CN114316991A - Iron-manganese composite carbon fiber material, preparation method thereof and soil remediation method - Google Patents
Iron-manganese composite carbon fiber material, preparation method thereof and soil remediation method Download PDFInfo
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Abstract
The invention belongs to the field of soil remediation, and particularly relates to a ferro-manganese composite carbon fiber material, a preparation method thereof and a soil remediation method. The iron-manganese composite carbon fiber material provided by the invention comprises a carbon fiber material, a Fe simple substance, iron oxide and manganese oxide, wherein the loading capacity of the Fe simple substance is 0.1-10 wt%, the loading capacity of the iron oxide is 3-30 wt%, and the loading capacity of the manganese oxide is 0.5-10 wt%. The iron-manganese composite carbon fiber material can realize the stabilizing or degrading effect on arsenic, thallium and/or organic pollutants by regulating and controlling the proportion; the material is simple in preparation process, the original solution in the preparation process can be repeatedly utilized, the preparation cost is low, the material can be prepared in batch, and the material has the effect of stably repairing the soil polluted by arsenic, thallium and/or organic pollutants as a soil repairing material, is environment-friendly and has better biocompatibility.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to a ferro-manganese composite carbon fiber material, a preparation method thereof and a soil remediation method.
Background
With the industrial activity and the farmland heavy metal pollution caused by mining, the farmland heavy metal pollution is gradually known to the public, and particularly frequent agricultural product safety events drive the comprehensive treatment of the farmland heavy metal pollution in China. Under the drive of policy documents such as 'soil pollution prevention and control law' and 'action plan for soil pollution prevention and control', the department of science and technology and the department of agricultural rural area respectively develop 'comprehensive prevention and control and repair technology research and development of agricultural non-point source and heavy metal pollution farmland' and 'prevention and control of heavy metal pollution of soil in agricultural product production areas of China', and China successively popularizes and forms repair and safe utilization technologies such as engineering measures, phytoremediation, chemical stabilization, agricultural regulation and control, alternative planting and the like aiming at farmland repair and treatment.
The remediation of farmland contaminated soil is very different from the field. Firstly, farmland soil pollutants are mainly concentrated in the range of 0-30 cm on the surface layer, but the distribution area is wide, and the traditional field restoration method is easy to generate overhigh economic cost. Secondly, the goal of remediation of contaminated farmlands is to restore normal production functions to the land. The farmland heavy metal pollution in China is various and complex, and different technologies have the defects of unstable effect, narrow application range, uncontrollable cost and the like when different types of soil are polluted.
Arsenic is one of the most common pollutants which cause the most serious harm to public health at present, is a trace element widely distributed in the nature, and is often applied to the production of industries such as pesticides, herbicides, insecticides, alloys and the like. Due to high background value of arsenic in soil, frequent mining activities of arsenic-containing mineral resources, excessive use of arsenic-containing agricultural preparations and the like, arsenic pollution in soil and crops in partial areas of China is serious.
Thallium is a rare-dispersing element and exists in sulfide ores such as iron and zinc in trace amount. Thallium-containing waste gas, waste water and waste residue enter the environment in the operation process of thallium-containing smelters, thermal power plants and various thallium-containing materials and medicament manufacturing plants, so that the thallium concentration in drinking water and irrigation water in parts of China is increased rapidly, and serious hidden dangers and threats are caused to human health.
At present, the organic pollution of soil in China is very common and serious, and according to statistics, the area of the soil polluted by pesticides in China exceeds 1300-1600 ten thousand hectares. Even if the organochlorine pesticide is forbidden in 1983, the residual quantity in the soil is greatly reduced compared with the prior art, but the detection rate is still high. According to the recent agricultural soil survey results of Nanjing soil institute of Chinese academy of sciences around a certain iron and steel group, the average value of the total amount of 15 Polycyclic Aromatic Hydrocarbons (PAHs) in the agricultural soil is 4.3mg/kg, mainly contains more than 4 rings of pollutants with carcinogenic effect, accounts for about 85% of the total content, and only 6% of sampling points are in safety level.
By combining the analysis, the farmland soil in many areas of China has the problem of composite pollution of heavy metal/metalloid-pesticide, heavy metal/metalloid-polycyclic aromatic hydrocarbon and the like.
The method mainly solves the two problems of the prior farmland composite pollution, namely the general lack of attention on the farmland soil with the composite pollution and the lack of an effective treatment mode, and mainly embodies that the farmland soil composite pollution cannot adopt the common restoration technology of the organic and inorganic composite pollution of the field like the farmland polluted soil, such as the technology of stabilization after thermal desorption, cement kiln cooperative treatment, stabilization after advanced oxidation, leaching and the like. Aiming at the special requirements that the physical and chemical properties of soil are not greatly changed and the using function of the soil is not changed in farmland restoration, a stabilization/passivation restoration technology is one of the common technologies and is often applied to restoration treatment of heavy metal/metalloid pollutants in the farmland.
For organic pollutants in the farmland, a biodegradation method is usually adopted, but few researches focus on the bioremediation or degradation process and action mechanism of soil under the condition of organic pollutants or heavy metal-organic matter combined pollution at present. Therefore, for coexisting pollutants existing in farmlands, such as metal/metalloid + herbicide/pesticide/refractory organic pollutants, a new way or technology is urgently needed to be found, and migration and enrichment of heavy metal/metalloid pollutants into plant fruit grains are reduced to the greatest extent possible.
Passivation repair is the main technique of popularization at present, and its technical advantage lies in its implementability and strong operability, and the effect is showing, and repair cycle is short simultaneously, can implement at reaping crop interval, does not influence grain production etc..
The key to the stabilization (passivation) repair technique is the selection of the stabilization (passivation) repair material.
Compared with other stabilized repair materials, the iron-based oxide has the advantages of high adsorption capacity, high arsenic adsorption kinetic rate and the like on the repair target object arsenic, is the most widely applied stabilizer in chemical stabilization at present, but still has the medicamentLarge dosage, insufficient stability, high engineering cost, secondary pollution and the like, and needs to be optimized and improved. The iron-manganese oxide has the advantages of high surface charge, large specific surface area, strong adsorption capacity, easy separation and the like, and can be widely used as an adsorption material for removing arsenic in water. The adsorption of iron manganese oxide surface to arsenic mainly belongs to inner layer specific adsorption, in the adsorption process, hydroxyl on the iron oxide surface and arsenic (III) generate ligand exchange and complex reaction of solid/liquid interface, but because iron oxide can not directly participate in oxidation, the adsorption capacity is limited; the manganese oxide has certain oxidation and adsorption capacity to arsenic, arsenic (III) is adsorbed on the surface of manganese oxide, the arsenic (III) on the surface can be oxidized into arsenic (V), and the arsenic (V) performs coordination reaction on the surface of the manganese oxide to form arsenic (V) -MnO2Bidentate dinuclear bridging complexes.
The ferro-manganese modified biochar material is applied to arsenic-polluted soil remediation and has a good effect, but the effect of the material on arsenic pollutants is only limited by oxidation and adsorption of ferro-manganese oxides, and the biochar material only serves as a carrier.
For arsenic pollution, the prior art generally adopts ferro-manganese modified materials to realize the stabilization and repair of arsenic. CN202010526972.X discloses a ferro-manganese modified coconut shell biochar material and a preparation method and application thereof, wherein soluble ferric salt and soluble permanganate are adopted to modify coconut shell biochar in an ultrasonic dispersion and high-temperature oxygen-isolation calcining manner, the calcined material is cooled, washed and dried to obtain the ferro-manganese modified coconut shell biochar material, and the ferro-manganese modified coconut shell biochar material can be used for efficiently passivating effective As in soil and effectively preventing and controlling the absorption and accumulation of As by paddy rice.
For thallium pollution, the application of the iron-based biochar has good thallium effect. Zhang Yu et al applied straw biochar, iron-based biochar and manganese-based biochar passivator to thallium-contaminated farmland soil in the study of thallium-contaminated soil passivation and remediation based on biochar materials, and the results show that the iron-based biochar has a good passivation effect on thallium in the farmland contaminated soil.
For organic pollution of farmland, the biological carbon can reduce the biological interest of organic pollutants in soil through adsorption and physical and chemical actionsDegree of use and leachability. The biochar prepared by utilizing agricultural wastes such as Zhang Xueyang and the like can achieve a good removing effect on three common volatile gas organic pollutants (acetone, cyclohexane and toluene) in soil. In the research on the combined pollution passivation and restoration effect of cadmium and atrazine in farmland soil, by adding sepiolite and a biochar passivation material into Cd and organic combined pollution farmlands thereof, Qinhua and the like, the Cd and the atrazine in the soil can be fixed and passivated by the modes of large specific surface area adsorption, group coordination, pH rise and the like, so that the biological effectiveness of the Cd and the atrazine is obviously reduced. In order to treat organic pollution of farmlands, researches on bioremediation technologies, such as phytoremediation technologies and microbial remediation technologies, which are usually adopted in addition to chemical stabilization technologies, have been applied to environmental remediation of organic pollutants. After being absorbed by plants, organic pollutants can be stored in new tissues through lignification and can be mineralized or metabolized into H2O and CO2It can also be volatilized or converted into intermediate metabolite without toxic effect by plant. Enzymes released by plants into the environment, such as dehalogenase, peroxidase, laccase, dehydrogenase and the like, can degrade organic pollutants which are difficult to degrade by bacteria, such as trinitrotoluene (TNT), trichloroethylene, PAHs, polychlorinated biphenyl (PCBs) and the like.
In conclusion, the high-purity iron and manganese materials are added into a large-area farm land at a low dosage, so that certain construction difficulty is caused; when the adding amount is increased, the permanganate has darker color, so that the soil is discolored to cause sensory discomfort, and the color reaction is obvious; when the iron-based material is applied, soil acidification is easy to occur, the soil physicochemical properties such as soil loosening degree, aggregate structure, soil salinization degree and the like are easily negatively affected, agricultural product planting is affected, and unnecessary raw material resource consumption and carbon emission are caused. Moreover, compared with materials such as ferro-manganese modified biochar, ferro-manganese modified clay mineral materials and the like, the ferro-manganese material or the iron-based material has limited effect on organic pollution; in the prior art, materials with high surface activity or specific surface area and pore channel structure, such as biochar, clay ore and the like, are selected as much as possible, and ferro-manganese is loaded on the materials in various modes, but the main functions of the biochar and the clay mineral materials are only to provide ferro-manganese loading media with certain specific surface area and pore channel structure and the like, and no other additional value is provided. And the existing ferro-manganese modification method is generally prone to a high-temperature calcination mode, belongs to a high-energy consumption mode, is a material production mode which is not easily accepted by the society from the viewpoint of environmental protection and carbon emission reduction, and is not easily popularized in large-scale preparation. The existing ferro-manganese modified biochar and ferro-manganese modified clay mineral materials are not applied to arsenic, thallium and organic pollutant combined polluted soil and have no report on the effect of the arsenic, thallium and organic pollutant combined polluted soil on organic pollutants.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a fe-mn composite carbon fiber material, a preparation method thereof, and a soil remediation method, and the fe-mn composite carbon fiber material provided by the present invention has the effects of stabilizing (passivating) and remediating arsenic and thallium, and synergistically degrading organic pollutants.
The invention provides a ferro-manganese composite carbon fiber material, which comprises the following components:
a carbon fiber material;
fe simple substance, iron oxide and manganese oxide loaded on the carbon fiber material;
the loading amount of the Fe simple substance is 0.1-10 wt%;
the loading amount of the iron oxide is 3-30 wt%;
the loading amount of the manganese oxide is 0.5-10 wt%.
The invention takes the carbon fiber material as the main material, has no special limitation on the type and the source of the carbon fiber material, adopts the carbon fiber material which is well known by the technical personnel in the field, and can be purchased and obtained from the market; for example, the carbon felt material is used as an environment-friendly material, has good mechanical property and conductivity, has the characteristics of strong oxidation resistance, high temperature resistance, corrosion resistance and the like, has good environmental stability, has a very small specific surface and has no special pore structure. The carbon felt material is added into soil as a carrier material, is environment-friendly, has better biocompatibility, can improve the physical and chemical properties of the soil, increases the soil loosening degree, is beneficial to the formation of aggregates, increases the permeability and the air permeability of the soil, is beneficial to the growth of aerobic microorganisms in the soil, improves the oxidation-reduction potential of the soil, increases the species and the quantity of the microorganisms in the soil, and realizes the stabilization/passivation of arsenic and thallium through additional values.
The length of the carbon fiber-containing material is less than 3 mm.
The iron-manganese composite carbon fiber material provided by the invention is loaded with Fe simple substance, iron oxide and manganese oxide. Wherein the loading amount of the Fe simple substance is 0.1-10 wt%, preferably 1-5 wt%, more preferably 1.29-4.35 wt%, and most preferably 4.35 wt%; the Fe simple substance loaded on the carbon fiber material can form a tiny primary battery with the carbon fiber material, and the carbon fiber material has good conductivity and can promote electron transfer, so that the Fe simple substance loaded on the carbon fiber material can quickly capture pollutants with charges and can jointly degrade organic pollutants dissolved in soil pore water with high-valence manganese oxide.
In one embodiment, the loading amount of the iron oxide is 3 to 30 wt%, preferably 5 to 29 wt%, and more preferably 5.94 to 28.43 wt%. Hydroxyl on the surface of the iron oxide and arsenic (III) can generate ligand exchange and complex reaction on a solid/liquid interface, and the iron oxide has the advantages of high adsorption capacity, high adsorption kinetic rate and the like on the arsenic.
In one embodiment, the loading amount of the manganese oxide is 0.5 to 10 wt%, preferably 1 to 6 wt%, and more preferably 1.01 to 5.60 wt%. The manganese oxide has certain oxidation and adsorption capacity to arsenic, arsenic (III) adsorbed on the surface of the manganese oxide can be oxidized into arsenic (V), and the arsenic (V) performs coordination reaction on the surface of the manganese oxide to form arsenic (V) -MnO2Bidentate dinuclear bridging complexes.
In fact, in the iron-manganese composite carbon fiber material provided by the invention, the Fe simple substance is loaded on the carbon fiber material, one part of the iron oxide is deposited on the Fe simple substance, and the other part of the iron oxide is loaded on the carbon fiber material; one part of manganese oxide is deposited on the Fe simple substance, and the other part of manganese oxide is loaded on the carbon fiber material. According to the invention, the carbon fiber material can be locally loaded with Fe simple substance, iron oxide and manganese oxide, and for the carbon fiber material area locally loaded with Fe simple substance, the Fe simple substance on the carbon fiber material can be oxidized except for self passivation in the dipping process, so that an iron (III)/(II) oxide active intermediate is continuously generated, and then an iron-manganese oxide deposition layer is further generated on the surface to form a laminated structure. Wherein the iron manganese oxide comprises iron oxide and manganese oxide. Due to the existence of Fe simple substance, the loading amount of the iron oxide and the manganese oxide in the local carbon fiber material is higher, thereby being more beneficial to the removal of pollutants.
The invention provides a preparation method of the iron-manganese composite carbon fiber material, which comprises the following steps:
carrying out electrodeposition on a carbon fiber material in a ferrous salt solution to obtain a carbon fiber material loaded with a Fe simple substance;
and soaking the carbon fiber material loaded with the Fe simple substance in a ferric iron salt and permanganate solution, and performing heat treatment to obtain the carbon fiber material loaded with the Fe simple substance, the iron oxide and the manganese oxide.
Firstly, depositing Fe simple substance on the surface of the carbon fiber material to obtain the carbon fiber material loaded with the Fe simple substance. Specifically, the deposition method is as follows:
and (3) respectively taking the carbon fiber material as an anode and a cathode, placing the carbon fiber material in a ferrous salt solution, performing electrodeposition, and forming Fe simple substance on the carbon fiber material of the cathode by ferrous ions under the action of voltage.
In one embodiment, the concentration of the ferrous salt solution is 0.1-0.5 mol/L, preferably 0.5 mol/L; the specific parameters of the electrodeposition are as follows: the electrified voltage is 6-12V, the electrified time is 10-60 min, and the electrified current is 0.1-0.5A.
In one embodiment, the ferrous salt is one or more of ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous citrate, ferrous acetate, and ferrous lactate, preferably one or more of ferrous citrate, ferrous gluconate, ferrous acetate, and ferrous lactate.
After the carbon fiber material loaded with the Fe simple substance is obtained, carrying out loading of the iron-manganese oxide on the carbon fiber material, specifically, the loading method comprises the following steps:
and soaking the carbon fiber material loaded with the Fe simple substance in a ferric iron salt and permanganate solution, and performing heat treatment to obtain the carbon-containing fiber loaded with the Fe simple substance, the iron oxide and the manganese oxide.
The method comprises the steps of firstly soaking and heat treating the carbon fiber material loaded with the Fe simple substance in a trivalent ferric salt and permanganate solution to load iron oxide and manganese oxide on the carbon fiber material.
In one embodiment, the concentration of the ferric salt is 0.1-1 mol/L, and preferably 0.5 mol/L.
In one embodiment, the ferric salt is one or more of ferric sulfate, ferric chloride, ferric nitrate and ferric citrate and ferric acetate, preferably ferric chloride.
In one embodiment, the concentration of the permanganate is 0.1-1 mol, preferably 0.5 mol/L;
in one embodiment, the permanganate salt is one or more of sodium permanganate, potassium permanganate, magnesium permanganate, preferably sodium permanganate.
In one embodiment, the solid-to-liquid ratio of the Fe-simple-substance-loaded carbon fiber material to the trivalent ferric salt and the permanganate solution is 1: 10-50, preferably 1: 10; the molar ratio of the trivalent ferric salt to the permanganate is 2-3: 1.
In one embodiment, the heat treatment is heating in a water bath, wherein the temperature of the water bath is 90-100 ℃; the time of the water bath is more than 2 hours, preferably 2 to 8 hours, and more preferably 4 hours. In one embodiment, the heat treatment is carried out under the condition of stirring, and the stirring speed is 100-150 r/min.
Before the heat treatment, the dipped product can also be subjected to ultrasonic vibration;
in one embodiment, the time of the ultrasonic oscillation is 10min or more, preferably 10-30 min.
After the heat treatment, the method also comprises the steps of drying and crushing the product.
In one embodiment, the product is comminuted to a length of less than 3 mm.
According to the invention, the Fe simple substance is loaded on the carbon fiber material, and then the oxide is loaded, so that the oxide can be loaded on the Fe simple substance, and the material with high oxide loading capacity in a local area is obtained.
In one embodiment, the local area iron loading of the iron-manganese composite carbon fiber material can reach 50.62 wt%, and the local area manganese loading can reach 9.62 wt%; thereby increasing the remediation effect on the soil.
The iron-manganese composite carbon fiber material can be used for removing one or more of arsenic, thallium and organic pollutants.
The invention provides a soil remediation method, which comprises the following steps:
and mixing the iron-manganese composite carbon fiber material with soil.
In one embodiment, the addition amount of the iron-manganese composite carbon fiber material in soil is 0.1-1%.
The invention provides a ferro-manganese composite carbon fiber material, which comprises the following components: a carbon fiber material; elemental Fe, iron oxide, and manganese oxide supported on the carbonaceous fibrous material; the loading amount of the Fe simple substance is 0.1-10 wt%; the loading amount of the iron oxide is 3-30 wt%; the loading amount of the manganese oxide is 0.5-10 wt%. The carbon fiber material is loaded with the Fe simple substance, the iron oxide and the manganese oxide, has good removal effect on arsenic, thallium and/or organic pollutants, and can be used for the stabilization and restoration of arsenic, thallium and/or organic pollutant composite polluted soil. Experimental results show that when the arsenic-thallium-doped organic pollutant-based soil remediation material is used for stabilizing arsenic, thallium and/or organic pollutant combined contaminated soil, the reduction rate of arsenic reaches 51.47%, the reduction rate of thallium reaches 83.9%, and the reduction rate of organic pollutants reaches 69.2%, which is superior to the level of the prior art.
Furthermore, the preparation method provided by the invention has simple process, and the original solution can be repeatedly utilized in the preparation process; the preparation cost is low, the preparation can be carried out in batch, and the method has an industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a scanning electron microscope image of a ferro-manganese composite carbon fiber material;
FIG. 2 is a diagram of the energy spectrum analysis of a ferro-manganese composite carbon fiber material;
fig. 3 is a diagram of energy spectrum analysis of the iron-manganese composite carbon fiber material in the cross-marked area of fig. 2.
Detailed Description
The invention discloses a ferro-manganese composite carbon fiber material, a preparation method thereof and a soil remediation method. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
Placing two 10cm × 10cm carbon fiber materials as an anode and a cathode respectively in 0.1mol/L ferrous sulfate solution for electrodeposition, wherein the output voltage is 6V, and the electrifying time is 30min to obtain the carbon fiber material loaded with the Fe simple substance; and (3) dipping the carbon felt which is connected with the cathode and loaded with the Fe simple substance in 200mL of 1mol/L ferric chloride and 0.5mol/L potassium permanganate solution, ultrasonically dispersing for 30min, heating in a constant-temperature water bath at 95 ℃ for 4h, taking out, drying, and crushing to the length of less than 3mm to obtain the iron-manganese composite carbon fiber material.
Scanning electron microscope analysis and characterization are carried out on the obtained iron-manganese composite carbon fiber material, the result is shown in figure 1, figure 1 is a scanning electron microscope image of the iron-manganese composite carbon fiber material, a rod-shaped carbon fiber material can be clearly seen in the figure, and the surface of the carbon fiber material is covered with flaky and layered iron-manganese oxides;
performing energy spectrum analysis on the obtained iron-manganese composite carbon fiber material, and referring to the figure 2, the figure 3 and the table 1 as the result, wherein the figure 2 is an energy spectrum analysis diagram of the iron-manganese composite carbon fiber material; the cross marked area in the figure is a corresponding area for analyzing the composition of the energy spectrum elements; FIG. 3 is a graph of an energy spectrum analysis of the FeMn composite carbonaceous fibrous material in the cross-marked area of FIG. 2; table 1 is the results of elemental quantitative analysis for energy spectral analysis of the cross-marked region:
table 1: quantitative analysis result of energy spectrum analysis element of cross mark area
As can be seen from fig. 2, fig. 3 and table 1, the main constituent elements of the obtained Fe-Mn composite carbon-containing fiber are carbon (C), chlorine (Cl), potassium (K), manganese (Mn) and iron (Fe), and the mass percentages thereof are respectively: 30.27%, 30.04%, 3.67%, 9.62% and 26.40%.
Example 2
The difference from example 1 is that the mixture is heated in a thermostatic water bath at 95 ℃ for 8 h.
Comparative example 1
Putting 3.36g of biochar into a corundum crucible, respectively adding 40mL of potassium permanganate with the concentration of 0.18mol/L and 40mL of ferric nitrate with the concentration of 0.06mol/L, uniformly mixing, performing ultrasonic treatment for 2 hours, uniformly stirring, and evaporating to dryness in a constant-temperature water bath at 95 ℃; then put into a muffle furnace with the flow rate of 600cm3And (3) carrying out anaerobic pyrolysis for 0.5h at 600 ℃ by using nitrogen gas/min as protective gas, cooling to room temperature, and taking out to obtain the biochar-iron-manganese oxide composite material.
Example 3: example 1 the material prepared
Taking soil polluted by some As and Tl in Guangdong As an example, the concentration of the effective As is 0.564mg/kg, the concentration of the Tl is 1.18 mu g/L, the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) is 0.107mg/kg, and the pH value of the soil is 6.20.
And (2) air-drying and uniformly mixing the soil, uniformly dividing the mixture into 100g of each part, adding a repairing material accounting for 0.5 wt% of the dry weight of the soil, uniformly stirring, adding water, and maintaining to ensure that the water content of the soil is 30%. And (5) curing for 3 days, then air-drying, and detecting the concentration and pH value of each pollution index in the soil.
For the determination of the effective As concentration, pretreating a sample to be detected according to DB 31/T661-2012, pretreating the sample to be detected by adopting HJ/T299-2007 for the determination of Tl concentration, and then respectively determining by adopting ICP-MS; the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) was determined from HJ 805-2016.
Table 2 compares the repair effect of the inventive material with the prior art material. Wherein, the comparative example 2 is that FeCl with the ratio of 2:1 is directly added3And KMnO4。
Table 2: the repairing effect of the material of the invention is compared with that of the material of the prior art
As can be seen from table 2, the remediation materials of examples 1 and 2 had better effects on available arsenic, thallium, and polycyclic aromatic hydrocarbons in soil. Compared with the commercial biochar and the comparative example 2, the repair materials of the example 1 and the example 2 have larger improvement on the degradation rate of arsenic, thallium and polycyclic aromatic hydrocarbon, wherein the improvement on the degradation rate of thallium and polycyclic aromatic hydrocarbon is particularly obvious. In example 1, the longer the time of heating in the water bath, the more favorable the degradation of arsenic and the less favorable the degradation of thallium than in example 2, but the less favorable the degradation of polycyclic aromatic hydrocarbons, so that the time of heating in the water bath needs to be controlled within a suitable range.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A ferro-manganese composite carbon fiber comprising:
a carbon fiber material;
fe simple substance, iron oxide and manganese oxide loaded on the carbon fiber material;
the loading amount of the Fe simple substance is 0.1-10 wt%;
the loading amount of the iron oxide is 3-30 wt%;
the loading amount of the manganese oxide is 0.5-10 wt%.
2. The ferro-manganese composite carbon fiber material according to claim 1,
the load capacity of the Fe simple substance is 1-5 wt%;
the load capacity of the iron oxide is 5-29 wt%;
the loading amount of the manganese oxide is 1-6 wt%.
3. A method of preparing a material according to claim 1 or 2, comprising the steps of:
carrying out electrodeposition on a carbon fiber material in a ferrous salt solution to obtain a carbon fiber material loaded with a Fe simple substance;
and soaking the carbon fiber material loaded with the Fe simple substance in a ferric iron salt and permanganate solution, and performing heat treatment to obtain the carbon fiber material loaded with the Fe simple substance, the iron oxide and the manganese oxide.
4. The method for preparing the material according to claim 3, wherein the ferrous salt is one or more of ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous citrate, ferrous gluconate, ferrous acetate and ferrous lactate.
5. The method of claim 3, wherein the ferric salt is one or more of ferric sulfate, ferric chloride, ferric nitrate, ferric citrate, and ferric acetate.
6. The method of claim 3, wherein the permanganate salt is one or more of sodium permanganate, potassium permanganate, and magnesium permanganate.
7. The preparation method according to claim 3, wherein the molar ratio of the trivalent iron salt to the permanganate is 2-3: 1.
8. Use of a ferro-manganese composite carbon fibre material according to claim 1 or 2 for the removal of arsenic, thallium and/or organic contaminants.
9. A method of soil remediation comprising the steps of:
mixing the iron-manganese composite carbon fiber material according to claim 1 or 2 with soil.
10. The soil remediation method of claim 9, wherein the iron-manganese composite carbon fiber material is added to the soil in an amount of 0.1 to 1 wt%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| WO2016058228A1 (en) * | 2014-10-13 | 2016-04-21 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based biochar material, preparation process therefor and use thereof in soil pollution treatment |
| CN112958036A (en) * | 2021-02-02 | 2021-06-15 | 暨南大学 | Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof |
| CN113426454A (en) * | 2021-06-03 | 2021-09-24 | 华中科技大学 | Three-dimensional porous graphene loaded nano zero-valent iron/manganese oxide composite material and preparation method and application thereof |
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2021
- 2021-12-31 CN CN202111676010.3A patent/CN114316991A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016058228A1 (en) * | 2014-10-13 | 2016-04-21 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron-based biochar material, preparation process therefor and use thereof in soil pollution treatment |
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| CN112958036A (en) * | 2021-02-02 | 2021-06-15 | 暨南大学 | Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof |
| CN113426454A (en) * | 2021-06-03 | 2021-09-24 | 华中科技大学 | Three-dimensional porous graphene loaded nano zero-valent iron/manganese oxide composite material and preparation method and application thereof |
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