CN112457851A - Heavy metal contaminated soil remediation material and preparation method and application thereof - Google Patents
Heavy metal contaminated soil remediation material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112457851A CN112457851A CN202011270973.9A CN202011270973A CN112457851A CN 112457851 A CN112457851 A CN 112457851A CN 202011270973 A CN202011270973 A CN 202011270973A CN 112457851 A CN112457851 A CN 112457851A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- contaminated soil
- metal contaminated
- soil remediation
- remediation material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- 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
The invention provides a heavy metal contaminated soil remediation material and a preparation method and application thereof. The repair material is pyrolytic biochar, the pyrolytic biochar is loaded with iron ions, phosphorus elements and hydroxyl groups, and the pyrolytic biochar further has a pore channel structure. When the soil is repaired, the phosphorus element and the hydroxyl group are preferentially acted in the soil, then the iron ions are slowly released, and the heavy metal polluted soil with antagonistic factors can be effectively treated through different sequences of the action of the iron ions, the phosphorus element and the hydroxyl group in the soil, so that the antagonistic influence is reduced.
Description
Technical Field
The invention belongs to the technical field of heavy metal contaminated soil treatment, and particularly relates to a heavy metal contaminated soil remediation material and a preparation method and application thereof.
Background
At present, the heavy metal pollution condition of soil is not optimistic, and the problem of multiple heavy metal combined pollution exists. Particularly, the over-standard position point of heavy metal in the mining area soil is As high As 33.4%, the main elements polluted by the heavy metal soil are Cd, Pb and As, and the heavy metal pollution of the soil around the non-ferrous metal mining area is more serious.
The stabilization and remediation are one of the main technologies for soil heavy metal pollution remediation, and the stabilization material is the core of the stabilization and remediation technology. The stabilizing materials comprise clay materials, phosphorus-containing materials, organic materials and the like, and promote the migration of pollutants in soil and reduce environmental risks through the effects of adsorption, surface complexation, oxidation reduction, precipitation, coprecipitation and the like of the stabilizing materials on heavy metals. However, on the one hand, the remediation effect of heavy metal contaminated soil by the stabilizing material is different due to the influence of various factors in the soil; on the other hand, compared with single pollution, the heavy metal compound polluted soil has interaction among elements or compounds, and the interaction can influence the remediation of the polluted soil.
The existing research mainly improves the stabilizing effect on the heavy metal in the soil by compounding various stabilizing agents, but most of stabilizing agents with better effect have chemical toxicity, so that the secondary pollution to the soil is easily caused by improper application. In addition, most stabilizing agents aim at single heavy metal contaminated soil or soil contaminated by several heavy metals with similar remediation principles, and research and development on remediation materials of heavy metal composite contaminated soil with antagonistic factors (such as cadmium, lead and arsenic) are few.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a heavy metal contaminated soil remediation material, which is pyrolytic biochar loaded with iron ions, phosphorus elements and hydroxyl groups, and has a pore structure. When the soil is repaired, the phosphorus element and the hydroxyl group are preferentially acted in the soil, and then the iron ions are slowly released. Through different sequences of applying iron ions, phosphorus elements and hydroxyl groups to soil, the heavy metal polluted soil with antagonistic factors can be effectively treated, and the antagonistic influence is reduced.
The invention also provides a preparation method of the heavy metal contaminated soil remediation material.
The invention also provides application of the heavy metal contaminated soil remediation material in heavy metal contaminated soil remediation.
The invention provides a heavy metal contaminated soil remediation material in a first aspect, which comprises:
pyrolyzing biochar;
the pyrolytic biochar is loaded with iron ions, phosphorus elements and hydroxyl groups, and has a pore structure.
The preparation method of the pyrolytic biochar comprises the following steps: taking crushed biomass as raw materials, including rice straw, palm leaves, pine logs and bamboos, placing in a vacuum tube furnace, charging nitrogen, keeping at 650 ℃ for 2.5h, carbonizing, cooling to room temperature, grinding and sieving to obtain the pyrolytic biochar.
The heavy metal contaminated soil described in the present invention mainly refers to soil which is compositely contaminated with cadmium, lead and arsenic.
Meanwhile, in the soil compositely polluted by cadmium, lead and arsenic, compared with the soil singly polluted, the soil has different physical and chemical properties and characteristics of pollutants, and the complexity of soil pollution is increased. In general, interactions between complex contaminants occur, manifested as antagonism, additivity and synergy. Antagonism refers to the presence of one contaminant that inhibits the absorption of another contaminant and its biological effects. During the transportation and absorption of various pollutants in animals and plants, the binding sites on the carrier are subjected to mutual competition, so that the absorption of a certain pollutant is influenced. When cadmium and lead coexist, lead can capture the adsorption sites of cadmium in soil, increase the activity of cadmium and improve the bioavailability of cadmium in soil. Under the coexistence condition of lead in soil, the absorption of arsenic by plants is obviously reduced.
The fixation of heavy metals in soil is greatly influenced by pH, and different heavy metals show different mobility characteristics under the influence of pH. The solubility of cadmium in the range of pH 3-8 is reduced along with the increase of pH; lead solubility is increased after pH is higher than 6, and As has stronger solubility in alkaline solution. The above-mentioned influence makes it difficult to fix three heavy metals simultaneously.
The phosphate passivator comprises solubility (phosphoric acid, monopotassium phosphate, monocalcium phosphate and the like) and insolubility (phosphogypsum, phosphate rock, hydroxyapatite and the like). Whether the insoluble phosphate can well passivate heavy metals in soil is mainly limited by the pH value of the soil. At pH 5, lead is deactivated relatively quickly, mainly because of the formation of Pb at this pH5(PO4)3The OH speed is very fast. Soluble phosphates, when added to soil, lower the pH of the soil and thereby increase the leaching of other heavy metals such as arsenic. Phosphorus andas is a group element, both of which have similar properties and produce antagonism, resulting in PO4 3-With AsO4 3-Formation of competitive adsorption, PO4 3-To replace AsO in soil4 3-Thereby releasing arsenic and enhancing its mobility.
After the heavy metal contaminated soil remediation material disclosed by the invention is contacted with heavy metal contaminated soil, phosphorus elements and hydroxyl groups loaded on the surface of the pyrolytic biochar firstly react with lead and cadmium in the heavy metal contaminated soil, then iron ions are slowly released and coprecipitated with arsenic, lead and cadmium in the heavy metal contaminated soil, and finally the treatment of the heavy metal contaminated soil with the influence of antagonistic factors is realized.
According to one embodiment of the invention, the specific surface area of the heavy metal contaminated soil remediation material is more than 240m2/g。
According to one embodiment of the invention, the particle size of the heavy metal contaminated soil remediation material is less than or equal to 0.25 mm.
The second aspect of the invention provides a preparation method of a heavy metal contaminated soil remediation material, which comprises the following steps:
s1: adding the pyrolytic biochar into an alkali solution, soaking at normal temperature, and performing primary pyrolysis;
s2: adding the pyrolytic biochar treated in the step S1 into a mixed solution of ferric salt and urea, and carrying out second pyrolysis after the first heating treatment;
s3: and (4) uniformly mixing the pyrolytic biochar treated in the step (S2) with a phosphorus source solution, carrying out heating treatment for the second time, filtering, and carrying out pyrolysis on filter residues for the third time to obtain the heavy metal contaminated soil remediation material.
In the preparation method, the pyrolytic biochar is firstly subjected to iron modification and then phosphorus modification, and the order of the pyrolytic biochar and the phosphorus modification cannot be changed. If phosphorus modification is carried out first and then iron modification is carried out, iron contacts soil first, arsenic, lead and cadmium in the soil can be reduced by the iron, shunting can be caused, the best stabilizing effect on arsenic can not be achieved, and then phosphorus is released continuously to activate the arsenic.
According to one embodiment of the invention, the alkali solution is a NaOH solution or a KOH solution.
The pyrolysis of the biochar can generate solid inorganic salt, liquid tar and gaseous byproducts such as carbon monoxide, carbon dioxide and methane during the preparation process, and the ash can affect the adsorption performance of the biochar. The alkali modification can reduce the ash content to a great extent, thereby increasing the specific surface area of the biochar and further improving the adsorption capacity. The alkali modification can also increase basic groups such as hydroxyl, amino and the like of the biochar, and provide more adsorption sites. The alkali solution has strong corrosivity on the biochar, so that fragments among gaps of the biochar and hole walls are corroded, and inner pore channels of the biochar are dredged to form micropores, and the specific surface area and the pore diameter of the micropores are increased.
In step S1, adding the pyrolytic biochar into an alkali solution can improve the surface structure, enhance the adsorption activation performance, increase the specific surface area, and introduce oxygen-containing functional groups (such as hydroxyl, amino, carboxyl, etc.), which belongs to a covalent bond modification method.
According to one embodiment of the invention, the time for normal-temperature immersion is 12-36 h.
According to one embodiment of the invention, the iron salt is a trivalent iron salt.
According to a preferred embodiment of the invention, the iron salt is iron nitrate.
Ferric nitrate and urea can be used for synthesizing urea iron (III) complex, and gamma-Fe can be obtained after thermal decomposition2O3The nano powder has better heavy metal stabilizing effect.
In step S2, on one hand, iron modification can increase the CEC (Cation Exchange Capacity) on the surface of the charcoal, and improve the adsorption Capacity for heavy metals; on the other hand, iron ions are attached to the pores of the biochar and can be coprecipitated with heavy metals in soil, so that the stabilizing effect on the heavy metals is improved. The iron ions have stabilizing effect on cadmium, lead and arsenic, wherein the stabilizing effect on arsenic is the best.
According to an embodiment of the present invention, in step S1, the temperature of the first pyrolysis is 600 to 700 ℃.
According to an embodiment of the invention, in step S2, the temperature of the second pyrolysis is 250 to 350 ℃.
According to an embodiment of the invention, in the step S3, the temperature of the third pyrolysis is 250 to 350 ℃.
According to an embodiment of the invention, in step S3, the mass ratio of the pyrolytic biochar to the phosphorus source solution is (1.25-2.5): 1.
in step S3, the phosphorus modification of the pyrolytic biochar can improve the hydrophilicity of the biochar, change the specific surface area and active functional groups of the biochar, and thus improve the stabilizing effect on heavy metals, particularly lead.
In step S3, the phosphorus source is micron-sized hydroxyapatite.
The third aspect of the invention provides an application of the heavy metal contaminated soil remediation material in heavy metal contaminated soil remediation.
The heavy metal contaminated soil remediation material disclosed by the invention at least has the following technical effects:
the heavy metal contaminated soil remediation material disclosed by the invention is green, pollution-free, safe and efficient. The raw material of the repairing material is a biomass material, and in the preparation and modification processes of the material, all used reagents are nontoxic reagents and do not contain ions polluting soil.
The heavy metal contaminated soil remediation material is small in using amount, neutral and free of significant influence on the pH and physical properties of soil.
The heavy metal contaminated soil remediation material can simultaneously reduce the content of Cd, Pb and As in a soil standard Toxicity Leaching method (TCLP for short) Leaching liquor by more than 90%.
Drawings
FIG. 1 is a microscopic topography of the pyrolytic biochar prepared in example 1.
FIG. 2 is a micro-topography of the heavy metal contaminated soil remediation material prepared in example 1.
Fig. 3 is an XRD pattern of the pyrolytic biochar prepared in example 1.
FIG. 4 is an XRD (X-ray diffraction) spectrum of the heavy metal contaminated soil remediation material prepared in example 1.
FIG. 5 is a Fourier transform infrared spectroscopy test of the pyrolytic biochar prepared in example 1.
FIG. 6 shows the Fourier transform infrared spectroscopy test results of the heavy metal contaminated soil remediation material prepared in example 1.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares the heavy metal contaminated soil remediation material, and specifically comprises the following steps:
s1: placing crushed palm leaves in a vacuum tube furnace, filling nitrogen for 0.5h, keeping the temperature at 650 ℃ for 2.5h, cooling to room temperature after carbonization, grinding and sieving with a 60-mesh sieve to obtain pyrolytic biochar, wherein the microstructure of the pyrolytic biochar is detected by a scanning electron microscope, and the result is shown in figure 1, and the pyrolytic biochar prepared from the palm leaves is regular in appearance and has a pore channel structure as can be observed from figure 1;
s2: adding 1mol/L KOH solution into pyrolytic biochar at a ratio of 1:2(g: mL), stirring in a constant-temperature water bath at 80 ℃ for 1h, and soaking at normal temperature for 24 h. After drying, reacting for 1h in a tube furnace at 650 ℃, cooling and then grinding and sieving with a 60-mesh sieve;
s3: mixing the pyrolytic biochar treated in the previous step according to the proportion of 1g of pyrolytic biochar, 5mL of ferric nitrate and 0.36g of urea, wherein the concentration of the ferric nitrate is 0.1-0.5 mol/L, heating to 90 ℃ by using a water bath kettle, standing to room temperature, filtering, drying, and cracking for 1h at 300 ℃ to obtain iron modified pyrolytic biochar;
s4: adding the pyrolytic biochar treated in the previous step and micron-sized hydroxyapatite (mass ratio is 5:3) into a beaker, adding distilled water, magnetically stirring for 1h at 50 ℃, filtering, drying, and putting into a vacuum tube furnace for pyrolysis at 650 ℃ for 1 h. And (3) washing with deionized water for several times until the pH value is neutral, and drying at 80 ℃ to obtain the heavy metal contaminated soil remediation material.
S5: the microstructure of the heavy metal contaminated soil remediation material is detected by a scanning electron microscope, the result is shown in fig. 2, and as can be seen by comparing fig. 2 with fig. 1, in fig. 2, a new substance is loaded on the surface of the pyrolytic biochar.
X-ray energy spectrum detection is carried out on the pyrolytic biochar prepared in the step S1 and the heavy metal contaminated soil remediation material finally prepared in the step S5, and the results are shown in Table 1.
TABLE 1 results of X-ray energy spectrum analysis
As can be seen from table 1, after the iron phosphorus modification is performed on the pyrolytic biochar, the content of O, P and Fe is increased because the pyrolytic biochar is loaded with iron ions, phosphorus elements and hydroxyl groups.
In addition, the pyrolytic biochar prepared in the step S1 and the heavy metal contaminated soil remediation material prepared in the step S5 are subjected to X-ray diffraction characterization, and the results are shown in fig. 3 and 4. As can be seen from FIGS. 3 and 4, the mineral component on the surface of the biochar is not known to contain quartz, while the composite modified biochar contains quartz and apatite, which is related to the hydroxyapatite adopted by the phosphorus modification, and the existence of iron oxide is not detected, which indicates that iron is adsorbed on the voids and the surface of the biochar in the form of ions.
The pyrolytic biochar prepared in step S1 and the heavy metal contaminated soil remediation material prepared in step S5 in example 1 were also examined by Fourier Transform Infrared spectroscopy (FTIR Spectrometer for short), and the results are shown in fig. 5 and 6. As can be seen from FIGS. 5 and 6, similar absorption peaks, mainly comprising 3454.35cm, appeared before and after the modification of the biochar-1、1108.36cm-1、509.61cm-1Nearby peak of vibration, 3454.35cm of which-1The modified biomass is treated by an associated hydroxyl (-OH) stretching vibration peak, the hydroxyl is mainly derived from carbohydrate in the biomass, and the peak strength is increased after modification, which indicates that hydroxyl groups are increased by modification; 1108.36cm-1is a symmetric stretching vibration peak (-C-O-C-) of the cellulose or the hemicellulose, so that the content of the cellulose or the hemicellulose is increased in the modification process; 509.61cm-1The vibration absorption of Si-O-Si shows that the modification process increases the release of the silicon-containing substance.
Unmodified charcoal is 2946.26, 2889.07cm-1Is aliphatic CH2Asymmetric and symmetric (-CH) stretching vibration peak of 2741.07cm-1C-H stretching vibration peak of aldehyde-CHO (2694.59 cm)-1Is the stretching vibration peak of carboxylic acid (-OH) of 1467.10cm-1The peak is the bending vibration peak of carboxylic acid (-OH), 1413.11 and 1359.99cm-1The peak is the stretching vibration peak of carboxylic acid (C-O), 1280.44 and 1241.46cm-1The compound modified biochar is an in-plane deformation bending vibration peak of alcohols or phenols (-OH), and the groups can not be detected or reduced, which indicates that the compound modification reduces the fatty CH2Aldehydes and carboxylic acid groups.
Comparative example 1
This example prepared a heavy metal contaminated soil remediation material, which was compared with example 1 except that phosphorus modification was not performed, that is, step S4 was not performed, and the remaining steps were the same as example 1.
Comparative example 2
This example prepared a heavy metal contaminated soil remediation material, which was compared with example 1 except that no iron modification, i.e., step S3, was performed, and the remaining steps were the same as example 1.
Comparative example 3
This example prepared a heavy metal contaminated soil remediation material, which was different from example 1 in that only KOH alkali modification in step S2 was performed, and iron modification and phosphorus modification were not performed. The rest of the procedure was the same as in example 1.
Comparative example 4
This example prepared a heavy metal contaminated soil remediation material, which was the same as in example 1 except that the KOH alkali modification in step S2 was changed to the HCl acid modification, as compared to example 1.
Detection example 1
The treatment effect of the leaching liquor is as follows: the suspension of the test soil sample is extracted by TCLP extraction method. Respectively adding modified biochar samples into the suspension, fully and uniformly mixing, placing in a constant-temperature shaking table, and performing shake culture for 24 hours at the set temperature of 25 ℃ and the rotation speed of 180 r/min. Filtering, and performing chemical detection on the supernatant, wherein the detection items are cadmium, lead and arsenic.
The soil treatment effect is as follows: accurately weighing 30.00 +/-0.05 g of a soil sample to be tested, placing the soil sample into a 50mL centrifuge tube, adding modified biochar samples in different proportions into the centrifuge tube, fully and uniformly mixing, adding ultrapure water, and controlling the water content to be 50%. Placing the centrifugal tube in a constant-temperature shaking table for shake culture, wherein the temperature is set to be 25 ℃, and the rotating speed is 180 r/min. After 3 days of culture, the mixture is dried and ground to 20 meshes. And detecting the content of cadmium, lead and arsenic extracted by the TCLP of the soil.
The stabilizing effect of the heavy metal contaminated soil remediation material prepared in example 1 and the soil remediation materials prepared in comparative examples 1 and 2 on cadmium, lead and arsenic in the TCLP leaching liquor of soil is shown in Table 2.
TABLE 2
The removal effects of unmodified pyrolytic biochar, the heavy metal contaminated soil remediation material prepared in the comparative example 3 and the heavy metal contaminated soil remediation material prepared in the comparative example 4 on cadmium, lead and arsenic in the TCLP leach liquor of soil are shown in Table 3.
TABLE 3
| Sample (I) | Cadmium stabilization Rate/% | Lead quantification/% | Arsenic (II)Percent conversion% |
| Unmodified pyrolytic biochar | 6.67 | 25.22 | 74.01 |
| Heavy metal contaminated soil remediation material prepared in comparative example 3 | 28.20 | 90.75 | 90.45 |
| Heavy metal contaminated soil remediation material prepared in comparative example 4 | 6.55 | 61.29 | 90.06 |
Detection example 2
The heavy metal contaminated soil remediation material prepared in example 1 was applied to soil in different amounts, cultured at 25 ℃ for three days at 180r/min, and tested for the removal effect on soil in the available state, cadmium, lead and arsenic. The control is the condition of the soil remediation material without heavy metal pollution. As shown in Table 4, the stabilization effect of the heavy metal contaminated soil remediation material with the addition amount of 5% is the best, and the effective states of Cd, Pb and As in the soil are reduced by 42.61mg/kg, 747.32mg/kg and 0.72mg/kg respectively.
TABLE 4
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A heavy metal contaminated soil remediation material, comprising:
pyrolyzing biochar;
the pyrolytic biochar is loaded with iron ions, phosphorus elements and hydroxyl groups, and has a pore structure.
2. The heavy metal contaminated soil remediation material of claim 1, wherein the specific surface area of the heavy metal contaminated soil remediation material is greater than 240m2/g。
3. The heavy metal contaminated soil remediation material of claim 1, wherein the particle size of the heavy metal contaminated soil remediation material is no greater than 0.25 mm.
4. The preparation method of the heavy metal contaminated soil remediation material of any one of claims 1 to 3, comprising the steps of:
s1: adding the pyrolytic biochar into an alkali solution, soaking at normal temperature, and performing primary pyrolysis;
s2: adding the pyrolytic biochar treated in the step S1 into a mixed solution of ferric salt and urea, and carrying out second pyrolysis after the first heating treatment;
s3: and (4) uniformly mixing the pyrolytic biochar treated in the step (S2) with a phosphorus source solution, carrying out heating treatment for the second time, filtering, and carrying out pyrolysis on filter residues for the third time to obtain the heavy metal contaminated soil remediation material.
5. The method according to claim 4, wherein in step S1, the temperature of the first pyrolysis is 600-700 ℃.
6. The method according to claim 4, wherein in step S2, the temperature of the second pyrolysis is 250-350 ℃.
7. The preparation method according to claim 4, wherein in the step S3, the temperature of the third pyrolysis is 250-350 ℃.
8. The method according to claim 4, wherein the iron salt is a trivalent iron salt.
9. The preparation method according to claim 4, wherein in step S3, the mass ratio of the pyrolytic biochar to the phosphorus source solution is (1.25-2.5): 1.
10. use of the heavy metal contaminated soil remediation material of any one of claims 1 to 3 for remediation of heavy metal contaminated soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011270973.9A CN112457851B (en) | 2020-11-13 | 2020-11-13 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011270973.9A CN112457851B (en) | 2020-11-13 | 2020-11-13 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112457851A true CN112457851A (en) | 2021-03-09 |
| CN112457851B CN112457851B (en) | 2021-07-27 |
Family
ID=74836248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011270973.9A Active CN112457851B (en) | 2020-11-13 | 2020-11-13 | Heavy metal contaminated soil remediation material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457851B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293001A (en) * | 2021-06-22 | 2021-08-24 | 广东省农业科学院农业资源与环境研究所 | Preparation and application of phosphorus-rich biochar based on mulberry branch waste |
| CN115109596A (en) * | 2022-07-21 | 2022-09-27 | 湖南有色金属研究院有限责任公司 | Soil heavy metal stabilizer and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140137917A (en) * | 2013-05-24 | 2014-12-03 | 현대건설주식회사 | System and method for remediation of soil being contaminated by concentrated heavy metal |
| CN105367346A (en) * | 2015-12-11 | 2016-03-02 | 华南农业大学 | Slow-release fertilizer for soil improvement and preparation method and application thereof |
| CN105670643A (en) * | 2016-03-08 | 2016-06-15 | 华南师范大学 | Preparation method and application of repair material for heavy metal cadmium polluted soil |
| WO2016126601A1 (en) * | 2015-02-06 | 2016-08-11 | Biocharnow, Llc | Contaminant removal from water bodies with biochar |
| CN107880892A (en) * | 2017-11-08 | 2018-04-06 | 安徽省宗正农业科技开发有限公司 | A kind of modified biomass charcoal for reducing heavy metal in soil content |
| CN108262022A (en) * | 2018-02-01 | 2018-07-10 | 佛山市铁人环保科技有限公司 | A kind of modification biological charcoal and preparation method thereof |
| CN108359470A (en) * | 2018-02-26 | 2018-08-03 | 北京三聚绿能科技有限公司 | A kind of preparation method and application of straw biomass charcoal |
| CN108607507A (en) * | 2018-03-21 | 2018-10-02 | 中国科学院生态环境研究中心 | A kind of preparation method of the high stability charcoal base cementite of degradation of dye |
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN110317611A (en) * | 2019-07-25 | 2019-10-11 | 中国林业科学研究院亚热带林业研究所 | A kind of metal oxide/biology carbon composite, preparation method and its application |
| CN110653248A (en) * | 2019-10-09 | 2020-01-07 | 安徽省农业科学院土壤肥料研究所 | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field and application thereof |
| CN110699084A (en) * | 2019-10-09 | 2020-01-17 | 东南大学 | Soil heavy metal pollution curing and repairing composite reagent and curing and repairing method |
| CN111349441A (en) * | 2020-04-10 | 2020-06-30 | 绍兴市农业科学研究院 | Method for safely utilizing As and Pb composite pollution of farmland soil |
-
2020
- 2020-11-13 CN CN202011270973.9A patent/CN112457851B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140137917A (en) * | 2013-05-24 | 2014-12-03 | 현대건설주식회사 | System and method for remediation of soil being contaminated by concentrated heavy metal |
| WO2016126601A1 (en) * | 2015-02-06 | 2016-08-11 | Biocharnow, Llc | Contaminant removal from water bodies with biochar |
| CN105367346A (en) * | 2015-12-11 | 2016-03-02 | 华南农业大学 | Slow-release fertilizer for soil improvement and preparation method and application thereof |
| CN105670643A (en) * | 2016-03-08 | 2016-06-15 | 华南师范大学 | Preparation method and application of repair material for heavy metal cadmium polluted soil |
| CN107880892A (en) * | 2017-11-08 | 2018-04-06 | 安徽省宗正农业科技开发有限公司 | A kind of modified biomass charcoal for reducing heavy metal in soil content |
| CN108262022A (en) * | 2018-02-01 | 2018-07-10 | 佛山市铁人环保科技有限公司 | A kind of modification biological charcoal and preparation method thereof |
| CN108359470A (en) * | 2018-02-26 | 2018-08-03 | 北京三聚绿能科技有限公司 | A kind of preparation method and application of straw biomass charcoal |
| CN108607507A (en) * | 2018-03-21 | 2018-10-02 | 中国科学院生态环境研究中心 | A kind of preparation method of the high stability charcoal base cementite of degradation of dye |
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN110317611A (en) * | 2019-07-25 | 2019-10-11 | 中国林业科学研究院亚热带林业研究所 | A kind of metal oxide/biology carbon composite, preparation method and its application |
| CN110653248A (en) * | 2019-10-09 | 2020-01-07 | 安徽省农业科学院土壤肥料研究所 | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field and application thereof |
| CN110699084A (en) * | 2019-10-09 | 2020-01-17 | 东南大学 | Soil heavy metal pollution curing and repairing composite reagent and curing and repairing method |
| CN111349441A (en) * | 2020-04-10 | 2020-06-30 | 绍兴市农业科学研究院 | Method for safely utilizing As and Pb composite pollution of farmland soil |
Non-Patent Citations (1)
| Title |
|---|
| 鲍丙露: "磷基生物炭对重金属的吸附效果及其环境风险分析", 《安徽农学通报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293001A (en) * | 2021-06-22 | 2021-08-24 | 广东省农业科学院农业资源与环境研究所 | Preparation and application of phosphorus-rich biochar based on mulberry branch waste |
| CN115109596A (en) * | 2022-07-21 | 2022-09-27 | 湖南有色金属研究院有限责任公司 | Soil heavy metal stabilizer and preparation method and application thereof |
| CN115109596B (en) * | 2022-07-21 | 2023-11-24 | 湖南有色金属研究院有限责任公司 | Soil heavy metal stabilizer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112457851B (en) | 2021-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111036174B (en) | Magnetic biochar based on iron-enriched plants and preparation method and application thereof | |
| Yang et al. | Remediation of lead contaminated soil by biochar-supported nano-hydroxyapatite | |
| Zhou et al. | Sorption of heavy metals on chitosan-modified biochars and its biological effects | |
| CN104941583B (en) | A kind of cadmium arsenic adsorbent material, Preparation method and use | |
| CN115254020B (en) | Modified hydrothermal carbon material for treating heavy metal contaminated soil and preparation method and application thereof | |
| Sun et al. | Biochars derived from various crop straws: characterization and Cd (II) removal potential | |
| Bashir et al. | Efficiency of KOH-modified rice straw-derived biochar for reducing cadmium mobility, bioaccessibility and bioavailability risk index in red soil | |
| CN112457851B (en) | Heavy metal contaminated soil remediation material and preparation method and application thereof | |
| Liu et al. | CO2 activation promotes available carbonate and phosphorus of antibiotic mycelial fermentation residue-derived biochar support for increased lead immobilization | |
| CN115109596B (en) | Soil heavy metal stabilizer and preparation method and application thereof | |
| Zhang et al. | Stabilization process and potential of agro-industrial waste on Pb-Contaminated soil around Pb–Zn mining | |
| Li et al. | Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals | |
| Chen et al. | Biosorption of V (V) onto Lantana camara biochar modified by H3PO4: Characteristics, mechanism, and regenerative capacity | |
| Su et al. | Zero-valent iron doped carbons readily developed from sewage sludge for lead removal from aqueous solution | |
| CN111570494B (en) | Heavy metal contaminated soil remediation method | |
| CN111871370A (en) | Preparation method of C-O-Fe biochar aiming at soil heavy metal passivation | |
| Salam et al. | Biochar production and characterization as a measure for effective rapeseed residue and rice straw management: an integrated spectroscopic examination | |
| CN112642850B (en) | Remediation method for antagonistic heavy metal contaminated soil | |
| Liu et al. | Natural bioaugmentation enhances the application potential of biochar for Cd remediation | |
| KR102456298B1 (en) | Preparing method of hydrochar stabilizers based on wood waste comprising iron nanoparticles and Stabilization method for contaminated soil comprising arsenic and cation mixed using thereof | |
| CN114130356A (en) | Zinc ferrite-based material and preparation method and application thereof | |
| CN115125017A (en) | Method for preparing biochar through alkali fusion fly ash-straw co-pyrolysis and application of biochar | |
| CN110420624B (en) | Porous biomass charcoal-based phosphate adsorbent and preparation method and application thereof | |
| KR20210115107A (en) | Preparing method of hydrochar stabilizers based on wood waste comprising magnesium ferrite nanoparticles and Stabilization method for contaminated soil comprising arsenic and cation mixed using thereof | |
| CN116786081A (en) | Soil cadmium-arsenic combined pollution passivator and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No.99, neiya Road, Longping hi tech park, Furong district, Changsha City, Hunan Province, 410000 Applicant after: Hunan Nonferrous Metals Research Institute Co.,Ltd. Address before: No.99, neiya Road, Longping hi tech park, Furong district, Changsha City, Hunan Province, 410000 Applicant before: HUNAN Research Institute FOR NONFERROUS METALS |
|
| CB02 | Change of applicant information | ||
| CB03 | Change of inventor or designer information |
Inventor after: OuYang Kun Inventor after: Wang Bing Inventor after: Wan Si Inventor after: Cao Bailin Inventor after: Yin Liujuan Inventor after: Peng Xinping Inventor after: Wan Wenyu Inventor after: Zhu Anling Inventor after: You Ping Inventor after: Li Qian Inventor after: Peng Da Inventor after: Zhou Rui Inventor after: Li Can Inventor after: Ye Shimin Inventor after: Yuan Cuiyu Inventor after: Chen Wei Inventor before: OuYang Kun Inventor before: Wang Bing Inventor before: Wan Si Inventor before: Cao Bailin Inventor before: Yin Liujuan Inventor before: Peng Xinping Inventor before: Wan Wenyu Inventor before: Zhu Anling Inventor before: You Ping Inventor before: Li Qian Inventor before: Peng Da Inventor before: Zhou Rui Inventor before: Li Can Inventor before: Ye Shiming Inventor before: Yuan Cuiyu Inventor before: Chen Wei |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |