CN113304740B - Adsorption-photocatalysis bifunctional composite material and preparation method and application thereof - Google Patents
Adsorption-photocatalysis bifunctional composite material and preparation method and application thereof Download PDFInfo
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 6
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Classifications
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- B01J35/19—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides an adsorption-photocatalysis bifunctional composite material which comprises amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is S and N co-doped amorphous carbon. The preparation method of the adsorption-photocatalysis bifunctional composite material comprises the following steps: dissolving industrial byproduct magnesium slag, melamine and urea in a solvent, stirring and mixing, and heating to evaporate the solvent to obtain a mixed material, wherein the main components of the magnesium slag are magnesium hydroxide and magnesium borate; mixing the mixed material in H 2 S and N 2 The mixture is roasted at constant temperature and then cooled to room temperature, and the adsorption-photocatalysis dual-function composite material is prepared. The magnesium slag adopted by the invention is the salt lake lithium extraction byproduct magnesium slag, and the composite material not only realizes resource utilization of the salt lake lithium extraction byproduct magnesium slag, but also is beneficial to solving the problems of resource waste and environmental pollution. In addition, the composite material can adsorb and photocatalytically degrade pollutant molecules in wastewater, and can be applied to treatment of water body pollution.
Description
Technical Field
The invention belongs to the technical field of environmental materials, and particularly relates to an adsorption-photocatalysis dual-functional composite material as well as a preparation method and application thereof.
Background
The main components of the magnesium slag as the by-product in the lithium extraction in the salt lake are magnesium hydroxide and magnesium borate, and the magnesium slag has serious environmental pollution due to the characteristics of fine particles, large adhesion capacity and strong alkalinity. Because a large amount of magnesium slag has no reliable, mature and effective utilization method, most of the magnesium slag is used as waste to be stacked on site, which not only occupies land, costs money, but also pollutes environment, and the magnesium slag treatment becomes a bottleneck restricting the development of magnesium industry. The research on the resource utilization of the magnesium slag is an urgent requirement for the sustainable development of the magnesium industry and is also a requirement for the strategy of the sustainable development of the recycling of the industrial waste slag.
In recent years, with rapid development of economy and industry, environmental problems have become more serious, and particularly, pollution of halogenated aromatic hydrocarbons, aromatic amines, dyes, and the like in the environment has attracted much attention. Research shows that the pollutants have strong mutation and carcinogenicity, seriously affect human health, and are not easily degraded and eliminated in the environment and exist persistently.
The adsorption method plays an important role in sewage treatment. The adsorption method is to utilize the selective adsorption capacity of adsorbent to certain component in liquid or gas to enrich it on the surface of adsorbent and separate it from the mixture. Adsorption methods can be divided into physical adsorption, chemical adsorption, and exchange adsorption. The physical adsorption mainly utilizes Van der Waals force, has small adsorption heat, is close to liquefaction heat, is reversible and has poor selectivity, and can be a monomolecular layer or a polymolecular layer. Compared with physical adsorption, the chemical adsorption acting force depends on hydrogen bonds, the released heat is large, and the monomolecular layer has strong selectivity. Exchange adsorption is the process whereby ions of a solute are accumulated at charged sites on the surface of an adsorbent by electrostatic attraction and are displaced from other ions originally immobilized at these charged sites. The adsorbing material can be divided into: inorganic adsorption materials and organic adsorption materials; depending on the source of the adsorbent material, it can be divided into: natural adsorbing material and synthetic adsorbing material. At present, the synthetic adsorbent material has attracted extensive attention of researchers due to its good adsorption performance and wide source.
The photocatalytic degradation technology for organic pollutants refers to the technology that when a semiconductor catalyst exists in organic wastewater, organic matters can be degraded after being irradiated by light with certain intensity, and then the purpose of treating the organic matters is achieved.
The development of composite materials with dual functions of adsorption and photocatalysis has become a current research hotspot, and is an urgent need for treating complex environmental systems at present. At present, the development of the adsorption-photocatalysis dual-function composite material for treating wastewater pollutants by applying the magnesium slag as the by-product of lithium extraction in salt lakes is not involved.
Disclosure of Invention
In view of the defects in the prior art, the invention provides an adsorption-photocatalysis dual-function composite material and a preparation method and application thereof, and aims to solve the problems of resource utilization of the existing salt lake lithium extraction by-product magnesium slag and water pollution treatment.
In order to achieve the above object, the present invention provides an adsorption-photocatalysis bifunctional composite material, comprising amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is co-doped with S and N.
Preferably, in the adsorption-photocatalysis bifunctional composite material, the amorphous carbon component content is 10-60 parts, the magnesium borate component content is 10-30 parts, and the magnesium oxide component content is 10-80 parts by mass.
Another aspect of the present invention provides a method for preparing the adsorption-photocatalytic bifunctional composite material as described above, which comprises:
s10, dissolving and stirring industrial byproduct magnesium slag, melamine and urea in a solvent, and heating to evaporate the solvent to obtain a mixed material; wherein the main components of the industrial byproduct magnesium slag are magnesium hydroxide and magnesium borate;
step S20, placing the mixed material into a reaction furnace, and reacting in H 2 S and N 2 The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H 2 S and N 2 Cooling in the mixed gas atmosphere to prepare the adsorption-photocatalysis bifunctional composite material.
Preferably, in the step S10, the industrial byproduct magnesium slag is byproduct magnesium slag generated in a lithium extraction process in a salt lake; according to the mass part, the industrial byproduct magnesium slag is 50-80 parts, the melamine is 5-30 parts, and the urea is 5-30 parts.
Preferably, the step S10 specifically includes:
putting industrial byproducts of magnesium slag, melamine and urea into a mixing tank containing a solvent according to a predetermined mass part ratio, and stirring and dissolving to obtain a mixed suspension;
and heating the mixed suspension in the dosing tank to increase the temperature, and continuously stirring to completely evaporate the solvent to obtain the mixed material.
Preferably, the step S20 specifically includes:
placing the mixed material in a high-temperature converter, and introducing H into the high-temperature converter 2 S and N 2 In said H mixed gas 2 S and N 2 Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
Further preferably, the temperature rise speed of the high-temperature converter is 5 ℃/min to 10 ℃/min, the roasting temperature is 500 ℃ to 800 ℃, and the constant-temperature roasting time is 2h to 6h.
Preferably, in the step S30, the temperature reduction rate of the roasted product is 5 ℃/min to 20 ℃/min, and the roasted product is cooled to room temperature.
Further preferably, said H 2 S and N 2 In the mixed gas of (2), H 2 The volume percentage of S is 5-30%; in the step S20, the H 2 S and N 2 The flow rate of the mixed gas is 50mL/min to 100mL/min; in the step S30, the H 2 S and N 2 The flow rate of the mixed gas is 30 mL/min-60 mL/min.
The invention also provides application of the adsorption-photocatalysis dual-function composite material in water pollution treatment.
The adsorption-photocatalysis bifunctional composite material provided by the embodiment of the invention comprises amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is S and N co-doped amorphous carbon. The S and N co-doped amorphous carbon has rich surface active sites and electron capture capacity, and is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material, so that the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants can be effectively improved.
According to the preparation method of the adsorption-photocatalysis dual-function composite material provided by the embodiment of the invention, the salt lake lithium extraction byproduct magnesium slag is used as a raw material for preparation, so that resource utilization of the salt lake lithium extraction byproduct magnesium slag is realized, and the problems of resource waste and environmental pollution are solved.
The embodiment of the invention provides application of an adsorption-photocatalysis dual-function composite material, which can adsorb and photocatalytically degrade pollutant molecules in wastewater and is beneficial to treatment of water body pollution.
Drawings
FIG. 1 is a process flow diagram of a method for preparing an adsorption-photocatalytic bifunctional composite material according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of a magnesium slag as a by-product of lithium extraction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides an adsorption-photocatalysis bifunctional composite material which comprises amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is S and N co-doped amorphous carbon.
Preferably, in the adsorption-photocatalysis bifunctional composite material, the amorphous carbon component content is 10-60 parts, the magnesium borate component content is 10-30 parts, and the magnesium oxide component content is 10-80 parts by mass
When the semiconductor catalyst exists in the organic wastewater, after the semiconductor catalyst is irradiated by light with certain intensity, a certain amount of active oxygen and free radicals in various forms are generated in the system, and the active oxygen and the free radicals have higher oxidation potential, so that the organic matter can be degraded and mineralized into water or carbon dioxide. The S and N co-doped amorphous carbon has abundant electron capture capacity and surface active sites, and is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material, so that the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants can be effectively improved.
The embodiment of the invention also provides a preparation method of the adsorption-photocatalysis bifunctional composite material, and referring to fig. 1, the preparation method comprises the following steps:
s10, dissolving the industrial byproduct magnesium slag, melamine and urea in a solvent, stirring and mixing, and heating to evaporate the solvent to obtain a mixed material; wherein the main components of the industrial byproduct magnesium slag are magnesium hydroxide and magnesium borate.
Preferably, the industrial byproduct magnesium slag is a byproduct magnesium slag produced in a lithium extraction process in a salt lake, the magnesium slag is mainly a mixture of magnesium hydroxide and magnesium borate, and the result of X-ray diffraction (XRD) analysis of the magnesium slag is shown in figure 2.
Further preferably, the industrial byproduct magnesium slag is 50-80 parts by mass, the melamine is 5-30 parts by mass, and the urea is 5-30 parts by mass.
Specifically, according to a preset mass part ratio, putting industrial byproducts of magnesium slag, melamine and urea into a mixing tank containing a solvent, and stirring and dissolving to obtain a mixed suspension; the solvent can be deionized water, the dosage of the solvent is 50-150 mL, the stirring speed of the batching tank at room temperature is 200-500 r/min, and the stirring and dissolving time is 0.5h.
Heating the mixed suspension in the batching tank, and continuously stirring to completely evaporate a solvent to obtain the mixed material; wherein the heating temperature of the mixed suspension is 55-85 ℃.
S20, mixing the mixed materialThe material is placed in a reaction furnace at H 2 S and N 2 The mixed gas atmosphere of (2) is roasted to obtain a roasted product.
Specifically, the mixed material is placed in a high-temperature converter, and H is introduced into the high-temperature converter 2 S and N 2 In said H mixed gas 2 S and N 2 Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
Preferably, the rotating speed of the high-temperature converter is 5 r/min-30 r/min, the heating speed of the high-temperature converter is 5 ℃/min-10 ℃/min, the roasting temperature is 500 ℃ -800 ℃, and the constant-temperature roasting time is 2 h-6 h.
Further preferably, said H 2 S and N 2 In the mixed gas of (2), H 2 S is 5-30% by volume, and H is 2 S and N 2 The flow rate of the mixed gas is 50mL/min to 100mL/min.
Preferably, the waste gas generated in the reaction process in the step S20 is reversely absorbed by lime water, the absorbed waste gas is discharged after reaching the standard through detection, and the solid waste obtained by evaporating the waste liquid is delivered to a third-party company for treatment.
Further preferably, the concentration of the lime water is 0.3-3.0 g/L, the flow rate of the lime water is 5-10L/min, and the flow rate of the waste gas absorbed by the lime water is 150-130 mL/min.
S30, reacting the roasted product with hydrogen 2 S and N 2 Cooling in the mixed gas atmosphere to prepare the adsorption-photocatalysis bifunctional composite material.
Preferably, the cooling rate of the roasted product is 5-20 ℃/min, and the roasted product is cooled to room temperature.
Further preferably, said H 2 S and N 2 In the mixed gas of (2), H 2 S is 5-30% by volume, and H is 2 S and N 2 The flow rate of the mixed gas is 30mL/min to 60mL/min.
The adsorption-photocatalysis dual-function composite material is prepared by taking the salt lake lithium extraction byproduct magnesium slag as a raw material, so that the resource utilization of the salt lake lithium extraction byproduct magnesium slag is realized, and the problems of land and capital waste and environmental pollution caused by the fact that a large amount of magnesium slag is stacked on site and is mostly used as waste due to no reliable, mature and effective utilization method are solved. And moreover, the waste gas generated in the reaction process is absorbed by lime water in a countercurrent way, and the absorbed waste gas is discharged after reaching the standard through detection, so that the damage of three-waste discharge to the ecological environment is reduced.
The embodiment of the invention also provides application of the adsorption-photocatalysis bifunctional composite material.
The adsorption-photocatalysis dual-function composite material can adsorb and photocatalytically degrade pollutant molecules in wastewater, and is beneficial to treatment of water pollution.
The above adsorption-photocatalytic dual-function composite material, the preparation method and the application thereof will be described with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above adsorption-photocatalytic dual-function composite material, the preparation method and the application thereof, and are not intended to limit the entirety thereof.
Example 1
Step one, 70g of magnesium slag 1 (the specific composition table of the magnesium slag is shown in the following table 1) as a lithium extraction byproduct is weighed, 15g of melamine and 15g of urea are placed into a mixing tank containing 100mL of deionized water, and stirring is carried out at the rotating speed of 300r/min for 0.5h at room temperature. After stirring, the suspension in the batching tank is heated to 70 ℃ and stirred at constant temperature until the deionized water is completely evaporated, thus obtaining the mixed material.
Step two, the mixed material is sent to a high-temperature converter with the rotating speed of 10r/min, and the flow rate of the mixed material is 80 mL/min and H 2 H with S volume fraction of 10% 2 S and N 2 And (3) removing air in the furnace from the mixed gas, heating to 550 ℃ at the speed of 10 ℃/min under the atmosphere, and roasting at constant temperature for 3 hours to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using lime water with the flow rate of 5L/min, the absorbed waste gas is emptied after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, enabling the obtained roasting product to flow at the flow rate of 40mL/min, H 2 H with S volume fraction of 10% 2 S and N 2 Cooling to room temperature at 5 ℃/min in the mixed gas atmosphere to obtain S, N codoped amorphous carbon and Mg 3 (BO 3 ) 2 And MgO adsorption-photocatalysis bifunctional composite material.
The adsorption-photocatalysis dual-function composite material is used for removing pollutant molecules in wastewater, and can adsorb 65.2 percent of antibiotic tetracycline hydrochloride (200 mg/L) degraded by 33.7 percent under the specific conditions of 1h of adsorption and 1h of visible light degradation; ciprofloxacin (200 mg/L) capable of adsorbing 61.8% and degrading 36.4%; 67.2 percent of rhodamine B can be adsorbed and 31.9 percent of rhodamine B can be degraded (150 mg/L); methylene blue (300 mg/L) which can absorb 66.3% and degrade 32.5%.
Example 2
Step one, 75g of magnesium slag 2 (the specific composition table of the magnesium slag is shown in the following table 1) as a lithium extraction byproduct is weighed, 10g of melamine and 15g of urea are placed in a dosing tank containing 120mL of deionized water, and stirring is carried out at the rotating speed of 330r/min for 0.5h at room temperature. After stirring is completed, the suspension in the batching tank is heated to 65 ℃ and stirred at constant temperature until the deionized water is completely evaporated, so as to obtain the mixed material.
Step two, the mixed material is sent to a high-temperature converter with the rotating speed of 15r/min, and the flow rate of H and 100mL/min is introduced 2 H with 8% S volume fraction 2 S and N 2 The mixed gas in the furnace is exhausted, the temperature is raised to 600 ℃ at the speed of 15 ℃/min under the atmosphere, and the mixture is roasted for 2.5 hours at constant temperature, so that a roasted product is obtained.
The waste gas generated in the reaction process is reversely absorbed by lime water with the flow rate of 6L/min, the absorbed waste gas is emptied after reaching the standard through detection, and the solid waste obtained by evaporating the waste liquid is delivered to a third-party company for treatment.
Step three, enabling the obtained roasting product to flow at the flow rate of 50mL/min, H 2 H with 8% S volume fraction 2 S and N 2 Cooling to room temperature at the speed of 5 ℃/min in the mixed gas atmosphere to obtain S, N codoped amorphous carbon and Mg 3 (BO 3 ) 2 And MgO adsorption-photocatalysis bifunctional composite material.
The adsorption-photocatalysis dual-function composite material is used for removing pollutant molecules in wastewater, and can adsorb 64.7 percent of antibiotic tetracycline hydrochloride (200 mg/L) degraded by 34.1 percent under the specific conditions of 1 hour of adsorption and 1 hour of visible light degradation; ciprofloxacin (200 mg/L) capable of adsorbing 63.3% and degrading 35.8%; rhodamine B (150 mg/L) which can adsorb 66.5 percent and degrade 32.7 percent; methylene blue (300 mg/L) which can adsorb 67.0% and degrade 31.8%.
Example 3
Step one, 65g of magnesium slag 3 (the specific composition table of the magnesium slag is shown in table 1 below) as a lithium extraction byproduct is weighed, 18g of melamine and 17g of urea are placed in a dosing tank containing 110mL of deionized water, and stirring is carried out at the rotating speed of 260r/min for 0.5h at room temperature. After stirring, the suspension in the batching tank is heated to 70 ℃ and stirred at constant temperature until the deionized water is completely evaporated, thus obtaining the mixed material.
Step two, the mixed material is sent to a high-temperature converter with the rotating speed of 20r/min, and the flow rate of H and 60mL/min is introduced 2 H with S volume fraction of 15% 2 S and N 2 And (3) removing air in the furnace from the mixed gas, heating to 600 ℃ at the speed of 10 ℃/min in the atmosphere, and roasting at constant temperature for 4 hours to obtain a roasted product.
The waste gas generated in the reaction process is reversely absorbed by lime water with the flow rate of 5L/min, the absorbed waste gas is emptied after reaching the standard through detection, and the solid waste obtained by evaporating the waste liquid is delivered to a third-party company for treatment.
Step three, enabling the obtained roasting product to flow at the flow rate of 40mL/min, H 2 H with S volume fraction of 15% 2 S and N 2 Cooling to room temperature at a speed of 10 ℃/min in the atmosphere of the mixed gas to obtain S, N codoped amorphous carbon and Mg 3 (BO 3 ) 2 And MgO adsorption-photocatalysis double-function composite material.
The adsorption-photocatalysis dual-function composite material is used for removing pollutant molecules in wastewater, and under the specific conditions of 1h of adsorption and 1h of visible light degradation, the adsorption-photocatalysis dual-function composite material can adsorb 66.1% of tetracycline hydrochloride (200 mg/L) which is antibiotic and degrades 32.5%; ciprofloxacin (200 mg/L) capable of adsorbing 65.2% and degrading 36.9%; can adsorb 67.3 percent of degraded rhodamine B (150 mg/L) and 31.0 percent of rhodamine B; methylene blue (300 mg/L) which can absorb 66.0% and degrade 32.5%.
Example 4
Step one, weighing 80g of magnesium slag 4 (the specific composition table of the magnesium slag is shown in the following table 1) as a lithium extraction byproduct, putting 15g of melamine and 5g of urea into a mixing tank containing 90mL of deionized water, and stirring at room temperature at the rotating speed of 350r/min for 0.5h. After stirring, the suspension in the batching tank is heated to 75 ℃ and stirred at constant temperature until the deionized water is completely evaporated, thus obtaining the mixed material.
Step two, the mixed material is sent to a high-temperature converter with the rotating speed of 10r/min, and the flow rate of H and 50mL/min is introduced 2 H with 12% S volume fraction 2 S and N 2 The air in the furnace is removed from the mixed gas, the temperature is raised to 570 ℃ at the speed of 15 ℃/min under the atmosphere, and the mixture is roasted for 5 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by lime water with the flow rate of 6L/min, the absorbed waste gas is discharged after reaching the standard through detection, and solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment.
Step three, enabling the obtained roasting product to flow at the flow rate of 30mL/min, H 2 H with S volume fraction of 10% 2 S and N 2 Cooling to room temperature at the speed of 5 ℃/min in the mixed gas atmosphere to obtain S, N codoped amorphous carbon and Mg 3 (BO 3 ) 2 And MgO adsorption-photocatalysis bifunctional composite material.
The adsorption-photocatalysis dual-function composite material is used for removing pollutant molecules in wastewater, and can adsorb 68.6 percent of antibiotic tetracycline hydrochloride (200 mg/L) degraded by 30.1 percent under the specific conditions of adsorption for 1 hour and visible light degradation for 1 hour; ciprofloxacin (200 mg/L) capable of adsorbing 62.7% and degrading 35.6%; rhodamine B (150 mg/L) which can adsorb 64.8 percent and degrade 34.3 percent; methylene blue (300 mg/L) which can adsorb 67.2% and degrade 30.6% can be absorbed.
Table 1: composition of magnesium slag as by-product of lithium extraction
The adsorption-photocatalysis bifunctional composite material provided by the embodiment of the invention comprises amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is S and N co-doped amorphous carbon. The S and N co-doped amorphous carbon has abundant surface active sites and electron capture capacity, and is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material, so that the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants can be effectively improved. In addition, the adsorption-photocatalysis dual-function composite material is prepared by using the salt lake lithium extraction byproduct magnesium slag as a raw material, so that the resource utilization of the salt lake lithium extraction byproduct magnesium slag is realized, the resource waste and the environmental pollution problem are favorably solved, and meanwhile, the composite material can be used for adsorbing and carrying out photocatalysis degradation on pollutants in wastewater, and the water body pollution problem is favorably treated.
The foregoing is illustrative of the present disclosure and it will be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles of the disclosure, the scope of which is defined by the appended claims.
Claims (8)
1. The adsorption-photocatalysis bifunctional composite material is characterized by comprising amorphous carbon, magnesium borate and magnesium oxide, wherein the amorphous carbon is S and N co-doped amorphous carbon;
the composite material comprises, by mass, 10-60 parts of amorphous carbon, 10-30 parts of magnesium borate and 10-80 parts of magnesium oxide.
2. A method for preparing the adsorption-photocatalysis bifunctional composite material as claimed in claim 1, which comprises:
s10, dissolving and stirring industrial byproduct magnesium slag, melamine and urea in a solvent, and heating to evaporate the solvent to obtain a mixed material; wherein the main components of the industrial byproduct magnesium slag are magnesium hydroxide and magnesium borate;
step S20, placing the mixed material into a reaction furnace, and reacting in H 2 S and N 2 The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H 2 S and N 2 Cooling in the mixed gas atmosphere to prepare and obtain the adsorption-photocatalysis bifunctional composite material;
in the step S10, the industrial byproduct magnesium slag is byproduct magnesium slag generated in a salt lake lithium extraction process; according to the mass parts, the industrial byproduct magnesium slag is 50-80 parts, the melamine is 5-30 parts, and the urea is 5-30 parts.
3. The method for preparing an adsorption-photocatalytic bifunctional composite material according to claim 2, wherein the step S10 specifically comprises:
putting the industrial byproducts of the magnesium slag, the melamine and the urea into a mixing tank containing a solvent according to a predetermined mass part ratio, and stirring and dissolving to obtain a mixed suspension;
and heating the mixed suspension in the dosing tank to increase the temperature, and continuously stirring to completely evaporate the solvent to obtain the mixed material.
4. The method for preparing an adsorption-photocatalytic bifunctional composite material according to claim 2, wherein the step S20 specifically comprises: placing the mixed material in a high-temperature converter, and introducing H into the high-temperature converter 2 S and N 2 In said H mixed gas 2 S and N 2 Heating to a temperature ofAnd (4) roasting at constant temperature after the set roasting temperature to obtain a roasted product.
5. The preparation method of the adsorption-photocatalysis dual-function composite material according to claim 4, wherein the temperature rise speed of the high-temperature converter is 5 ℃/min to 10 ℃/min, the roasting temperature is 500 ℃ to 800 ℃, and the constant-temperature roasting time is 2h to 6h.
6. The preparation method of the adsorption-photocatalytic bifunctional composite material as claimed in claim 2, wherein in the step S30, the temperature reduction rate of the calcined product is 5 ℃/min to 20 ℃/min, and the calcined product is cooled to room temperature.
7. Method for preparing an adsorption-photocatalytic bifunctional composite material according to any one of claims 4 to 6, characterized in that said H is 2 S and N 2 In the mixed gas of (2), H 2 The volume percentage of S is 5-30%; in the step S20, the step H 2 S and N 2 The flow rate of the mixed gas is 50mL/min to 100mL/min; in the step S30, the step H 2 S and N 2 The flow rate of the mixed gas is 30 mL/min-60 mL/min.
8. Use of the adsorption-photocatalytic bifunctional composite material according to claim 1 in water pollution control.
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