CN114272896A - Preparation and application of iron-based biochar for removing hexavalent chromium and dye through mediated oxalic acid - Google Patents
Preparation and application of iron-based biochar for removing hexavalent chromium and dye through mediated oxalic acid Download PDFInfo
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Abstract
The invention relates to preparation and application of iron-based biochar for removing hexavalent chromium and dye through mediating oxalic acid, and belongs to the technical field of environmental materials. The invention is characterized in that (1) natural iron-containing minerals and biomass are crushed and ground into powder, and the powder is respectively sieved by 325-mesh sieve and 70-mesh sieve, and then is stored in a dry environment; (2) and (3) mixing the sieved natural iron-containing minerals and biomass according to a mass ratio of 1:2, uniformly mixing; (3) and placing the mixed substance in inert gas, roasting for 2h at a certain temperature, cooling to room temperature, taking out nitrogen and storing to obtain the iron-based biological carbon material. The obtained material can efficiently mediate oxalic acid to remove the Cr (VI) in the water body to 98 percent, and the Methylene Blue (MB) to 100 percent, and has the characteristics of high efficiency, wide pH adaptation, no secondary pollution and the like. The novel iron-based biochar has wide source and low price, can be prepared in a large scale, and has wide application prospect in treating wastewater containing Cr (VI) and MB.
Description
Technical Field
The invention belongs to the field of environment functional materials, and relates to preparation and application of iron-based biochar for removing hexavalent chromium and dyes through mediated oxalic acid.
Background
With the continuous development of modern textile, leather, medicine and other industries, the discharged wastewater contains various pollutants including some metal cations, organic dyes and the like. If not properly handled, serious harm can be caused to human health and the natural environment. Chromium and methylene blue are taken as representatives, chromium is a common toxic trace metal, chromium in a water body mainly exists in the forms of hexavalent chromium (Cr (VI)) and trivalent chromium (Cr (III)), and the hexavalent chromium (Cr (VI)) is taken as a form with higher oxidation degree, has higher mobility and toxicity in the environment than the trivalent chromium (Cr (III)), is more than one hundred times of the toxicity, and has larger harm to human beings and ecological systems. Dyes and chromium are usually present together in industrial waste water, and Methylene Blue (MB) is a cationic dye commonly used to dye wool, cotton and silk. Prolonged exposure to MB can lead to hypertension, shock, nausea, anemia, red blood cell failure, serotonin syndrome, tissue necrosis, jaundice, and the like.
The methods for simultaneously removing Cr (VI) and dye mainly include biological methods, adsorption methods, photochemical methods, etc., however, biological removal has certain limitations such as low chemical and heat resistance. Photochemical methods require complex operations and equipment. Therefore, the simultaneous removal of cr (vi) and dyes from wastewater remains a great challenge.
In recent years, people pay more and more attention to solving environmental problems by using a sustainable development mode, and the biochar is widely concerned in the aspect of water treatment as a green and environment-friendly low-cost material and is often used as an adsorbent for removing heavy metals and dyes. Due to its small specific surface area, it is difficult to separate heavy metals and dyes after adsorption, and is often limited in industrial applications. Various physical, chemical, mineral impregnation and magnetic methods are used to modify the biochar. The biochar/iron composite material has multiple functions of adsorption, reduction, complexation and the like. Researches show that the biochar/ferric oxide composite material remarkably enhances the adsorption capacity of arsenic. Many low cost metal oxides have been added to composite adsorbents for the treatment of various contaminants. In the biochar/metal oxide composite material, the biochar serves as a porous carbon body modified by the surface of the metal oxide, and the surface area of the biochar can be effectively increased. In the aspect of processing cationic dyes, the adsorption effect is effectively improved due to the electrostatic interaction.
Oxalic Acid (OA) is commonly discharged in industrial wastewater along with heavy metals and dyes. Interestingly, the carboxyl groups in OA can expand the coordination number of cr (vi) to drive the reduction process, which is thermodynamically feasible, but the reduction process is slow. Therefore, researchers mediate the reduction of Cr (VI) by oxalic acid through adding goethite, alumina and clay minerals, but the treatment time is still longer. Other studies have shown that under the influence of light, mediators convert OA into a reducing radical (. CO) within a few hours2 -) But must provide illumination.
Therefore, the development of an environment material which is low in cost, simple in preparation and capable of being prepared in a large scale to mediate the oxalic acid to remove heavy metals and dyes in a short time has important practical application significance.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide an iron-based biochar mediating oxalic acid to remove hexavalent chromium and dyes.
The invention also aims to provide a preparation method of the iron-based biochar for mediating the removal of hexavalent chromium and dyes by oxalic acid.
Still another object of the present invention is to provide an application of iron-based biochar mediating the removal of hexavalent chromium and dyes by oxalic acid.
The preparation and application of the iron-based biochar for removing hexavalent chromium and dye by mediating oxalic acid comprise the following steps:
(1) the natural biomass and the iron-containing minerals are used as raw materials, and are dried, crushed, sieved and stored in a dry environment;
(2) grinding the screened biomass and the iron-containing minerals in a mortar according to different proportions, and uniformly mixing;
(3) and placing the mixed material in inert gas, roasting for 2 hours at a certain temperature, cooling to room temperature, and taking out nitrogen for storage.
(4) In a preferred embodiment of the present invention, the biomass used in step (1) is sieved with a 70-mesh sieve, and the natural iron-containing mineral is sieved with a 300-mesh sieve.
(5) As one of the preferable modes of the invention, the biomass and the iron-containing mineral used in the step (2) are respectively prepared by mixing 1:1,1: 2,2: 1,1: 3,3: 1 proportion for mixing and grinding.
(6) In a preferred embodiment of the present invention, the iron-based biochar in step (3) is obtained by calcining in a tube furnace at 500, 700, and 900 ℃ for two hours at an inert gas flow rate of 1.5L/min and a temperature rise rate of 10 ℃/min, cooling to room temperature, and introducing nitrogen gas for storage.
(7) As one of the preferable modes of the present invention, the iron-based biochar is applied to water bodies polluted by cr (vi) and dyes.
Due to the adoption of the scheme, the invention has the beneficial effects that:
1. the raw materials for preparing the product are biomass and iron-containing minerals, the price is low, the source is wide, the preparation method is simple and feasible, and large-scale industrial production is easy to realize;
2. the iron-based biochar prepared by the invention has the characteristics of high efficiency, high stability, wide pH adaptation, no secondary pollution and the like when mediating oxalic acid to remove hexavalent chromium and dyes, and has a very obvious repairing effect on wastewater containing heavy metal hexavalent chromium and dyes.
Drawings
FIG. 1 is a scanning electron micrograph of a natural siderite in example 1 of the present invention (a is a natural siderite, b is a biochar, and c-j are iron-based biochar under different thermal modification conditions);
FIG. 2 is EDS-mapping diagram of iron-based biochar in example 2 of the present invention (diagram A is before material reaction, diagram B is after material-mediated oxalic acid reaction with Cr (VI) and MB);
FIG. 3 is an XRD pattern of iron-based biochar of example 3 of the present invention;
FIG. 4 is a graph of the effect of iron-based biochar mediated oxalic acid on Cr (VI) and MB removal at different pH's of example 4 of the present invention;
FIG. 5 is a graph showing the effect of different initial material concentrations and oxalic acid concentrations on the efficient removal of Cr (VI) and MB by Fe-based biochar-mediated oxalic acid at different reaction times in example 5 of the present invention.
Detailed Description
The following examples of the present invention will be described in detail, and the present invention is implemented on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation and application of the iron-based biochar for mediating oxalic acid to remove hexavalent chromium and dye in the embodiment comprises the following steps:
(1) the biomass such as natural bagasse, straws and the like and iron-containing minerals are used as raw materials, and are dried, crushed, sieved and stored in a dry environment;
(2) grinding the screened biomass and the iron-containing minerals in a mortar according to different proportions, and uniformly mixing;
(3) and placing the mixed material in argon gas, roasting for 2 hours at a certain temperature, cooling to room temperature, and taking out nitrogen for storage.
Further, the biomass used in the step (1) is sieved by a 70-mesh sieve, and the natural iron-containing minerals are sieved by a 300-mesh sieve.
Further, the biomass and the iron-containing minerals used in the step (2) are respectively mixed according to the ratio of 1:1,1: 2,2: 1,1: 3,3: 1 proportion for mixing and grinding.
Further, the iron-based biochar in the step (3) is obtained by calcining in a tube furnace at 500, 700 and 900 ℃ for two hours at the flow velocity of argon gas flow of 1.5L/min and the heating rate of 10 ℃/min, cooling to room temperature, and introducing nitrogen for storage.
As shown in fig. 1, (a) is a topography of natural siderite, (b) is a topography after bagasse pyrolysis, (c-i) is a topography of iron-based biochar pyrolyzed under different conditions, and (j) is a topography after Fe @ BC ═ 1:2-700 ℃ mediated oxalic acid removal of Cr (VI) and dye. The biomass forms a lamellar porous carbon material after pyrolysis, and after natural minerals are added and pyrolyzed together, the iron-based material is uniformly dispersed on the surface of the biochar, so that reduction of hexavalent chromium and adsorption removal of dyes are facilitated.
Example 2
This example illustrates the morphological characterization of iron-based biochar.
Fig. 2A and B are EDS-mapping diagrams before and after iron-based biochar (Fe @ BC ═ 1:2-700 ℃) mediates the removal of cr (vi) and MB by oxalic acid, and the results of comparing the surface element distribution before and after the material reaction indicate that trace amounts of nitrogen, sulfur and chromium element distribution exist on the surface of the material after the reaction, which indicates that the material has the performance of adsorbing chromium and dye during the reaction process.
Example 3
This example illustrates XRD analysis of iron-based biochar
Fig. 3(a, b) are XRD charts of iron-based biochar with different mixture ratios and different calcination temperatures, respectively. Siderite at 700 ℃ calcination conditions as shown in figure (a): the bagasse (Fe @ BC) ═ 1:1 material contains magnetite (Fe)3O4) Wurtzite (FeO) and zero-valent iron (Fe)0). The material containing Fe @ BC ═ 1:2 contains magnetite (Fe)3O4) And zero-valent iron (Fe)0). The materials Fe @ BC ═ 2:1, Fe @ BC ═ 1:3, and Fe @ BC ═ 3:1 contain wurtzite (FeO). Fe @ BC ═ 1:1 and Fe @ BC ═ 1:2 zero valent iron appears, which will favor the reduction of cr (vi). As shown in the figure (a), the material containing magnetite (Fe) under the calcination condition of 500 ℃ at Fe @ BC ═ 1:23O4) While Fe @ BC ═ 1:2 under the calcination condition of 900 ℃ mainly contains only zero-valent iron, because the temperature is too high and the biomass carbonization degree is high, the iron is completely reduced.
Example 4
This example illustrates the effect of iron-based biochar-mediated oxalic acid on cr (vi) and MB removal at different initial pH conditions.
As shown in fig. 4, the amount of iron-based biochar added was 1.5g/L and oxalic acid was 4mM, with Fe @ BC ═ 1: 2. At the pH values of 1.68, 4, 6, 8 and 10, at 90min, the removal rate of Cr (VI) is 100%, 99.3%, 98.8%, 92% and 92%, and the removal rate of the corresponding dye MB is 100%, the removal rate of Cr (VI) is increased along with the reduction of the pH value, and the removal efficiency of Cr (VI) and the dye can be obviously accelerated under the acidic condition. In general, the iron-based biochar can maintain ideal removal effects on Cr (VI) and MB under different pH conditions, the pH application range is wide, but the iron-based biochar is more obvious under acidic conditions.
Example 5
This example illustrates the effect of iron-based biochar-mediated oxalic acid on cr (vi) and MB removal at different initial "material concentrations" and "oxalic acid concentrations" at different reaction times.
As shown in FIG. 5(a, b), the material addition concentrations were 0.5, 1, 1.5 and 2g/L, the oxalic acid concentration was 4mM, the initial Cr (VI) concentration was 40mg/L, the initial MB concentration was 5mg/L, and the removal rates of Cr (VI) and MB were 51, 91.6, 98.2 and 97%, respectively, and 69, 98, 99.6 and 99.8% respectively at 90 min. The increased material concentration provides more redox sites for the reduction of cr (vi) by oxalic acid and the generation of free radicals for MB removal, and more iron-based biochar material also facilitates the adsorption removal of MB.
As shown in FIG. 5(c, d), at oxalic acid concentrations of 2, 4, 5, 6 and 8mM, respectively, the material-mediated removal efficiencies for Cr (VI) by oxalic acid were 55.6, 98, 97.7, 97.7 and 97.5%, respectively, and the removal efficiencies for MB were all 100% at 90 min. The oxalic acid is mainly used as an electron donor and can react with the iron-based biochar, so that electrons of the oxalic acid are transferred to Cr (VI) through materials to mediate reduction of the Cr (VI). The removal rate of Cr (VI) is not improved along with the increase of the concentration of oxalic acid, which indicates that the binding sites of the iron-based biochar and the oxalic acid are saturated, and more oxalic acid cannot directly react with Cr (VI) and the dye.
Claims (5)
1. Preparation and application of iron-based biochar for removing hexavalent chromium and dye by mediating oxalic acid are characterized by comprising the following steps:
(1) biomass such as natural bagasse, straws and the like and iron-containing minerals are used as raw materials, and are dried, crushed, sieved and stored in a dry environment;
(2) grinding the screened biomass and the iron-containing minerals in a mortar according to different proportions, and uniformly mixing;
(3) and placing the mixed material in inert gas, roasting for 2 hours at a certain temperature, cooling to room temperature, taking out, and introducing nitrogen for storage.
2. The preparation and application of the iron-based biochar for mediating the removal of hexavalent chromium and dyes by oxalic acid according to claim 1, wherein the biomass used in the step (1) is sieved by a 70-mesh sieve, and the natural iron-containing minerals are sieved by a 300-mesh sieve.
3. The preparation and use of an iron-based biochar mediating the removal of hexavalent chromium and dyes by oxalic acid according to claim 1, wherein the biomass and iron-containing minerals used in step (2) are respectively prepared in a ratio of 1:1,1: 2,2: 1,1: 3,3: 1 proportion for mixing and grinding.
4. The preparation and use of an iron-based biochar mediating the removal of hexavalent chromium and dyes by oxalic acid according to claim 1, wherein the iron-based biochar in step (3) is obtained by calcining in a tube furnace at an inert gas flow rate of 1.5L/min, a heating rate of 10 ℃/min, at 500, 700, 900 ℃ for two hours, cooling to room temperature, and introducing nitrogen for storage.
5. The preparation and use of an iron-based biochar mediating the removal of hexavalent chromium and dyes by oxalic acid according to claim 1, wherein said iron-based biochar is used in water bodies contaminated by cr (vi) and dye MB.
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Cited By (2)
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| CN114768761A (en) * | 2022-04-15 | 2022-07-22 | 广东省科学院生态环境与土壤研究所 | Preparation of biochar containing high-durability free radicals and application of biochar in removing heavy metals |
| CN115869979A (en) * | 2022-10-10 | 2023-03-31 | 华东交通大学 | Preparation method of porous nitrogen-doped lignin biochar and application of porous nitrogen-doped lignin biochar in mediating reduction of hexavalent chromium |
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Application publication date: 20220405 |