双晟科技信息咨询有限公司 | A kind of mercury contaminated soil passivation conditioner and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031651A (en) * | 2014-07-07 | 2014-09-10 | 爱土工程环境科技有限公司 | Passivation improver for heavy metal pollution farmland and using method thereof |
| CN105623670A (en) * | 2015-12-21 | 2016-06-01 | 农业部规划设计研究院 | Heavy metal passivator and application thereof |
| US20180119008A1 (en) * | 2016-02-01 | 2018-05-03 | Guangdong Institute Of Eco-Environmental Science & Technology | Preparation and use of slow-release iron-based biochar soil heavy metal passivator |
| CN110184075A (en) * | 2019-07-12 | 2019-08-30 | 湖南双晟科技信息咨询有限公司 | A kind of mercury contaminated soil passivation conditioner and preparation method thereof |
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| CN113913190A (en) * | 2021-10-14 | 2022-01-11 | 上海市农产品质量安全中心 | Preparation method of soil heavy metal passivator based on electrostatic effect |
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