CN116393089A - Sulfur-modified magnetite-loaded biochar material and preparation method and application thereof - Google Patents
Sulfur-modified magnetite-loaded biochar material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000004098 Tetracycline Substances 0.000 claims abstract description 15
- 229960002180 tetracycline Drugs 0.000 claims abstract description 15
- 229930101283 tetracycline Natural products 0.000 claims abstract description 15
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 15
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 15
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 7
- 235000009566 rice Nutrition 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000012265 solid product Substances 0.000 claims abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 3
- 239000002351 wastewater Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 241000209094 Oryza Species 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 238000010669 acid-base reaction Methods 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 239000002069 magnetite nanoparticle Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
-
- 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
- C02F2101/103—Arsenic 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
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a sulfur-modified magnetite-loaded biochar material and a preparation method and application thereof. According to the invention, rice hulls are used as biomass materials, firstly, original biochar is obtained through limited oxygen pyrolysis, then ferrous salt and ferric salt are uniformly mixed with the biochar after being dissolved by ultrasound, then the pH value is adjusted after water bath heating until precipitation is formed, and the generated solid product is further vulcanized after washing and drying, so that the sulfur-modified magnetite-loaded biochar material is obtained. The prepared sulfur-modified magnetite-loaded biochar material has uniform magnetite nano particles and sulfonic acid group reaction sites, shows excellent tetracycline and trivalent arsenic removal performance, and can be applied to the treatment of composite polluted wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental remediation materials, and particularly relates to a sulfur-modified magnetite-loaded biochar material, and a preparation method and application thereof.
Background
With the rapid development of industry and agriculture and the increasing demand of substances for human beings, the problem of water pollution has evolved from single pollution to combined pollution of heavy metals and organic matters. Due to the emission of animal husbandry and aquaculture waste, tetracycline antibiotics and arsenic are detected in water simultaneously. Related studies have shown that the presence of tetracycline reduces the stability of arsenic in solution, and that the presence of arsenic also affects the removal of tetracycline, and the interaction between the two affects the removal efficiency of the complex contaminants. Therefore, development of a green and efficient composite polluted water body restoration technology is urgently needed.
Among conventional water treatment techniques, adsorption is one of simple and efficient methods. In recent years, biochar has been widely used as an adsorption material for heavy metals and antibiotics due to its characteristics of large specific surface area, developed pore structure, rich oxygen-containing functional groups, and the like. However, the adsorption capacity of the original biochar is limited and difficult to recycle from the water body, thus limiting its practical application potential. Meanwhile, the composite pollutants easily compete for active sites of the biochar, so that the water treatment efficiency is reduced. In recent years, the iron modified biochar can effectively improve the specific surface area and oxygen-containing functional groups of the biochar, but the loaded iron nanoparticles can occupy the reaction sites of the original biochar and block the porous structure. To solve the above problems, nonmetallic modification strategies are used to further regulate the surface properties of biochar and introduce rich functional groups.
Disclosure of Invention
The invention aims to provide a sulfur-modified magnetite-loaded biochar material, and a preparation method and application thereof. The invention prepares the material with Fe by a simple synthesis method 3 O 4 The nanoparticle and sulfonic acid double active sites show high stability and the capability of simultaneously removing tetracycline and arsenic.
The technical scheme adopted by the invention is as follows:
1. sulfur-modified magnetite-loaded biochar material
The biochar precursor is rice husk biomass, and is produced in Zhejiang Hangzhou. Magnetite has main component of Fe 3 O 4 The material mainly comprises biochar and Fe 3 O 4 And sulfur-containing groups.
Fe 3 O 4 The size of the nano particles is about 20nm, and the main component of the sulfur-containing group is sulfonic acid group.
2. Preparation method of sulfur-modified magnetite-loaded biochar material
The method comprises the following steps:
step 1) leaching the rice hull biomass raw material with deionized water to remove residual minerals, and then crushing the dried water by a high-speed crusher and sieving for standby. Placing a certain amount of biomass into a ceramic crucible, placing into a muffle furnace with temperature programming for oxygen limiting pyrolysis, cooling, taking out, washing with deionized water for multiple times, and drying to obtain biochar;
step 2) uniformly mixing ferrous salt and ferric salt after ultrasonic dissolution with the biochar obtained in the step 1), heating in a water bath, adjusting pH until precipitation is formed, washing the obtained solid product with deionized water to neutrality, and drying;
and 3) dissolving the dried product obtained in the step 2) in sodium hydroxide and tetraminobenzenesulfonic acid, continuously stirring and heating, and sequentially adding sodium nitrite and hydrochloric acid solution until the grafting reaction is completed after the acid-base reaction is finished. And washing the residual product to neutrality, and drying to obtain the sulfur-modified magnetite-loaded biochar material.
In the step 1): the temperature rising rate is 15 ℃ for min -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 700 ℃; the drying temperature is 60-80 ℃; the drying time is 24 hours; the screen size was 0.15mm.
In the step 2): the ferrous and ferric salts are FeSO 4 ·7H 2 O and FeCl 3 The molar ratio of the two is 1:2; the water bath temperature is 70 ℃; the reaction time is 1h; the pH value when forming the sediment is 10-11; after the reaction, the mixture was washed three times with deionized water and the drying temperature was 80 ℃.
In the step 3): the mass ratio of the sodium hydroxide to the tetraminobenzenesulfonic acid is 1:8.3; the reaction temperature is 70 ℃; the mass of the added sodium nitrite is 1.59g; the concentration of hydrochloric acid is 4mol/L; the drying temperature is 80 ℃; the drying time is 12 hours; the remaining product is washed with deionized water and acetone for at least three times.
3. Application of sulfur-modified magnetite-loaded biochar material
The sulfur-modified magnetite-loaded biochar material is applied to the treatment of the composite polluted wastewater; the sulfur-modified magnetite-loaded biochar material simultaneously removes tetracycline and trivalent arsenic.
The key of the technical proposal of the invention is that the metal nano particles Fe 3 O 4 Simultaneous modification of biochar with non-metallic sulfur, fe 3 O 4 The specific surface area of the biochar is improved, and more abundant functional groups are introduced by sulfur modification. The metal and nonmetal based dual-function modification strategy provides more active sites for the biochar, and simultaneously enhances the stability and the reactivity of the biochar.
The invention has the beneficial effects that:
(1) The sulfur-modified magnetite-loaded biochar material provided by the invention simultaneously realizes the aim of double-function modification of biochar, not only improves the specific surface area and magnetism of the biochar, but also introduces sulfonic functional groups with oxidability, and effectively promotes the removal of tetracycline and arsenic.
(2) The preparation method of the sulfur-modified magnetite-loaded biochar material provided by the invention is simple, environment-friendly and can be synthesized in a large scale.
(3) The sulfur-modified magnetite-loaded biochar material provided by the invention can realize the simultaneous removal of tetracycline and arsenic through a two-step process in a short time, and the mutual influence of the tetracycline and the arsenic is reduced to the maximum extent, thereby laying a foundation for the application in the field of water body composite pollution restoration.
Drawings
FIG. 1 is an XRD pattern of a sulfur-modified magnetite-supported biochar material prepared in example 2;
FIG. 2 is an SEM image of the sulfur-modified magnetite-supported biochar material prepared in example 2;
FIG. 3 is a FTIR diagram of a sulfur-modified magnetite-loaded biochar material prepared in example 2;
FIG. 4 is a hysteresis graph of the sulfur-modified magnetite-loaded biochar material prepared in example 2;
FIG. 5 is an S2 p XPS diagram of the sulfur-modified magnetite-loaded biochar material before and after reaction;
FIG. 6 is a graph showing the kinetics of removal of tetracycline and sodium arsenite by the sulfur-modified magnetite-loaded biochar material prepared in example 2.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, further detailed description of the present invention is provided with reference to the accompanying drawings and examples, it being understood that the specific examples described herein are intended to illustrate the present invention and not to limit the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are within the scope of the present invention.
Unless otherwise defined, the experimental methods described in the following examples are defined by the terms of art as commonly understood in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise indicated, reagents, materials, instruments and the like used in the present invention are commercially available.
Example 1
(1) Washing rice hull biomass with deionized water for multiple times, drying at 80 ℃, crushing by a high-speed crusher, and sieving with a 0.15mm sieve for later use;
(2) And (3) placing a certain amount of biomass into a ceramic crucible, transferring the crucible into a muffle furnace with temperature programmed, pyrolyzing at 700 ℃ for 6 hours, taking out, washing with deionized water for multiple times, and drying to obtain the rice husk biochar.
Example 2
(1) FeSO is carried out 4 ·7H 2 O and FeCl 3 Dissolved in 200mL at a molar ratio of 1:2Obtaining a solution A in ionized water;
(2) Weighing 5g of biochar, pouring the biochar into the solution A, and performing ultrasonic treatment for 30min to obtain a mixed solution B;
(3) Heating the mixed solution B in a water bath at 70 ℃ for 1h, then dropwise adding 5mol/L NaOH solution until the pH value is 11, centrifuging the generated black solid product, washing the product with deionized water to be neutral, and then drying the product at 80 ℃ to obtain Fe 3 O 4 @BC；
(4) 1.0g of Fe is weighed 3 O 4 Dissolving @ BC, 0.48g NaOH and 4.0g tetra-aminobenzenesulfonic acid in 120mL deionized water, stirring continuously at 70deg.C to obtain a mixed solution C, followed by 1.59g NaNO 2 To solution C, 8mL of 4mol/L HCl solution was then added dropwise. And after the reaction is finished, washing the residual solid with deionized water and acetone for a plurality of times, and drying at 80 ℃ for 12 hours to obtain the sulfur-modified magnetite-loaded biochar material.
FIG. 1 is a diagram of Fe prepared in example 2 3 O 4 XRD patterns of the@BC and sulfur-modified magnetite-loaded biochar materials are shown in the figure: in XRD patterns can be observed to belong to Fe 3 O 4 And sulfur modification does not affect Fe 3 O 4 Is a crystal structure of (a).
FIG. 2 is a diagram of Fe prepared in example 2 3 O 4 SEM images of @ BC and sulfur-modified magnetite-loaded biochar material, as follows: fe (Fe) 3 O 4 The nano particles are uniformly dispersed on the surface of the biochar, and sulfur modification does not affect Fe 3 O 4 The spherical structure of the nano particles and the porous structure of the biochar.
FIG. 3 is a diagram of Fe prepared in example 2 3 O 4 FTIR plot of @ BC and sulfur modified magnetite loaded biochar material, from the plot: fe (Fe) 3 O 4 While the Fe-OH groups are present in the @ BC, the sulfur is predominantly present in the sulfonic acid group form in the sulfur-modified magnetite-loaded biochar material.
FIG. 4 is a hysteresis curve of the sulfur-modified magnetite-supported biochar material prepared in example 2, as can be seen: the sulfur-modified magnetite-loaded biochar material has stronger magnetism and can be rapidly separated and recovered under the action of an external magnetic field.
Fig. 5 is an S2 p XPS diagram of the sulfur-modified magnetite-supported biochar material before and after reaction, as can be seen from the diagram: after the reaction, part of the sulfonic acid groups are converted into mercapto groups.
Application example 1
The kinetics of removal was tested with tetracycline and arsenic as target contaminants. 0.2g/L of the sulfur-modified magnetite-supported charcoal material prepared in example 2 was taken and placed in 22mL of a solution (initial pH 5) containing 1mg/L and 5mg/L of tetracycline and sodium arsenite, and the shaking was continued at room temperature for 240min. 1mL of the sample was withdrawn at regular intervals using a disposable syringe, filtered, and the concentrations of tetracycline and arsenic were measured using a high performance liquid chromatograph or hydride-atomic fluorescence photometer, and the results are shown in FIG. 6.
As can be seen from FIG. 6, the sulfur-modified magnetite-loaded biochar material prepared in example 2 of the present invention can remove about 85% of arsenic and tetracycline simultaneously in 120min at a concentration of 0.2g/L, and the whole removal process comprises two stages of adsorption and oxidation, so that the sulfur-modified magnetite-loaded biochar material prepared in example 2 of the present invention has a high removal efficiency for tetracycline and arsenic.
Furthermore, it should be understood that, although the present disclosure describes embodiments, not every embodiment contains only a single embodiment, and such descriptions are provided for clarity only, and those skilled in the art will recognize that the embodiments described herein may be suitably combined to form other embodiments as would be understood by those skilled in the art.
Claims (8)
1. A sulfur-modified magnetite-loaded biochar material is characterized in that: the magnetite and sulfur-containing group modified biochar are used for obtaining a sulfur-modified magnetite-loaded biochar material; the magnetite comprises Fe 3 O 4 Nanoparticles, size 20nm; the sulfur-containing group includes a sulfonic acid group; the biochar precursor is rice husk biomass.
2. The method for preparing the sulfur-modified magnetite-supported biochar material according to claim 1, comprising the steps of:
step 1), leaching a rice hull biomass raw material with deionized water to remove residual minerals, and then crushing the dried water by a high-speed crusher and sieving for later use;
placing the sieved biomass into a ceramic crucible, placing the ceramic crucible into a muffle furnace with temperature programming for oxygen limiting pyrolysis, cooling, taking out, washing with deionized water for multiple times, and drying to obtain biochar;
step 2) uniformly mixing ferrous salt and ferric salt after ultrasonic dissolution with the biochar obtained in the step 1), heating in a water bath, adjusting pH until precipitate is formed, washing the obtained solid product with deionized water to neutrality, and drying;
step 3) dissolving the dried product obtained in the step 2) in sodium hydroxide and tetraminobenzenesulfonic acid, continuously stirring and heating, and sequentially adding sodium nitrite and hydrochloric acid solution after the acid-base reaction is finished until the grafting reaction is finished; and washing the residual product to neutrality, and drying to obtain the sulfur-modified magnetite-loaded biochar material.
3. The method according to claim 2, wherein in step 1):
the temperature rising rate in the muffle furnace is 15 ℃ for min -1 The reaction temperature is 700 ℃;
the drying temperature is 60-80 ℃ and the drying time is 24 hours;
the size of the screened screen was 0.15mm.
4. The method according to claim 2, wherein in step 2):
the ferrous salt and the ferric salt are FeSO respectively 4 ·7H 2 O and FeCl 3 The molar ratio of the two is 1:2;
the mass ratio of the biochar to the total ferric salt is 1:1.
5. The method according to claim 2, wherein in step 2):
the water bath temperature is 70 ℃, and the reaction time is 1h;
the pH value when forming the sediment is 10-11;
the obtained solid product was washed three times with deionized water and above, and the drying temperature was 80 ℃.
6. The method according to claim 2, wherein in the step 3):
the mass ratio of the sodium hydroxide to the tetraminobenzenesulfonic acid is 1:8.3;
the mass of the added sodium nitrite is 1.59g, and the concentration of hydrochloric acid is 4mol/L.
7. The method according to claim 2, wherein in the step 3):
the reaction temperature of the acid-base reaction is 70 ℃;
the drying temperature is 80 ℃ and the drying time is 12 hours;
the remaining product is washed with deionized water and acetone for at least three times.
8. The use of the sulfur-modified magnetite-loaded biochar material of claim 1, wherein:
the sulfur-modified magnetite-loaded biochar material is applied to the treatment of the composite polluted wastewater, and can simultaneously remove tetracycline and trivalent arsenic.
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