CN108359475B - Humic acid soil heavy metal restoration agent and preparation method and application thereof - Google Patents
Humic acid soil heavy metal restoration agent and preparation method and application thereof Download PDFInfo
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- CN108359475B CN108359475B CN201810176414.8A CN201810176414A CN108359475B CN 108359475 B CN108359475 B CN 108359475B CN 201810176414 A CN201810176414 A CN 201810176414A CN 108359475 B CN108359475 B CN 108359475B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
A humic acid soil heavy metal restoration agent and a preparation method and application thereof, the preparation process comprises the steps of (1) mixing; (2) molding; (3) drying; (4) forming a hole; (5) and (4) adding. The preparation method disclosed by the invention has the advantages that the preparation of the soil heavy metal restoration agent is carried out on the premise of considering the use value of the restored soil, and the obvious removal effect on typical soil heavy metal pollution ions is achieved.
Description
Technical Field
The invention relates to the technical field of heavy metal contaminated soil treatment and restoration, in particular to a green humic acid conditioner for restoring heavy metal contaminated soil.
Background
The rapid development of modern economy and the rapid expansion of urban scale, harmful heavy metals enter the soil through various ways, causing serious pollution to the soil. The heavy metal pollution of the soil can not only cause soil degradation and influence the reduction of crop yield and quality, but also pollute surface water and underground water through runoff and leaching loss and harm human health. Heavy metal pollution of soil has attracted high attention from all societies. The European Community Bureau of reference (European Community Bureau of reference) states that the heavy metal forms in soil are mainly 4 types: exchangeable and carbonate bound states (acid soluble states), iron (Fe)/manganese (Mn) oxide bound states (reducible states), organic and sulfide bound states (oxidizable states), and residue states. Wherein, the acid soluble state can directly poison soil microorganisms and plants, destroy the ecological structure of the soil, and also can be transferred and transformed through a food chain to harm the health of human bodies. The search for reasonably effective restoratives has become an urgent need for practical production.
The method belongs to three major technologies of engineering physics, biological remediation and soil chemical conditioning in the field of heavy metal contaminated soil treatment and remediation. The first is the engineering physical technology including the soil-bearing method, the leaching precipitation method, the heat treatment method and the electrokinetic chemical method, and is not suitable for large-area popularization and application due to the huge treatment cost of the heavy metal polluted soil and the unavoidable secondary pollution problem. Secondly, including the bioremediation technique including microbiological remediation method and phytoremediation method, the microbiological remediation method is influenced by environmental factor greatly, life cycle is short, the microorganism dies the back heavy metal and all returns the restriction of releasing in soil and the phytoremediation method receives the plant species of broad-spectrum high absorption heavy metal few, the biology is output lowly, the absorption efficiency is low and the restriction of long term in the period of remediation still stops in experimental stage. Thirdly, the soil chemical conditioning technology comprises the steps of applying organic fertilizer and quicklime, soaking in flooding water, using an adsorbent, a passivator, an antagonist and the like, and the biological effectiveness of soil heavy metal is reduced and the absorption of crops to the heavy metal is reduced by enhancing the adsorption, oxidation reduction, complexing precipitation and ion antagonism effects on the heavy metal, so that the content of the heavy metal in agricultural products is enabled to meet the national quality safety standard, but the problems of soil potential breeding, secondary potential breeding, low adsorption-passivation-antagonism efficiency on the heavy metal, stability deviation, secondary pollution and the like caused by long-term flooding are solved.
Research and application of the multifunctional heavy metal polluted soil conditioner which is powerful in heavy metal pollution treatment, has the effects of supplementing the fertilizer supply capacity, conditioning the soil characteristics and is beneficial and safe in ecological environment are urgent.
In the remediation and treatment of the heavy metal contaminated soil, compared with other remediation technologies, the solidification/stabilization technology has the advantages of short treatment time, wide application range and the like, and is called as the optimal technology for treating harmful and toxic wastes by the U.S. environmental protection agency, wherein the stabilization technology is a mature, economic and effective technology, and the technology utilizes the physicochemical actions of a stabilizer, the soil and heavy metals in the soil, such as precipitation, adsorption, chelation, oxidation reduction and the like, and achieves the remediation and treatment effects by changing the chemical forms of the heavy metals in the soil or reducing the mobility of the heavy metals.
CN201410723417.0 discloses a soil heavy metal passivator, which comprises the following components in parts by weight: 20-35 parts of humic acid, 30-35 parts of sulfhydryl compound, 10-30 parts of calcium phosphate and 3-10 parts of chitosan. The soil heavy metal passivator has the functions of passivating heavy metals, particularly mercury, and improving soil properties.
CN201510358365.6 discloses a curing agent for inhibiting tobacco from absorbing cadmium and lead elements in soil and an application thereof, which consists of 98 percent of a component A and 2 percent of a component B; wherein the component A is powder prepared by crushing 45 percent of sepiolite, 45 percent of humic acid, 4 percent of superphosphate and 4 percent of bone meal, sieving the crushed materials with a 200-mesh sieve and mixing the crushed materials; component B is a 2% aqueous solution of TMT15 at a concentration of 15%; the curing agent for inhibiting the tobacco from absorbing cadmium and lead elements in soil and the application thereof adopt inorganic curing agents such as sepiolite, calcium superphosphate and the like, and organic curing agents such as humic acid, bone meal, TMT15 (trimercaptotriazine trisodium salt) and the like, and an inorganic and organic composite curing agent for in-situ remediation of Cd and Pb pollution of tobacco-planting soil is prepared for remediation and treatment work of heavy metal polluted tobacco-planting soil.
The Chinese patent with application number of 201210248869.9 discloses a heavy metal stabilizer for removing heavy metal pollution and a using method thereof. The heavy metal stabilizer contains a compound lignin-based dithiocarbamate, wherein the lignin-based dithiocarbamate is one or the combination of more than one of lignin-based sodium dithiocarbamate, lignin-based potassium dithiocarbamate or lignin-based ammonium dithiocarbamate, and can be used for treating heavy metal pollution.
The Chinese patent with the application number of 201510897980.4 discloses a heavy metal repairing agent and an in-situ repairing method of heavy metal contaminated soil. The heavy metal restoration agent comprises a sulfur-containing compound solution and an iron-containing compound, wherein iron in the iron-containing compound and the sulfur-containing compound solution are mixed according to a solid-to-liquid ratio of 1kg: 20L-1 kg:1L to obtain the heavy metal restoration agent. The heavy metal repairing agent has the advantages that the liquid-solid ratio of the iron-containing compound to the sulfur-containing compound solution is appropriate, the mass concentration of the sulfur-containing compound solution is reasonable, and the trimercapto triazine trisodium salt can form a stable sulfide chelate coprecipitate with heavy metal ions in soil, so that the effect of fixing the heavy metals is achieved. The iron-containing compound helps to weaken the combination of plant root exudate and heavy metals in soil and stabilize the fixing effect of the heavy metals. The heavy metal repairing agent can fix various heavy metal ions in soil at the same time, has good stability of fixing the heavy metal ions, and can reduce the content of heavy metal in the soil in a short time.
The following problems exist in the existing heavy metal soil remediation technology: in the preparation process of the heavy metal stabilizer, a part of mineral substances are used more, so that the soil after restoration is hardened, the content of organic matters is greatly reduced, the soil after restoration cannot be cultivated, the original value of the soil after capacity increase is lost, and the practical application of the soil after restoration is large in limitation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a humic acid soil heavy metal restoration agent, a preparation method and an application thereof, and also aims to provide a restoration method of heavy metal contaminated soil.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a humic acid soil heavy metal restoration agent comprises the following steps:
(1) mixing: uniformly mixing 15-30 parts by weight of humic acid, 10-50 parts by weight of water, 0.2-5 parts by weight of polypropylene glycol, 1-10 parts by weight of hydroxypropyl methyl cellulose and 0.1-2 parts by weight of calcium carbonate to obtain a mixture;
(2) molding: fully mixing the mixture obtained in the step (1) at the temperature of 40-100 ℃ for 2-4h, and then extruding and molding to obtain molded particles of 1-3 cm;
(3) and (3) drying: drying the particles formed in the step (2) for 12-36h at the temperature of 80-120 ℃ to obtain dried particles;
(4) pore-forming: calcining the dried particles in the step (3) for 2-24h in an inert atmosphere at the calcining temperature of 100-300 ℃ to obtain the porous humic acid composite material;
(5) adding: 5-15 parts by weight of the porous humic acid composite material obtained in the step (4), 2-10 parts by weight of hydroxyapatite and 0.5-5 parts by weight of gamma-Al2O33-20 parts of quicklime, 2-15 parts of fly ash and 3-20 parts of attapulgite by weight are mixed to obtain the humic acid soil heavy metal restoration agent.
Preferably, in the mixing process in the step (1), the water used is ultrapure water.
Preferably, in the pore-forming process in the step (4), the inert atmosphere is high-purity nitrogen or high-purity argon, and the purity is 99.99%.
Preferably, in order to further improve the adsorption performance of the raw material, the attapulgite is treated for 2 to 4 hours in an air atmosphere at 350 to 400 ℃ in the adding process of the step (5).
Preferably, the calcium carbonate powder has a particle size of 100 mesh in the mixing step (1), and the attapulgite has a particle size of 100 mesh in the adding step (5).
A product prepared by the preparation method of the humic acid soil heavy metal restoration agent.
An application of humic acid soil heavy metal restoration agent in the restoration of heavy metal contaminated soil.
A method for restoring heavy metal contaminated soil comprises the following steps:
(1) crushing and screening soil sample particles to 100-200 meshes, and placing the soil sample particles in an impermeable container;
(2) uniformly mixing 100 parts by weight of the soil sample in the step (1) with 5-20 parts by weight of the humic acid soil heavy metal restoration agent prepared by the method of claim 1 in an impermeable container, adding water, and controlling the water content to be about 5-30%;
(3) after being uniformly mixed, the mixture is maintained for 5 to 30 days at the maintenance temperature of between 25 and 35 ℃ under the outdoor condition, the water content is controlled to be about 5 to 30 percent, sampling detection is carried out, and the heavy metal removal effect is detected.
Preferably, the heavy metal contaminated soil contains one or more of cadmium, lead, zinc, nickel and arsenic ions. The invention has the following beneficial effects:
(1) the heavy metal repairing agent is mainly humic acid which is a natural high molecular polymer. The structural unit of the material contains active groups such as hydroxyl, carboxyl, quinonyl, carbonyl and the like, and has strong adsorption, exchange and chelation capabilities. The chelate generated by humic acid and metal ions has higher stability, is a natural metal ion stabilizer, and the heavy metal adsorption capacity of the modified porous humic acid heavy metal stabilizer is further enhanced. Humic acid belongs to natural high molecular polymers, is an environment-friendly substance, and can increase the organic matter content and cation exchange capacity of soil and improve the soil texture.
(2) The main components of the repairing agent adopted by the invention are all natural materials, and the porous humic acid heavy metal stabilizer prepared by the technical means of the invention has developed pores and large specific surface area, and can quickly and effectively stabilize heavy metal ions in soil through various mechanisms such as chelation, precipitation, adsorption and the like. Thereby reducing the toxicity and the bioavailability of the heavy metal pollutants and reducing the risks of the heavy metal polluted soil to the environment and the human health.
(3) The components of the repairing agent prepared by the invention contain the components for improving the soil texture, so that the soil tiltability can be improved while the soil is repaired, the situation that the tiltability is poor after the repair in the current technology for repairing the heavy metal contaminated soil is changed, and an effective method is provided for the utilization of the repaired soil in the municipal garden construction.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1:
a preparation method of a humic acid soil heavy metal restoration agent comprises the following steps:
(1) and (4) mixing. Uniformly mixing 30g of humic acid, 40g of water, 0.5g of polypropylene alcohol, 5g of hydroxypropyl methyl cellulose and 0.5g of calcium carbonate to obtain a mixture.
(2) And (5) molding. And (3) fully mixing the mixture obtained in the step (1) at the temperature of 80 ℃ for 2h, and then extruding and molding to obtain 2cm molded particles.
(3) And (5) drying. Drying the granules formed in the step (2) at 105 ℃ for 12h to obtain dried granules.
(4) And (6) forming holes. And (4) calcining the dried particles in the step (3) for 4 hours at the calcining temperature of 250 ℃ in an inert atmosphere to obtain the porous humic acid composite material.
（5）And (4) adding. Mixing 15g of the porous humic acid composite material obtained in the step (4), 3g of hydroxyapatite and 2g of gamma-Al2O34g of quicklime, 5g of fly ash and 5g of attapulgite are mixed to obtain the humic acid soil heavy metal restoration agent.
The preparation technical scheme of the humic acid soil heavy metal restoration agent is further optimized or improved as follows: in the mixing process in the step (1), the water used is ultrapure water. In the pore-forming process in the step (4), the inert atmosphere is one of high-purity nitrogen or high-purity argon, and the purity is 99.99%. In the adding process in the step (5), the attapulgite is treated for 2 hours at 350 ℃ in an air atmosphere. In the mixing process in the step (1), the particle size of the calcium carbonate powder is 100 meshes, and in the adding process in the step (5), the particle size of the attapulgite is 100 meshes.
Example 2:
a preparation method of a humic acid soil heavy metal restoration agent comprises the following steps:
(1) and (4) mixing. Mixing 15g humic acid, 30g water, 1g polypropylene alcohol, 10g hydroxypropyl methyl cellulose and 0.5g calcium carbonate uniformly to obtain a mixture.
(2) And (5) molding. And (3) fully mixing the mixture obtained in the step (1) at the temperature of 80 ℃ for 2h, and then extruding and molding to obtain 2cm molded particles.
(3) And (5) drying. Drying the granules formed in the step (2) at 105 ℃ for 12h to obtain dried granules.
(4) And (6) forming holes. And (4) calcining the dried particles in the step (3) for 4 hours at the calcining temperature of 200 ℃ in an inert atmosphere to obtain the porous humic acid composite material.
(5) And (4) adding. Mixing 15g of the porous humic acid composite material obtained in the step (4), 3g of hydroxyapatite and 2g of gamma-Al2O34g of quicklime, 5g of fly ash and 5g of attapulgite are mixed to obtain the humic acid soil heavy metal restoration agent.
The preparation technical scheme of the humic acid soil heavy metal restoration agent is further optimized as follows: in the mixing process in the step (1), the water used is ultrapure water. In the pore-forming process in the step (4), the inert atmosphere is one of high-purity nitrogen or high-purity argon, and the purity is 99.99%. In the adding process in the step (5), the attapulgite is treated for 2 hours at 350 ℃ in an air atmosphere. In the mixing process in the step (1), the particle size of the calcium carbonate powder is 100 meshes, and in the adding process in the step (5), the particle size of the attapulgite is 100 meshes.
Example 3:
a preparation method of a humic acid soil heavy metal restoration agent comprises the following steps:
(1) and (4) mixing. Uniformly mixing 25g of humic acid, 40g of water, 0.5g of polypropylene alcohol, 10g of hydroxypropyl methyl cellulose and 0.5g of calcium carbonate to obtain a mixture.
(2) And (5) molding. And (3) fully mixing the mixture obtained in the step (1) at the temperature of 80 ℃ for 2h, and then extruding and molding to obtain 2cm molded particles.
(3) And (5) drying. Drying the granules formed in the step (2) at 105 ℃ for 12h to obtain dried granules.
(4) And (6) forming holes. And (4) calcining the dried particles in the step (3) for 4 hours at the calcining temperature of 250 ℃ in an inert atmosphere to obtain the porous humic acid composite material.
(5) And (4) adding. Mixing 15g of the porous humic acid composite material obtained in the step (4), 3g of hydroxyapatite and 2g of gamma-Al2O34g of quicklime, 5g of fly ash and 5g of attapulgite are mixed to obtain the humic acid soil heavy metal restoration agent.
The preparation technical scheme of the humic acid soil heavy metal restoration agent is further optimized as follows: in the mixing process in the step (1), the water used is ultrapure water. In the pore-forming process in the step (4), the inert atmosphere is one of high-purity nitrogen or high-purity argon, and the purity is 99.99%. In the adding process in the step (5), the attapulgite is treated for 2 hours at 350 ℃ in an air atmosphere. In the mixing process in the step (1), the particle size of the calcium carbonate powder is 100 meshes, and in the adding process in the step (5), the particle size of the attapulgite is 100 meshes.
Example 4
A restoration method of humic acid heavy metal soil is carried out by adopting the following steps:
(1) the soil sample 1 particles were crushed and sieved to 100 mesh and placed in an impermeable container.
(2) In an impermeable container, uniformly mixing 100g of the soil sample in the step (1) with 10g of the humic acid soil heavy metal restoration agent, adding water, and controlling the water content to be about 10%.
(3) After being uniformly mixed, the mixture is maintained for 15 days at the maintenance temperature of 25 ℃ under the outdoor condition, the water content is controlled to be about 10 percent, and sampling detection is carried out to detect the heavy metal removal effect.
In the experiment of the soil sample 1, the sample 1 is from the range of 1Km around the manganese ore tailing dam, and the effective concentrations of Cr and Pb in the soil are respectively 12.67mg/kg and 50.79mg/kg before the humic acid soil heavy metal restoration agent is added for restoration; after the humic acid soil heavy metal restoration agent is added for restoration, the effective state concentrations of Cr and Pb in the soil are respectively 0.84mg/kg and 1.85mg/kg, and the fixation rates of Cr and Pb in the soil are respectively 93.37% and 96.36%.
Examples 5,
A restoration method of humic acid heavy metal soil comprises the following steps:
(1) the soil sample 2 particles were crushed and sieved to 100 mesh and placed in an impermeable container.
(2) In an impermeable container, 100g of the soil sample in the step (1) and 12g of the humic acid soil heavy metal restoration agent are uniformly mixed, and water is added to the mixture and is controlled to be about 10 percent.
(3) After being uniformly mixed, the mixture is maintained for 15 days at the maintenance temperature of 25 ℃ under the outdoor condition, the water content is controlled to be about 10 percent, and sampling detection is carried out to detect the heavy metal removal effect.
In the experiment of the soil sample 2, the sample 2 is from the range of 1Km around the manganese ore tailing dam, and the effective state concentrations of Cd and Mn in the soil are respectively 9.48mg/kg and 267.79mg/kg before the humic acid soil heavy metal restoration agent is added for restoration; after humic acid soil heavy metal restoration agents are added for restoration, the effective state concentrations of Cd and Mn in the soil are respectively 0.21mg/kg and 5.70mg/kg, and the fixation rates of Cd and Mn in the soil are respectively 97.78% and 97.87%.
Example 6
A restoration method of humic acid heavy metal soil comprises the following steps:
(1) the soil sample 2 particles were crushed and sieved to 100 mesh and placed in an impermeable container.
(2) In an impermeable container, uniformly mixing 100g of the soil sample in the step (1) with 15g of the humic acid soil heavy metal restoration agent, adding water, and controlling the water content to be about 10%.
(3) After being uniformly mixed, the mixture is maintained for 15 days at the maintenance temperature of 25 ℃ under the outdoor condition, the water content is controlled to be about 10 percent, and sampling detection is carried out to detect the heavy metal removal effect.
In the experiment of the soil sample 2, the sample 2 is from the range of 1Km around the manganese ore tailing dam, and the effective state concentrations of Cd and Mn in the soil are respectively 9.48mg/kg and 267.79mg/kg before the humic acid soil heavy metal restoration agent is added for restoration; after humic acid soil heavy metal restoration agents are added for restoration, the effective state concentrations of Cd and Mn in the soil are respectively 0.27mg/kg and 4.55mg/kg, and the fixation rates of Cd and Mn in the soil are respectively 97.15% and 98.30%.
The heavy metal contaminated soil provided by the invention contains one or more of cadmium, lead, zinc, nickel and arsenic ions.
The above technical features constitute embodiments of the present invention, which have strong adaptability and better implementation effect, and unnecessary technical features can be increased or decreased according to actual needs to meet the requirements of different situations, and all belong to the protection scope of the present invention.
Claims (9)
1. A preparation method of a humic acid soil heavy metal restoration agent is characterized by comprising the following steps:
(1) mixing: uniformly mixing 15-30 parts by weight of humic acid, 10-50 parts by weight of water, 0.2-5 parts by weight of polypropylene glycol, 1-10 parts by weight of hydroxypropyl methyl cellulose and 0.1-2 parts by weight of calcium carbonate to obtain a mixture;
(2) molding: fully mixing the mixture obtained in the step (1) at the temperature of 40-100 ℃ for 2-4h, and then extruding and molding to obtain molded particles of 1-3 cm;
(3) and (3) drying: drying the particles formed in the step (2) for 12-36h at the temperature of 80-120 ℃ to obtain dried particles;
(4) pore-forming: calcining the dried particles in the step (3) for 2-24h in an inert atmosphere at the calcining temperature of 100-300 ℃ to obtain the porous humic acid composite material;
(5) adding: 5-15 parts by weight of the porous humic acid composite material obtained in the step (4), 2-10 parts by weight of hydroxyapatite and 0.5-5 parts by weight of gamma-Al2O33-20 parts of quicklime, 2-15 parts of fly ash and 3-20 parts of attapulgite by weight are mixed to obtain the humic acid soil heavy metal restoration agent.
2. The preparation method of the humic acid type soil heavy metal restoration agent according to claim 1, wherein in the mixing process in the step (1), the water is ultrapure water.
3. The preparation method of the humic acid soil heavy metal restoration agent according to claim 1, wherein in the pore-forming process in the step (4), the inert atmosphere is high-purity nitrogen or high-purity argon, and the purity is 99.99%.
4. The preparation method of the humic acid soil heavy metal restoration agent according to claim 1, wherein in order to further improve the adsorption performance of the raw materials, in the adding process in the step (5), the attapulgite is treated for 2-4h at 350-400 ℃ in an air atmosphere.
5. The preparation method of the humic acid soil heavy metal restoration agent according to claim 1, wherein in the mixing process of step (1), the particle size of the calcium carbonate powder is 100 meshes, and in the adding process of step (5), the particle size of the attapulgite is 100 meshes.
6. A product prepared by the preparation method of the humic acid soil heavy metal restoration agent according to claim 1.
7. The humic acid soil heavy metal restoration agent as claimed in claim 6, which is applied to restoration of heavy metal contaminated soil.
8. The method for restoring the heavy metal contaminated soil is characterized by comprising the following steps:
(1) crushing and screening soil sample particles to 100-200 meshes, and placing the soil sample particles in an impermeable container;
(2) uniformly mixing 100 parts by weight of the soil sample in the step (1) with 5-20 parts by weight of the humic acid soil heavy metal restoration agent prepared by the method of claim 1 in an impermeable container, and adding water to control the water content to be 5-30%;
(3) after being uniformly mixed, the mixture is maintained for 5 to 30 days at the maintenance temperature of between 25 and 35 ℃ under the outdoor condition, the water content is controlled to be between 5 and 30 percent, sampling detection is carried out, and the heavy metal removal effect is detected.
9. The method for remediating heavy metal contaminated soil according to claim 8, wherein the heavy metal contaminated soil contains one or more of cadmium, lead, zinc, nickel, and arsenic ions.
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| CN109332370B (en) * | 2018-11-22 | 2020-07-17 | 东北石油大学 | In-situ remediation method for heavy metal chromium ion contaminated soil |
| CN111842473A (en) * | 2020-07-29 | 2020-10-30 | 上海傲江生态环境科技有限公司 | Method for treating heavy metal contaminated soil by using macromolecular alcohol chelating agent |
| CN112457852B (en) * | 2020-11-24 | 2022-02-01 | 山东大学 | Red mud-based ferrate mixture soil remediation agent as well as preparation method and application thereof |
| CN115845788B (en) * | 2022-11-25 | 2024-02-23 | 重庆化工职业学院 | Application of natural manganese mineral powder in adsorbing mercury ions, application of removing mercury ions in wastewater and application of removing mercury ions in soil |
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| 腐殖酸改性及其对镉的吸附特性;陈荣平等;《南京林业大学学报》;20140731;第38卷(第4期);第1.3节第1段，第2.2节第1段，第2.3节第1段，第3节第1段 * |
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| CN108359475A (en) | 2018-08-03 |
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