CN112517026A - Persulfate-activated non-metallic composition, and preparation method and application thereof - Google Patents
Persulfate-activated non-metallic composition, and preparation method and application thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J35/40—
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- B01J35/613—
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- B01J35/633—
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- B01J35/643—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/345—Phenols
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
Adding activated carbon, sulfur powder and ball milling balls into a zirconium oxide ball milling tank, naturally cooling to room temperature after ball milling is finished, and sieving and separating to obtain a sulfur-doped carbon material with a micro-nano size, wherein the size of the sulfur-doped carbon material with the micro-nano size is 200-600 nm, and the pore volume is 0.023 cm3/gAverage pore diameter of 1.62 nm and specific surface area of 12.19 m2(ii) in terms of/g. The sulfur-doped carbon material composition prepared by the invention has a micro-nano structure and excellent catalytic performance, overcomes the limitations of narrow pH range, high Fe mud yield, low efficiency and the like in the traditional metal-dependent Fenton reaction process, and has wide application prospects in the aspects of organic polluted wastewater and soil remediation.
Description
Technical Field
The invention belongs to the technical field of organic polluted wastewater treatment, and particularly relates to a nonmetal composition for activating persulfate, and a preparation method and application thereof.
Technical Field
Monopersulfate (PMS) can be activated by metal oxide, transition metal and the like to generate high-activity sulfate radical (SO)4 •-2.5-3.1V) and hydroxyl radical (HO)•2.8V) has outstanding advantages in the aspect of efficiently degrading organic pollutants, and the catalytic oxidation technology based on PMS is widely concerned by the academic world. However, the practical application is challenged by the limitations of metal ion dissolution, narrow applicable pH range and the like. Meanwhile, the environmental friendliness of the non-metal catalyst has attracted much attention. Due to the characteristics of large specific surface area, no metal, and the like, carbon-based materials such as Carbon Nanotubes (CNTs) and activated persulfates such as Reduced Graphene Oxide (RGO) have been reported. On the basis, the carbon material is modified, such as heteroatom doping, so that the structure, electronic characteristics and the like of the carbon material can be effectively regulated and controlled, and more requirements are met. Recently, nitrogen-doped carbon materials, which have been greatly developed, have excellent performance in the field of catalysis. The excellent performance of the heteroatom doped carbon material catalyst attracts researchers to continuously expand the doping spectrum, such as heteroatoms like sulfur (S), phosphorus (P) and the like. Modification of carbon materials with hetero atoms, i.e. N, SThe heteroatom is introduced into the carbon backbone. The approximate atomic radii of N and C make it relatively easy for N to substitute carbon atoms in the carbon lattice, so that N is selected to dope the carbon material, and the result is more ideal. Different from N, S is much larger than the radius of C atoms, so that S is difficult to dope into a carbon skeleton, and a sulfur-doped carbon material indicates a new direction in the field of carbon materials, so that research work is relatively less. The influence of doping modes of various heteroatoms on the performance of carbon materials also arouses research interest of scholars. Heretofore, researchers have developed various methods such as a plasma method, a hydrothermal method, a ball milling method, and the like. The ball milling method is popular with researchers due to high yield, simple operation, environmental protection and easy scale production. In ball milling, the heteroatom and carbon-based materials are ball milled and the high speed ball milling balls mechanically reduce the solid particle size, creating surface defects and creating new functional groups that are believed to be the active sites of PMS.
In the present society of energy crisis and environmental pollution, "energy" becomes a hot point of competition among countries. CNTs, RGO and the like are not suitable for large-scale production, popularization and application due to complex preparation process, high price and the like. Therefore, the development of monopersulfate catalysts which are environmentally friendly, efficient and inexpensive is urgently needed.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical bottlenecks of complex operation, high manufacturing cost and the like of the traditional process for treating organic pollutants based on metal activated persulfate, the nonmetal composition of the activated persulfate and the preparation method and the application thereof are characterized in that activated carbon and sulfur powder are selected as raw materials, and a micro-nano sulfur-doped carbon material (nSACx, wherein x is the initial sulfur addition content and the unit is mmol) is prepared by a ball milling process, and the micro-nano sulfur-doped carbon material can efficiently activate monopersulfate (PMS) to degrade various organic pollutants in wastewater, including pollutants such as diethyl phthalate, sulfamethoxydiazine, bisphenol A, phenol and the like. The ball milling process is simple and environment-friendly, and is easy for large-scale production and application; the selected raw materials are activated carbon and sulfur powder, so that the price is low, the storage capacity is rich, and the environment is friendly; the prepared sulfur-doped carbon material has a micro-nano structure, and can provide a larger specific surface area and more excellent catalytic performance; the nSACx/PMS system has the advantages of wide pH application range, high degradation efficiency and the like, and the characteristics are new ideas and directions for initiating new carbon materials.
The technical scheme is as follows: the preparation method of the persulfate-activated nonmetal composition comprises the following steps: adding activated carbon, sulfur powder and ball milling balls into a zirconia ball milling tank, naturally cooling to room temperature after ball milling is finished, sieving and separating to obtain a sulfur-doped carbon material with micro-nano size, wherein the size of the sulfur-doped carbon material with micro-nano size is 200-600 nm, and the pore volume is 0.023 cm3G, average pore diameter of 1.62 nm, specific surface area of 12.19 m2/g。
Ball milling time: the ball milling is carried out for 15 min each time, the suspension is carried out for 15 min, the circulation is carried out for 96 times, and the ball milling is carried out for 24 h in total.
The ball-milling ball comprises the following components in percentage by weight: 40 g of 10 mm pellets, 50 g of 7 mm pellets, 40 g of 6 mm pellets, 30 g of 3 mm pellets.
The material ratio of ball milling is 40:1, the mass of a sample in single ball milling is 4 g, and the rotating speed is 450 rpm.
The persulfate-activated non-metallic composition prepared by the method is provided.
The sulfur content in the above material was 6.08 at%.
The use of a non-metallic composition of the above persulfate in the treatment of organic pollutants.
The organic pollutants are diethyl phthalate, bisphenol A, sulfamethoxydiazine and phenol, and the concentration of the pollutants is 100 mu M.
The application steps are as follows: adding monopersulfate and sulfur-doped carbon material into the waste water of the organic pollutants, wherein the concentrations of the monopersulfate and the sulfur-doped carbon material are 0.5-5.0 mM and 0.5-2.0 g/L respectively, and carrying out oscillation reaction for 4 hours.
Has the advantages that: (1) the ball milling process is simple to operate, environment-friendly, high in product rate, capable of being produced and applied in large scale and capable of overcoming the defects of complex operation, high manufacturing cost and the like of the traditional process. (2) The activated carbon and the sulfur powder are selected as raw materials, so that the method is low in price, rich in reserves and environment-friendly, and the cost is greatly reduced in the actual organic wastewater treatment. (3) The prepared sulfur-doped carbon nano material is a nonmetal catalyst and has low sulfur content, and the problems of toxic metal dissolution of the metal catalyst and the like are solved. (4) The prepared sulfur-doped carbon material has a micro-nano structure, provides a larger contact area and more active sites for activating monopersulfate, further shows excellent catalytic performance, and has the advantages of wide pH range, recyclability and the like. (5) The invention has simple process operation and low cost, and the product has high catalytic performance and high-efficiency degradation activity on diethyl phthalate, sulfamethoxydiazine, bisphenol A and phenol pollutants.
Drawings
FIG. 1 is a transmission electron micrograph of a sulfur-doped carbon material;
FIG. 2 is a graph comparing the effect of different sulfur doping levels of sulfur-doped carbon materials on pollutant degradation by activated monopersulfate;
FIG. 3 is a comparison graph of the effect of sulfur-doped carbon material activated monopersulfate on degrading diethyl phthalate;
FIG. 4 is a graph comparing the effect of sulfur-doped carbon material dose and monopersulfate concentration on contaminant degradation in a sulfur-doped carbon material activated monopersulfate system;
FIG. 5 is a graph comparing the degradation effect of activated monopersulfate from sulfur-doped carbon materials on different types of organic pollutants;
FIG. 6 is a graph comparing the effect of the sulfur-doped carbon material activated monopersulfate cycle experiment on degrading organic pollutants.
Detailed Description
The invention is further illustrated by the following examples, which illustrate the salient features and significant improvements of the invention, and which are intended to be illustrative only and are in no way limited to the following examples. The embodiment is a nonmetal composition for efficiently activating persulfate and application thereof.
Example 1: the nonmetal composition for efficiently activating persulfate and the application thereof are completed according to the following steps:
the method for preparing the sulfur-doped carbon material with the micro-nano size by the ball milling method comprises the following steps:
the method comprises the following steps: adding activated carbon, sulfur powder and ball milling balls into a 125 mL zirconia ball milling tank in proportion;
step two: and optimizing ball milling parameters, naturally cooling to room temperature after ball milling is finished, and sieving and separating to obtain a sample. The transmission electron microscope of the prepared sulfur-doped carbon material is shown in figure 1, is of a layered structure and has a micro-nano structure: 200-600 nm. Ball milling time: the ball milling is carried out for 15 min each time, the suspension is carried out for 15 min, the circulation is carried out for 96 times, and the ball milling is carried out for 24 h in total. The ball-milling ball comprises the following components in percentage by weight: 40 g of 10 mm pellets, 50 g of 7 mm pellets, 40 g of 6 mm pellets, 30 g of 3 mm pellets. The material ratio of ball milling is 40:1, the mass of a sample in single ball milling is 4 g, and the rotating speed is 450 rpm.
Secondly, premixing reactants and activating monopersulfate to degrade organic pollutants
Taking wastewater containing different types of organic pollutants, and adding monopersulfate with a certain concentration to obtain a premix of the pollutants and the monopersulfate; the initial concentration of monopersulfate is 0.5-5.0 mM; the types of organic pollutants in the pretreatment solution are diethyl phthalate, sulfamethoxydiazine, bisphenol A and phenol, and the concentration of the organic pollutants is 100 mu M.
Third, induction of catalytic degradation experiment
Adding the micro-nano sulfur-doped carbon material into a premixed solution of a pollutant and monopersulfate, and carrying out oscillation reaction for 4 hours, wherein the adding amount of the micro-nano sulfur-doped carbon material is 0.5-2.0 g/L.
Fourthly, adjusting the pH value of the reaction
The invention can realize the high-efficiency degradation of organic pollutants in a wide pH range (3-9), which shows that the influence of the environmental pH value on a reaction system is not great. The pH of the reaction system was adjusted to a predetermined value using sulfuric acid (0.05 mM) and sodium hydroxide solution before the induction of the catalytic degradation experiment.
Extraction and determination of organic pollutants
After the sulfur-doped carbon material with the micro-nano size is added into a premixed solution of organic pollutants and monopersulfate, the reaction is started, and the reaction system is 10 mL. Adding 0.1 mL of ethanol at fixed time intervals (10/20/30/60/120/240 min) to terminate destructive sampling of the reaction, obtaining supernatant and solids by high-speed centrifugation (3000 rpm/5 min), and filtering 1 mL of the supernatant through a 0.22 mu M aqueous filter membrane for determining the residual concentration of the target pollutant in the supernatant by a high performance liquid chromatograph; carefully pouring out the residual supernatant, adding 10 mL of methanol into the residual solid, performing ultrasonic extraction for 30 min and oscillation in an oscillation tank for 1 h, sampling through a 0.22 mu M organic filter membrane, and determining the concentration of the target pollutant adsorbed in the solid by using a high performance liquid chromatograph. And calculating the degradation rate of the pollutants by calculating the sum of the target pollutant concentrations in the liquid phase and the solid phase obtained by measurement.
Sixth, recovery and reuse of sulfur-doped carbon materials
And after the reaction is finished, recovering the sulfur-doped carbon nano material by vacuum filtration, washing the reacted solid by using ethyl acetate (solid/ethyl acetate =1:20, wt%), washing the organic pollutants adsorbed on the surface of the solid in the reaction process and intermediate products degraded by the organic pollutants, and collecting the cleaned and dried sulfur-doped carbon material.
Example 2: nonmetal composition for efficiently activating persulfate and effect comparison of application thereof
Carbon materials of different sulfur doping contents (1.78 at% of sulfur in ncac 2, 3.41 at% of sulfur in ncac 4, 6.08 at% of sulfur in ncac 8, and 8.69 at% of sulfur in ncac 12) were prepared according to the procedure of example 1, comparing the effects of carbon materials of different sulfur doping contents on activating monopersulfate to degrade organic contaminants. In the reaction system, the concentrations of the sulfur-doped carbon material, monopersulfate and organic pollutant diethyl phthalate are 1 g/L, 1 mM and 100 muM respectively.
The result is shown in fig. 2, the product (bm AC) obtained by ball milling of activated carbon alone activates monopersulfate, and has only 21% adsorption removal rate on organic pollutants; when the sulfur doping content in the activated carbon is increased from 1.78 at% (nSAC 2) to 6.08 at% (nSAC 8), the degradation efficiency of the organic pollutants is increased from 52% to 90%; when the doped sulfur content was further increased to 8.69 at% (ncac 12), the degradation of organic contaminants was instead inhibited, from 90% to 86%. Therefore, the optimum sulfur doping content is 6.08 at% (nSAC 8), and the optimum sulfur doping content in all sulfur-doped carbon materials is 6.08 at% (nSAC 8).
Example 3: nonmetal composition for efficiently activating persulfate and catalytic performance of nonmetal composition
The degradation removal effect of different systems on organic contaminants was compared according to the procedure of example 1, using diethyl phthalate as the target contaminant. The concentrations of sulfur-doped carbon material (nSAC 8), monopersulfate (PMS) and diethyl phthalate (DEP) were 1 g/L, 1 mM and 100. mu.M, respectively. The following treatments were designed:
（1）PMS/DEP；
（2）nSAC8/DEP；
（3）nSAC8/PMS/DEP；
the result is shown in fig. 3, the degradation effect of the PMS alone on DEP is negligible; the nSAC8 alone had only 12% adsorption removal of DEP; however, 90% of the DEP was completely degraded after 4 h reaction under the combined action of nSAC8 and PMS. The invention proves that the sulfur-doped carbon material capable of activating monopersulfate and efficiently degrading organic pollutants is successfully prepared by adopting a ball milling method.
Example 4: comparison of sulfur-doped carbon material dosage and monopersulfate concentration on organic pollutant degradation effect of system
According to the steps of example 1, the influence of the dosage of the sulfur-doped carbon material and the concentration of monopersulfate on the effect of the system on degrading organic pollutants is investigated. In the nSAC8/PMS/DEP system, the concentrations of nSAC8, PMS and DEP were 1.0 g/L, 1.0 mM and 100. mu.M, respectively. The dosage range of the nSAC8 is 0.5-2.0 g/L, and the concentration range of the PMS is 0.5-5.0 mM. The results are shown in fig. 4, where DEP degradation rate increased with increasing amounts of ncac 8 added; while the degradation rate of DEP increased when the concentration of PMS was increased from 0.5 mM to 1.0 mM, excessive PMS inhibited the degradation of DEP when the concentration of PMS was further increased to 5.0 mM. Considering the factors of degradation rate, cost and the like comprehensively, the optimum dosage of nSAC8 is 1.0 g/L, and the optimum concentration of PMS is 1.0 mM.
Example 5: comparison of degradation efficiency of sulfur-doped carbon material activated monopersulfate on different types of organic pollutants
Following the procedure of example 1, the suitability of sulfur-doped carbon materials for activating monopersulfate to degrade different types of organic contaminants was compared. In the nSAC8/PMS system, the concentrations of nSAC8 and PMS were 1.0 g/L and 1.0 mM, respectively, and the concentrations of organic contaminants Sulfamethoxypyrimidine (SMX), bisphenol A (BPA) and phenol were 100. mu.M, and the results are shown in FIG. 5.
The sulfur-doped carbon material can activate monopersulfate to realize efficient degradation of various pollutants. Within 4 h, the removal rate of sulfamethoxydiazine, bisphenol A and phenol can be 100%, which indicates that the invention is suitable for the degradation of various organic pollutants.
Example 6: stability of sulfur-doped carbon materials
According to the procedure of example 1, the stability of the sulfur-doped carbon material was examined, and 4 catalytic cycle experiments were performed in the nSAC8/PMS/DEP system at concentrations of nSAC8, PMS, and DEP of 1 g/L, 1 mM, and 100. mu.M, respectively. The results are shown in FIG. 6.
The sulfur-doped carbon material shows a high degradation effect on DEP in 4 catalytic cycles, and can still catalyze PMS to degrade 38% of DEP after 4 catalytic cycles, so that the sulfur-doped carbon material is stable in the aspect of activating monopersulfate and can be recycled for multiple times.
Claims (9)
1. A process for the preparation of a non-metallic persulfate-activating composition, characterized by the steps of: adding activated carbon, sulfur powder and ball milling balls into a zirconia ball milling tank, naturally cooling to room temperature after ball milling is finished, sieving and separating to obtain a sulfur-doped carbon material with micro-nano size, wherein the size of the sulfur-doped carbon material with micro-nano size is 200-600 nm, and the pore volume is 0.023 cm3G, average pore diameter of 1.62 nm, specific surface area of 12.19 m2/g。
2. The method of claim 1 for preparing a persulfate-activated non-metallic composition, wherein the ball milling time is: the ball milling is carried out for 15 min each time, the suspension is carried out for 15 min, the circulation is carried out for 96 times, and the ball milling is carried out for 24 h in total.
3. The method for preparing the persulfate-activated nonmetal composition according to claim 1, wherein the ball-milling balls are prepared in the following ratio: 40 g of 10 mm pellets, 50 g of 7 mm pellets, 40 g of 6 mm pellets, 30 g of 3 mm pellets.
4. The method for preparing the persulfate-activated nonmetal composition according to claim 1, wherein the ball milling material ratio is 40:1, the mass of a sample in one ball milling is 4 g, and the rotation speed is 450 rpm.
5. A persulfate-activated non-metallic composition produced by the process of any one of claims 1 to 4.
6. The non-metallic composition for activating persulfates of claim 5, wherein the material has a sulfur content of 6.08 at%.
7. Use of the non-metallic composition of a persulfate as set forth in claim 5 for the treatment of organic pollutants.
8. Use according to claim 7, characterized in that the organic contaminants are diethyl phthalate, bisphenol A, sulfamethoxydiazine and phenol, the concentration of contaminants being 100 μ M.
9. Use according to claim 7, characterized by the steps of: adding monopersulfate and sulfur-doped carbon material into the waste water of the organic pollutants, wherein the concentrations of the monopersulfate and the sulfur-doped carbon material are 0.5-5.0 mM and 0.5-2.0 g/L respectively, and carrying out oscillation reaction for 4 hours.
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