CN110327882B - Preparation method and application of multiposition activated and modified reed-triarrhena sacchariflora biochar - Google Patents
Preparation method and application of multiposition activated and modified reed-triarrhena sacchariflora biochar Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
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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
- B09C1/007—Reclamation of contaminated soil by removing contaminants floating on the water table
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to the field of heavy metal pollution treatment in water and soil, in particular to a preparation method of multi-site activated and modified reed-triarrhena biochar and application thereof in removing heavy metal zinc and cadmium. The preparation method comprises the steps of cleaning, drying and crushing the reed-triarrhena sacchariflora biomass, fully and ultrasonically stirring the reed-triarrhena sacchariflora biomass in a pyrolusite powder solution, then carrying out low-temperature hydrothermal carbonization on the biomass to prepare non-activated and modified biochar, soaking the biochar in a calcium chloride-hydrogen peroxide mixed solution, activating the biochar-calcium chloride-hydrogen peroxide mixed solution by microwaves, modifying the dried biochar by ultraviolet radiation to obtain the activated and modified biochar, and using the obtained biochar to remove heavy metals such as zinc and cadmium in water and soil. The application method comprises the following steps: adding activated and modified charcoal into heavy metal zinc and cadmium wastewater for adsorption reaction; or directly adding the mixture into soil polluted by heavy metal zinc and cadmium, fully and uniformly mixing, and aging for a period of time to finish the bioremediation of the soil polluted by the heavy metal zinc and cadmium.
Description
Technical Field
The invention relates to the field of heavy metal pollution treatment in water and soil, in particular to a preparation method of multi-site activated and modified reed-triarrhena biochar and application thereof in removing heavy metal zinc and cadmium.
Background
In subtropical monsoon climate in the west of the river, the soil belongs to red soil, the red soil has the characteristics of high development degree and strong leaching effect, and unreasonable development and utilization of red soil resources are adopted, so that the red soil acidification phenomenon is common, and is influenced by mining, smelting and industrial three wastes in the five river basins at the upstream of Yanghu, the heavy metal pollution of farmland soil and farmland irrigation water in partial areas is serious, especially the heavy metal pollution of zinc and cadmium. Because zinc and cadmium can be enriched in organisms and enter human bodies through food chains to cause chronic poisoning, the over-standard zinc and cadmium of rice becomes a big problem of food safety in the west and the river.
The wetland plant resources in the Jiangxi Yanghu region are rich, wherein the biomass of reed-triarrhena sacchariflora is more than 30 percent of the total biomass of Yanghu, the constituents of the wetland reed-triarrhena sacchariflora are mostly cellulose, hemicellulose, lignin and the like, and the wetland reed-triarrhena sacchariflora contains a large amount of active groups such as hydroxyl, carboxyl, carbonyl and the like; the basic skeleton is composed of carbon elements, the reed-triarrhena sacchariflora biomass is used as a raw material to prepare the biochar adsorbing material, the biochar has higher pH value, heavy metal precipitates are easily formed when the biochar is applied to soil, and the function of adsorbing and passivating heavy metals can be exerted.
The biochar mainly adsorbs heavy metals in passivated soil through five effects, including surface adsorption, surface complexation, precipitation, ion exchange and electrostatic interaction, wherein the effect of adsorbing and fixing heavy metals is as follows: precipitation > complexation > electrostatic interaction, ion exchange > physical adsorption. However, the adsorption and passivation capability of the biochar on heavy metal pollutants is limited, and the performance improvement of the biochar through a physical method and a chemical method becomes an important link for improving the adsorption and passivation capability of the biochar. Through the chemical oxidation of the hydrogen peroxide, the oxygen-containing functional groups on the surface of the biochar can be improved, and the adsorption capacity to heavy metals is improved. In addition, microwave heating activation can directly heat the inside of the biochar to obtain different pore structures and specific surface areas, and the method has the advantages of simplicity and practicability. The surface structure of the biochar can be changed by modifying the biochar through calcium chloride, so that the physical adsorption effect of the biochar surface is changed into the ion exchange effect, and the biochar has a more stable adsorption effect. Meanwhile, two methods (chemical activation and microwave activation) are adopted to increase the number of heavy metal zinc and cadmium adsorption sites and functional groups on the surface of the biochar and the surface area of the biochar, and a partial adsorption mode is changed, so that the adsorption and fixation capacity and stability of the biochar to heavy metal zinc and cadmium can be improved. Patent application No. CN 109401755A discloses a device for preventing and curing tumorThe straw biochar modification method for repairing the heavy metal contaminated soil adopts 30% sodium hydroxide for modification, and has better repairing effect on effective zinc and cadmium; patent application No. CN 108940203A discloses a preparation method and application of biochar for three gorges vegetation, and NaOH and H are adopted after carbon preparation2O2Method of combined modification of NH4The + -N ion has a strong adsorption power and is not verified against heavy metals. Application number CN 109110863A discloses a method for removing doxycycline in water by using a chemical activation/microwave digestion activation biochar material, mainly aiming at organic pollution and not relating to the field of heavy metal pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of multi-site activated and modified reed-triarrhena biological carbon. The specific technical scheme is as follows:
a preparation method of multi-site activated and modified reed-triarrhena biological carbon comprises the following steps: the method comprises the following steps:
(1) washing, drying and crushing reed-triarrhena sacchariflora biomass, adding the reed-triarrhena sacchariflora biomass into a manganite powder solution for immersion, fully and ultrasonically stirring and uniformly mixing, and performing low-temperature hydrothermal carbonization to prepare non-activated and modified charcoal;
(2) performing microwave activation on the biochar obtained in the step (1) in a calcium chloride-hydrogen peroxide mixed solution;
(3) and (3) carrying out ultraviolet radiation modification on the biochar obtained in the step (2) to obtain activated and modified biochar.
Further, in the step (1), the mass ratio of the reed to the triarrhena sacchariflora biomass is 3: 2, crushing to 1-2cm short rods, and sieving the manganite powder with a 100-mesh sieve, wherein the addition amount is 200 g/L; in the low-temperature hydrothermal carbonization process, the hydrothermal carbonization temperature is 180 ℃, and the hydrothermal carbonization time is 15 h.
Further, the step (2) comprises
(2.1) firstly, adding the biochar obtained in the step (1) into a calcium chloride-hydrogen peroxide mixed solution for soaking for 24 hours;
and (2.2) placing the biochar-calcium chloride-hydrogen peroxide mixture obtained in the step (2.1) in a microwave digestion furnace, performing microwave activation, and washing and drying the biochar after the microwave activation.
Further, the step (3) is to place the biochar prepared in the step (2) in an ultraviolet radiation test box for ultraviolet radiation modification, and finally obtain the activated and modified biochar.
Furthermore, the amount of the biochar added in each liter of the calcium chloride-hydrogen peroxide mixed solution is 100g, the mass concentration of the calcium chloride in the calcium chloride-hydrogen peroxide mixed solution is 50g/L, the mass concentration of the hydrogen peroxide in the calcium chloride-hydrogen peroxide mixed solution is 500g/L, and the concentration of the hydrogen peroxide in the calcium chloride-hydrogen peroxide mixed solution is 30%.
Further, the microwave power is set to be 2 watts per milliliter of mixed liquor, and the microwave activation time is 30 min;
further, the ultraviolet radiation adopts an ultraviolet lamp with the wavelength of 254nm, and the ultraviolet radiation intensity is 500 mu W/cm2The irradiation time was 36 hours.
Further, the application of the biochar prepared by the preparation method is that the prepared biochar is used for removing heavy metals of zinc and cadmium in water and soil.
Further, the removing method comprises the following steps: adding activated and modified biochar into heavy metal zinc and cadmium wastewater, carrying out adsorption reaction for a period of time, and then filtering or precipitating to separate and collect adsorbed biochar; or adding the biochar into the soil polluted by the heavy metals of zinc and cadmium, fully and uniformly mixing, and aging for a period of time to finish the bioremediation of the soil polluted by the heavy metals of zinc and cadmium.
Furthermore, the concentration of zinc and cadmium in the water body is controlled at 200-2000PPM and 5.0-100.0PPM, the pH is controlled at 2.0-10.0, and the temperature is controlled at 25 ℃.
Furthermore, the concentration of zinc in the soil is between 300-2000 PPM, and the concentration of cadmium in the soil is between 0.2-12 PPM.
Has the advantages that:
the cellulose and hemicellulose contents of the reed and the triarrhena sacchariflora selected by the invention are higher, the biochar prepared by pyrolysis has higher pH, and can easily form heavy metal precipitate when being applied to soil or water, thereby improving the stability of the passivation effect on heavy metal zinc and cadmium.
The biochar preparation method adopted by the invention adopts 180 ℃ low-temperature hydrothermal carbonization, the nanoparticles in the product are obvious, the nanoparticles are arranged in order, the aggregate form formed by the nanoparticles and the nano plate is presented, and the prepared biochar has the advantage of rich surface functional groups and better plays the adsorption role of heavy metal zinc and cadmium.
In the invention, the manganite is added in the hydrothermal carbonization process, has stronger adsorption and oxidation capacity, can be attached to the surface of the biochar, and improves the adsorption capacity to heavy metals; the manganite is alkaline and can be attached to the surface of the biochar to improve the pH value of the biochar and improve the precipitation effect on heavy metals.
The modification method adopted by the invention is physical and chemical modification. Firstly, raw materials are soaked in a mixed solution of calcium chloride and hydrogen peroxide, the surface structure of the biochar can be subjected to surface change through calcium chloride modification, calcium ions loaded on the surface of the biochar and heavy metal ions in water and soil have an ion exchange effect, and the stability of the biochar in heavy metal adsorption is stronger; the oxidant modification can introduce oxygen atoms on the surface of the biochar, and the oxygen content is increased, so that more oxygen-containing functional groups such as carboxyl and the like are more easily generated on the surface of the biochar.
After chemical modification, microwave activation is carried out to ensure that the surface functional groups of the activated carbon fully react with the modifying agent, so that dehydration and decarboxylation of the reed-triarrhena sacchariflora biomass-based biochar are carried out, the aromatizing degree of the biochar is improved, and the surface adsorption effect of the biochar on heavy metal zinc and cadmium can be enhanced; finally, the biological carbon material is radiated by ultraviolet, so that the quantity of oxygen-containing groups can be obviously improved, and the complexing effect of the biological carbon on heavy metals of zinc and cadmium can be enhanced.
The invention takes wetland plant reed-triarrhena sacchariflora biomass as raw material, has wide source and low production cost, and realizes the comprehensive utilization of resources; and the biochar is modified and activated in multiple directions, so that the adsorption performance of the biochar is greatly improved, the biochar is environment-friendly, and the biochar is suitable for removing heavy metals in natural ecological environment water or soil.
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FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples
Example 1
Example the adsorption of zinc and cadmium in solution by activated and modified biochar was analyzed in comparison to reed-triarrhena sacchariflora biomass biochar which was not activated and modified.
The preparation method of the biochar comprises the following steps:
1) washing, drying and crushing the soaked reed-triarrhena sacchariflora biomass, adding the dried and crushed soaked reed-triarrhena sacchariflora biomass into the manganite powder solution for immersion, fully and ultrasonically stirring and uniformly mixing, and carrying out low-temperature hydrothermal carbonization at the temperature of 180 ℃ for 15 hours to prepare the non-activated and modified charcoal;
2) adding 100g of unactivated and modified biochar into 1L of calcium chloride-hydrogen peroxide mixed solution for soaking, and fully reacting for 24 hours; the preparation method of the mixed solution of calcium chloride and hydrogen peroxide comprises the following steps: adding 500ml of pure water and 500ml of hydrogen peroxide into a container, then adding 50g of calcium chloride, fully and ultrasonically stirring and uniformly mixing, and controlling the temperature at room temperature;
3) placing the biochar mixed liquor obtained in the step (2) in a digestion tank, performing microwave activation, and cooling, wherein the microwave power is set to be 2 watts per milliliter of the mixed liquor, and the microwave activation time is 30 min; thoroughly washing the biomass with deionized water for multiple times, filtering, and drying at 75 ℃ to obtain microwave activated and modified biochar;
4) and (4) placing the biochar prepared in the step (3) in an ultraviolet radiation test box, irradiating by an ultraviolet radiation lamp with the wavelength of 254nm, carrying out ultraviolet radiation modification with the light intensity of the ultraviolet radiation being 500 mu W/cm2 and the irradiation time being 36 h, and obtaining the final activated modified biochar.
Adding the non-activated modified biochar and the activated modified biochar into the mixed solution of zinc and cadmium according to the concentration of 10mg/L, and preparing the mixed solution with the zinc concentration of 1000PPM and the cadmium concentration of 10 PPM. And (3) performing adsorption reaction for 24 hours, and measuring the concentrations of zinc and cadmium in the liquid to obtain that the adsorption rates of the unactivated modified biochar to zinc and cadmium are 74.8 percent and 82.1 percent, the adsorption rates of the activated modified biochar to zinc and cadmium in the solution are 85.2 percent and 97.7 percent, and the adsorption rate of the activated modified biochar is improved by 10.4 and 15.6 percent.
Example 2
Compared with reed-triarrhena sacchariflora biomass charcoal which is not subjected to activation modification, the activated and modified charcoal is analyzed to adsorb effective zinc and cadmium in the acidic red soil of the Guixi river, and the preparation steps of the charcoal are the same as those in the example 1.
Adding the non-activated modified biochar and the activated modified biochar into zinc and cadmium polluted soil of Guixi river according to the mass ratio of 1% (the pH value of the soil is 4.83, the total cadmium of the soil is 2.53PPM, and the total zinc is 80.81 PPM), fully mixing uniformly, and finishing bioremediation of heavy metal pollution of the soil after natural aging for 4 months. With 0.01 moL of CaCl2The solution is used for leaching the available Cd in the soil, and then the concentration of the Cd is measured by using a graphite furnace atomic absorption spectrometer, and the results are shown in Table 1 (cadmium) and Table 2 (zinc).
TABLE 1 effective cadmium and repair rate in soil before and after adding biochar into acidic red soil of Guixi river in Jiangxi
| Before aging | After aging | Rate of repair | |
| Non-activated modified biochar | 0.379±0.015 | 0.207±0.010 | 45.3% |
| Activated modified charcoal | 0.380±0.012 | 0.151±0.008 | 61.2% |
TABLE 2 effective zinc and restoration rate in soil before and after adding charcoal into acidic red soil of Jiangxi Guixi
| Before aging | After aging | Rate of repair | |
| Non-activated modified biochar | 10.023±0.021 | 1.663±0.013 | 83.4% |
| Activated modified charcoal | 10.018±0.019 | 0.441±0.009 | 95.6% |
Example 3
Compared with the reed-triarrhena sacchariflora biomass charcoal which is not subjected to activation modification, the activated and modified charcoal is analyzed to adsorb effective zinc and cadmium in soil benevolence of Guangdong, and the preparation steps of the charcoal are the same as those in example 1.
Adding the unactivated modified biochar and the activated modified biochar into zinc-cadmium polluted soil (the pH value of the soil is 5.52, the total cadmium of the soil is 3.93PPM, and the total zinc is 1160.37 PPM) benificated in Guangdong by the mass ratio of 1%, fully mixing uniformly, and naturally aging for 4 months to complete bioremediation of heavy metal pollution of the soil. With 0.01 moL of CaCl2The solution is used for leaching the available Cd in the soil, and then the concentration of the Cd is measured by a graphite furnace atomic absorption spectrometer, and the results are shown in tables 3 (cadmium) and 4 (zinc):
TABLE 3 effective cadmium in soil before and after adding biochar in Guangdong rensheng soil and restoring rate
| Before aging | After aging | Rate of repair | |
| Non-activated modified biochar | 0.442±0.011 | 0.220±0.011 | 50.3% |
| Activated modified charcoal | 0.441±0.015 | 0.175±0.010 | 60.4% |
TABLE 4 effective zinc in soil before and after addition of biochar in Guangdong benevolence soil and restoration rate
| Before aging | After aging | Rate of repair | |
| Non-activated modified biochar | 208.86±0.014 | 73.518±0.017 | 64.8% |
| Activated modified charcoal | 208.82±0.024 | 47.611±0.020 | 78.2% |
Example 4
And (3) carrying out adsorption analysis on the zinc and cadmium in the soil leachate by using the activated and modified charcoal.
The procedure for the preparation of biochar was the same as in example 1.
Adding activated and modified biochar into a soil sample (the pH value of the soil is 6.88, the total cadmium is 1.94PPM, and the total zinc is 926.14 PPM) uniformly applied to the soil in the paddy field of Yueyang in Hunan according to the mass ratio of 0.2%, keeping the soil humidity at the maximum field water holding capacity, and measuring the content of zinc and cadmium in leachate in the soil after reacting for 24 hours. The result shows that the cadmium content in the soil leachate is 0.0032mg/L, which is lower than the content limit value of 0.005mg/L in the Farmland irrigation Water quality Standard (GB 5084-2005).
Comparative example 1
In order to compare and understand the influence of ultraviolet radiation modification on adsorption and passivation of heavy metals by the biochar, the comparison example carries out comparison study on adsorption of heavy metals of zinc and cadmium on the biochar which is modified by ultraviolet radiation and is not modified by ultraviolet radiation, the preparation steps of the biochar are the same as example 1, except that whether the biochar prepared by the step (3) passes 254nm wavelength and has radiation intensity of 500 muW/cm2And the irradiation time is 36 h.
Adding biochar which is not modified by ultraviolet radiation and biochar which is modified by ultraviolet radiation into the mixed solution of zinc and cadmium according to the concentration of 10mg/L, and preparing the mixed solution with the zinc concentration of 1000PPM and the cadmium concentration of 10 PPM. And (3) performing adsorption reaction for 24 hours, and measuring the concentrations of zinc and cadmium in the liquid, and finding that the adsorption rate of the ultraviolet radiation modified biochar on heavy metals of zinc and cadmium in the water body is improved by 3.1% and 5.7% compared with the biochar which is not modified by ultraviolet radiation.
Although the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present patent within the knowledge of those skilled in the art.
Claims (9)
1. A preparation method of multi-position activated and modified reed-triarrhena biological carbon for removing zinc and cadmium in water or soil comprises the following steps: the method is characterized by comprising the following steps:
(1) washing, drying and crushing reed-triarrhena sacchariflora biomass, adding the reed-triarrhena sacchariflora biomass into a manganite powder solution for immersion, fully and ultrasonically stirring and uniformly mixing, and performing low-temperature hydrothermal carbonization to prepare unactivated and modified biochar, wherein the hydrothermal carbonization temperature in the hydrothermal carbonization process is 180 ℃, and the hydrothermal carbonization time is 15 hours;
(2) soaking the biochar obtained in the step (1) in a calcium chloride-hydrogen peroxide mixed solution for 24 hours, then performing microwave activation, and then washing and drying the biochar;
(3) and (3) carrying out ultraviolet radiation modification on the biochar obtained in the step (2) to obtain activated and modified biochar.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the reeds to the triarrhena sacchariflora biomass is 3: 2, crushing to 1-2cm short rods, and sieving the manganite powder with a 100-mesh sieve, wherein the addition amount is 200 g/L.
3. The method of claim 2, wherein: in the step (2), 100g of biochar is added per liter of calcium chloride-hydrogen peroxide mixed liquor, the mass concentration of calcium chloride in the calcium chloride-hydrogen peroxide mixed liquor is 50g/L, the mass concentration of hydrogen peroxide is 500g/L, and the concentration of hydrogen peroxide is 30%.
4. The method of claim 2, wherein: in the step (2), the power of the microwave activation is set to be 2 watts per milliliter of the mixed solution, and the microwave activation time is 30 min.
5. The method of claim 1, wherein: in the step (3), the ultraviolet radiation adopts an ultraviolet lamp with the wavelength of 254nm, and the ultraviolet radiation intensity is 500 mu W/cm2The irradiation time was 36 hours.
6. Use of biochar prepared by the method of any one of claims 1 to 5, wherein: the prepared activated and modified charcoal is used for removing heavy metals of zinc and cadmium in water or soil.
7. Use according to claim 6, characterized in that: the removing method comprises the following steps: adding activated and modified biochar into wastewater containing heavy metal zinc and cadmium, carrying out adsorption reaction for a period of time, and collecting the adsorbed biochar through filtration or precipitation separation to complete treatment of the heavy metal zinc and cadmium in the water body; or adding the biochar into the soil polluted by the heavy metals of zinc and cadmium, fully and uniformly mixing, and aging for a period of time to finish the bioremediation of the soil polluted by the heavy metals of zinc and cadmium.
8. Use according to claim 7, characterized in that: the concentration of zinc and cadmium in the water body is controlled at 200-2000PPM and 5.0-100.0PPM, the pH is controlled at 2.0-10.0, and the temperature is controlled at 25 ℃.
9. Use according to claim 7, characterized in that: the concentration of zinc in the soil is between 300-2000 PPM, and the concentration of cadmium in the soil is between 0.2-12 PPM.
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| CN109110863A (en) * | 2018-09-20 | 2019-01-01 | 湖南大学 | Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body |
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| CN105195093A (en) * | 2015-10-21 | 2015-12-30 | 四川大学 | Modified walnut shell active carbon adsorbent and preparation method thereof |
| CN106701091A (en) * | 2017-03-27 | 2017-05-24 | 江西省科学院生物资源研究所 | Preparation method of composite biomass improver for remedying heavy metal-polluted soil |
| CN106925222A (en) * | 2017-04-28 | 2017-07-07 | 安徽科技学院 | Hydrogen peroxide cooperates with raising charcoal oxy radical technique with ultraviolet irradiation |
| CN108148598A (en) * | 2017-12-12 | 2018-06-12 | 常州市雄泰纺织品有限公司 | A kind of heavy-metal contaminated soil passivator and preparation method thereof |
| CN109110863A (en) * | 2018-09-20 | 2019-01-01 | 湖南大学 | Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body |
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