CN114984956A - Preparation method of magnetic sludge biochar applied to activated peroxymonosulfate for efficiently degrading sulfamethoxazole in water - Google Patents
Preparation method of magnetic sludge biochar applied to activated peroxymonosulfate for efficiently degrading sulfamethoxazole in water Download PDFInfo
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- sulfamethoxazole
- sludge biochar
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- 229960005404 sulfamethoxazole Drugs 0.000 title claims abstract description 89
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000010802 sludge Substances 0.000 title claims abstract description 61
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical class [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000000593 degrading effect Effects 0.000 title description 5
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 31
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 31
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 31
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000005389 magnetism Effects 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 229910002056 binary alloy Inorganic materials 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 230000005294 ferromagnetic effect Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000005307 ferromagnetism Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 229920006132 styrene block copolymer Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 7
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical class [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- 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
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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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
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- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a preparation method of magnetic sludge biochar capable of being applied to activating peroxymonosulfate to efficiently degrade sulfamethoxazole, and particularly relates to the method for preparing the magnetic sludge biochar (ASBC) by putting Sludge Biochar (SBC) prepared by high-temperature pyrolysis into a beaker containing ferrous sulfate and ferric chloride solution and performing coprecipitation. The magnetic sludge biochar ASBC prepared by the invention can be used for activating a peroxymonosulfate system to realize the high-efficiency degradation of sulfamethoxazole in water, the removal rate of sulfamethoxazole in water can reach 96.1% after the reaction is carried out for 60min, and the strong magnetism of the magnetic sludge biochar ASBC can realize the cyclic utilization of sulfamethoxazole in water.
Description
Technical Field
The invention relates to the technical field of biochar preparation and water treatment, in particular to a preparation method of ferrous sulfate and ferromagnetic chloride sludge biochar applied to activated peroxymonosulfate for efficiently degrading sulfamethoxazole.
Background
In recent years, with the rapid development of society, water pollution is more and more serious, and the sustainable development of society is seriously influenced. Among the water pollutants, antibiotic pollutants derived from drugs and Personal Care Products (PPCPs) are difficult to remove and can accumulate in natural water, are called as novel pollutants, and have become a hot spot in water treatment research.
According to the market research results, China has become the first producing and using country of antibiotics in the world. Sulfamethoxazole (SMX) is a broad-spectrum antibiotic of sulfonamides, is white crystal powder, is difficult to dissolve in water, is easy to dissolve in acid and alkali, is mainly used for treating urinary tract infection, bird droppings and the like, has good antibacterial effect on gram-negative bacteria and gram-positive bacteria, but most of the Sulfamethoxazole which is not metabolized is discharged out of the body along with feces and urine after the medicament is taken by human bodies and animals, and then enters the water environment in different modes. At present, the antibiotic has become an antibiotic with high detection frequency and high content in water. Sulfamethoxazole has been listed as one of the most common 30 wastewater pollutants by the U.S. geological survey due to its frequent detection in aqueous environments. A large number of documents report that sulfonamides in the environment have toxic effects on microorganisms and aquatic organisms. Therefore, the research and development of the technology for removing the sulfamethoxazole in the water environment with high efficiency, low cost and good effect is very important.
The current main removal method of sulfamethoxazole comprises the following steps: biological methods, adsorption methods, advanced oxidation methods, and the like. Wherein, the period required by microbial degradation is long, the requirement on the growth environment is strict, and drug resistance genes can be generated, which is not beneficial to large-scale application; adsorption method althoughThe method has the advantages of simple operation, low cost, high efficiency, no generation of toxic by-products and the like, but can not realize the complete removal of the sulfamethoxazole in the environment. The persulfate-based advanced oxidation technology is considered to be a promising technology capable of efficiently removing sulfamethoxazole in water. SO generated by activating Peroxodisulfate (PDS) or Peroxomonosulfate (PMS) with transition metal, biochar, heat, electricity, etc 4 ·－ Has long half-life (28-40 μ s) and oxidation-reduction potential (E) 0 2.5-3.1V), wherein PMS is more easily activated due to its asymmetric structure. Among a plurality of activation methods, the biochar material has the advantages of high specific surface area, good pore structure, adjustable surface chemical property, good chemical stability, environmental protection and the like, so that the biochar material is used as a novel catalyst and is widely applied to the activation of PMS. The sludge is the main solid waste generated by sewage treatment plants, and is an ideal raw material for preparing the biochar due to the rich organic matters, and statistics shows that more than 5400 sewage treatment plants which are normally operated in China generate sludge with the yield of more than 6.0 multiplied by 10 8 Ton. The main treatment methods of the sludge include landfill, incineration and the like, and certain pollution is caused to the environment, for example, leachate generated after landfill can pollute underground water and soil, and harmful gas generated by incineration can pollute the atmosphere. Therefore, the sludge is pyrolyzed under the condition of oxygen limitation to produce sludge biochar, so that the generation of harmful gas can be reduced, and the sludge can be utilized to achieve the aim of environmental protection. However, the activation efficacy of sludge biochar on persulfate is limited by its limited pore structure and oxygen-containing functional groups. Studies have shown that the surface area, porosity and number of oxygen-containing functional groups of biochar can be increased by ferrous sulfate and iron chloride magnetism. Based on the activation characteristics of ferrous sulfate and ferric chloride, the ferrous sulfate and the ferric chloride are not combined to be used for modifying the biochar so as to improve the catalytic performance of the biochar, and the ferrous sulfate and the ferric chloride are combined to be used for modifying the sludge biochar so as to improve the catalytic performance of the biochar. The prepared ferrous sulfate and ferromagnetic chloride sludge biochar has the potential of activating peroxymonosulfate to efficiently degrade sulfamethoxazole, and the high magnetic sensitivity of the biochar can ensure the quick and efficient recovery of the biochar to realizeAnd (4) recycling the catalyst.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the magnetic sludge biochar capable of activating peroxymonosulfate and efficiently degrading sulfamethoxazole. The treatment technology can realize the resource utilization of municipal sludge, and can realize the efficient removal of sulfamethoxazole in water, thereby achieving the purpose of producing sewage by using waste.
In order to solve the technical problems, the invention provides a preparation method of ferrous sulfate and ferric chloride magnetic sludge biochar capable of activating peroxymonosulfate to efficiently degrade sulfamethoxazole, which comprises the following steps:
(1) preparing sludge biochar: cleaning and drying sludge to constant weight by using deionized water, then pyrolyzing at high temperature, grinding and sieving to obtain sludge biochar SBC;
(2) preparing the sludge biochar by using ferrous sulfate and iron chloride: and (2) mixing and dispersing the sludge biochar SBC obtained in the step (1), ferrous sulfate and ferric chloride in water to obtain a mixed solution, heating and stirring, then cooling, dropwise adding a NaOH solution and stirring, drying to constant weight after the reaction is finished, calcining, then washing and drying with deionized water, grinding and sieving to obtain ferrous sulfate and ferromagnetic chloride sludge biochar ASBC.
Preferably, the preparation method of the sludge biochar capable of activating the peroxymonosulfate to efficiently degrade the sulfamethoxazole and the ferric chloride magnet further comprises the following technical characteristics of part or all of the following steps:
as an improvement of the technical scheme, in the step (1), the drying temperature is 60-90 ℃; the pyrolysis condition is that the nitrogen flow rate is 0.2-0.8L/min, the heating rate is 5-15 ℃/min, and the pyrolysis is continuously carried out for 60-120min under the condition of 300-700 ℃; grinding, and sieving with 60-200 mesh sieve.
As an improvement of the above technical scheme, in the step (2), the sludge biochar SBC: FeSO 4 ·7H 2 0：FeCl 3 ·6H 2 O ═ 6.32-10.32 g: 1.66-3.66 g: 4.66-6.66g, the volume of water is 150-; reaction stripThe parts are as follows: continuously stirring and heating the mixed solution to 55-60 ℃, cooling the solution to 35-40 ℃, dropwise adding NaOH solution until the pH value reaches 10-12, stirring for 60-120min, drying at 60-90 ℃, calcining at 300-700 ℃, grinding, and sieving with a 60-200 mesh sieve.
The ferrous sulfate and the ferromagnetic chloride sludge biochar are prepared by any one of the methods.
The application of the ferrous sulfate and the ferromagnetic chloride sludge biochar in activating the peroxymonosulfate to efficiently degrade sulfamethoxazole is characterized by comprising the following steps of: the prepared magnetic sludge biochar ASBC is used as a catalyst for activating peroxymonosulfate to degrade sulfamethoxazole, and after the degradation process is finished, the solution after the sulfamethoxazole is removed and the ASBC which achieves the degradation balance are obtained by filtering.
Preferably, the application of the sludge biochar containing ferrous sulfate and ferric chloride provided by the invention in activating peroxymonosulfate to efficiently degrade sulfamethoxazole further comprises part or all of the following technical characteristics:
as the improvement of the technical scheme, the concentration of sulfamethoxazole in the sulfamethoxazole solution is 2-6mg/L, pH and is 3-11; the adding amount of the ferrous sulfate and the ferric chloride magnetic sludge biochar ASBC is 0.05-0.2 g/L; the concentration of the peroxymonosulfate is 0.1 to 5 mmol/L.
The method for regenerating the sludge biochar by using the ferrous sulfate and the ferromagnetic chloride comprises the following steps: and (3) performing magnetic separation on the ASBC which reaches the degradation balance, performing regeneration treatment for 20min by using ethanol, cleaning for 5-6 times by using ultrapure water, and drying the ASBC in an oven at the temperature of 50 ℃ to obtain the regenerated ASBC.
As an improvement of the technical scheme, the regenerated ASBC has continuous and stable degradation capability in subsequent cycle use, and the removal rate of sulfamethoxazole in a binary system after 5 cycles is still more than 83.3 percent
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the method for efficiently degrading sulfamethoxazole by activating the peroxymonosulfate by using the ferrous sulfate and the ferromagnetic chloride sludge biochar is provided, so that the resource utilization of the sludge can be realized, and the sulfamethoxazole in water can be efficiently degraded and removed.
(1) The prepared ferrous sulfate and ferromagnetic chloride sludge biochar ASBC has a simple preparation process, and can activate the potassium monopersulfate PMS to remove sulfamethoxazole with the concentration of 5mg/L within 60min to reach 96.1%.
(2) Compared with other technologies (adsorption, microbial degradation and the like), the prepared ferrous sulfate and ferromagnetic chloride sludge biochar ASBC can realize the efficient mineralization of sulfamethoxazole in an activated Potassium Monopersulfate (PMS) system, so that the sulfamethoxazole is completely removed, meanwhile, the high magnetism of the activated ferric sulfate and ferromagnetic chloride sludge biochar ASBC can realize the efficient separation and cyclic utilization of the degraded catalyst and the aqueous solution, and the technology has the prospect of simple operation, low cost and large-scale application.
The foregoing description is only an overview of the technical solutions of the present invention, and in order that the technical means of the present invention may be clearly understood, and the technical solutions may be implemented in accordance with the content of the description, and in order that the above and other objects, features, and advantages of the present invention may be more clearly understood, the following detailed description is given with reference to the preferred embodiments.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1(a) shows the removal rate of sulfamethoxazole at 5mg/L at 0-60min for SBC and ASBC at a dose of 20 mg;
FIG. 1(b) is the removal rate of 5mg/L sulfamethoxazole at 0-60min at PMS concentration of 1mmol/L for SBC and ASBC at a dose of 20 mg;
FIG. 2(a) shows the removal rate of sulfamethoxazole of 5mg/L at 0-60min for ASBC (20mg), PMS (1mmol/L) alone or in combination;
FIG. 2(b) is the effect of PMS concentration (0.1-5mmol/L) in ASBC/PMS system on the removal rate of sulfamethoxazole of 5mg/L at 0-60 min;
FIG. 3(a) is the effect of humic acid (1-10mg/L) on the removal rate of sulfamethoxazole of 5mg/L in ASBC/PMS system at 0-60 min;
FIG. 3(b) is the effect of pH (3-11) on the removal rate of sulfamethoxazole of 5mg/L at 0-60min in an ASBC/PMS system;
FIG. 4(a, b, c, d, e and f) is K 2 CO 3 、K 2 SO 4 、KCl、KH 2 PO 4 、KNO 3 And KHCO 3 The concentration of (b) is 1, 5 and 10mmol/L, the influence on the removal rate of sulfamethoxazole of 5mg/L in an ASBC/PMS system is 0-60 min; (ii) a
FIG. 5 is a graph of the ability of regeneration of ASBC to degrade sulfamethoxazole.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example one: drying the municipal sludge in an oven at 80 ℃ to constant weight, and transferring the sludge into a high-temperature tube furnace (N) 2 The flow rate is 0.5L/min, the heating rate is 10 ℃/min) and the sludge is pyrolyzed for 120min at the temperature of 600 ℃, and the sludge is ground and sieved by a 100-mesh sieve to obtain the sludge biochar SBC. Taking 10.32g of SBC and 3.66g of FeSO 4 ·7H 2 0 and 6.66g FeCl 3 ·6H 2 O mix was dispersed in a beaker containing 200mL of ultrapure water. Stirring was continued on a magnetic stirrer and the mixture was heated to 60 ℃ to ensure Fe 2+ And Fe 3+ Are able to penetrate into SBCs. The solution was then cooled to 40 ℃ and NaOH solution was added dropwise until pH 11 was reached. Stirring the suspension for 60min, drying at 60 deg.C, calcining at 600 deg.C, grinding, and sieving with 100 mesh sieve.
Example two: SBC and ASBC with the dose of 20mg are added into sulfamethoxazole solution with the concentration of 5mg/L (the volume is 50mL) or sulfamethoxazole solution with the concentration of 5mg/L (the volume is 50mL) and containing 1mol/L PMS, the mixture is stirred by a magnetic stirrer with the speed of 500r/min, samples are taken at the set time (0-60min), the residual concentration of the sulfamethoxazole is measured by utilizing high performance liquid chromatography-mass spectrometry, and the removal rate of the sulfamethoxazole at different times is calculated.
As shown in FIG. 1(a), the removal rate of sulfamethoxazole by biochar is improved with the increase of reaction time, and the removal capability is shown as follows: ASBC > SBC, the removal rate of sulfamethoxazole by ASBC at 60min was 29.5%. As can be seen from FIG. 1(b), the biochar can activate PMS to improve the removal capability of sulfamethoxazole, wherein the removal capability of the ASBC/PMS system to sulfamethoxazole is stronger than that of the SBC/PMS system, and the removal rate at 60min is 96.1%.
Example three: comparing the removal effect of the univalent (ASBC (20mg) and PMS (1mmol/L)) and the binary (ASBC (20mg) + PMS (1mmol/L)) systems on a 5mg/L (volume is 50mL) sulfamethoxazole solution at 0-60min, stirring the systems by a magnetic stirrer at 500r/min, sampling the systems at set time (0-60min), measuring the residual concentration of sulfamethoxazole by using high performance liquid chromatography-mass spectrometry, and calculating the removal rate of sulfamethoxazole at different times.
As can be seen from FIG. 2(a), the removal rate and the removal rate of sulfamethoxazole by the binary system (ASBC (20mg) + PMS (1mmol/L)) are significantly higher than those of the unitary system, and the removal rate of sulfamethoxazole can reach 96.1% after reaction for 60min, which indicates that ASBC can activate PMS to efficiently degrade sulfamethoxazole.
Example four: the dosage of ASBC in a binary system is 20mg, the concentration of sulfamethoxazole is 5mg/L, the volume is 50mL, the concentration of PMS is set to be 0.1, 0.5, 1, 2 and 5mmol/L, stirring is carried out in a magnetic stirrer of 500r/min, sampling is carried out at set time (0-60min), the residual concentration of sulfamethoxazole is determined by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the concentration of PMS in the binary system on the removal of sulfamethoxazole is researched.
As shown in FIG. 2(b), the removal rate of sulfamethoxazole in the binary system is increased with the increase of PMS concentration, and the removal rate of sulfamethoxazole is close to 100% after the reaction is carried out for 45min when the PMS concentration is 5 mmol/L. When PMS concentration is 1mmol/L and 5mmol/L, the removal rate of sulfamethoxazole is close to 100% without obvious difference when the PMS is reacted for 60 min.
Example five: the dosage of ASBC in a binary system is 20mg, the concentration of PMS is 1mmol/L, the concentration of sulfamethoxazole is 5mg/L, the volume is 50mL, the concentration of Humic Acid (HA) is set to be 0, 1, 5 and 10mg/L, stirring is carried out in a magnetic stirrer at 500r/min, sampling is carried out at set time (0-60min), the residual concentration of sulfamethoxazole is determined by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the concentration of humic acid in the binary system on the removal of sulfamethoxazole is researched.
As is clear from FIG. 3(a), the removal rate of sulfamethoxazole decreased with the increase of humic acid concentration in the binary system, and when HA concentration was 10mg/L, the removal rate of sulfamethoxazole was 69.9% at 60min of the reaction.
Example six: the dosage of ASBC in a binary system is 20mg, the concentration of PMS is 1mmol/L, the concentration of sulfamethoxazole is 5mg/L, the volume is 50mL, the pH value of the solution is set to be 3, 5, 7, 9 and 11, the solution is stirred in a magnetic stirrer at 500r/min, sampling is carried out at set time (0-60min), the residual concentration of sulfamethoxazole is determined by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the pH value of the solution in the binary system on the removal of the sulfamethoxazole is researched.
As shown in FIG. 3(b), the removal rate of sulfamethoxazole by the binary system was different depending on the pH of the solution. The removal rate of sulfamethoxazole by the binary system under the acidic condition is higher than that under the alkaline condition, and when the pH of the solution is 3, the removal rate of sulfamethoxazole by the binary system is 96.7 percent at most.
Example seven: in a binary system, the dosage of ASBC is 20mg, the concentration of PMS is 1mmol/L, the concentration of sulfamethoxazole is 5mg/L, the volume is 50mL, K 2 CO 3 、K 2 SO 4 、KCl、KH 2 PO 4 、KNO 3 And KHCO 3 When the concentration of (1) and (5) and the concentration of (10) were reached, the mixture was stirred by a magnetic stirrer at 500r/min, sampled at a set time (0-60min), and the residual concentration of sulfamethoxazole was measured by high performance liquid chromatography-mass spectrometry to investigate the effect of coexisting inorganic ions on the removal of sulfamethoxazole.
As can be seen from FIG. 4(a, b, c, d, e and f), K 2 CO 3 And KHCO 3 The inhibition of the ability of the binary system to degrade sulfamethoxazole is enhanced with the increase of the concentration thereof, wherein K 2 CO 3 The inhibitory effect of the compound is stronger than that of KHCO 3 。K 2 SO 4 、KCl、KH 2 PO 4 、KNO 3 The inhibition effect on the binary system degradation sulfamethoxazole is not obvious and can be basically ignored.
Example eight: in a binary system, the dosage of ASBC is 20mg, the concentration of PMS is 1mmol/L, the concentration of sulfamethoxazole is 5mg/L, the volume is 50mL, the mixture is stirred by a magnetic stirrer at 500r/min, a sample is taken when the reaction is balanced (60min), and the residual concentration of sulfamethoxazole is determined by utilizing high performance liquid chromatography-mass spectrometry. And (3) carrying out magnetic separation on the ASBC which reaches the degradation balance, carrying out regeneration treatment for 20min by using ethanol (analytically pure), cleaning for 5-6 times by using ultrapure water, drying the ASBC in an oven with the temperature of 50 ℃, and then carrying out the degradation experiment again. The regeneration and degradation capacity of the ASBC was determined by repeating the above 5 times.
As can be seen from FIG. 5, the ethanol treatment can maintain the continuous and stable degradation capability of the ASBC in the subsequent cycle use, and the removal rate of sulfamethoxazole in the binary system is still 83.3% after 5 cycles.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (8)
1. A preparation method of magnetic sludge biochar applied to activating peroxymonosulfate to efficiently degrade sulfamethoxazole is characterized by comprising the following steps:
(1) preparing sludge biochar: cleaning and drying sludge to constant weight by using deionized water, then pyrolyzing at high temperature, grinding and sieving to obtain sludge biochar SBC;
(2) preparing the sludge biochar by using ferrous sulfate and iron chloride: and (2) mixing and dispersing the sludge biochar SBC obtained in the step (1), ferrous sulfate and ferric chloride in water to obtain a mixed solution, heating and stirring, then cooling, dropwise adding a NaOH solution and stirring, drying to constant weight after the reaction is finished, calcining, then washing and drying with deionized water, grinding and sieving to obtain ferrous sulfate and ferromagnetic chloride sludge biochar ASBC.
2. The preparation method of the sludge biochar containing ferrous sulfate and ferric chloride for activating peroxymonosulfate to efficiently degrade sulfamethoxazole, as claimed in claim 1, is characterized in that: in the step (1), the drying temperature is 60-90 ℃; the pyrolysis condition is that the nitrogen flow rate is 0.2-0.8L/min, the heating rate is 5-15 ℃/min, and the pyrolysis is continuously carried out for 60-120min at the temperature of 300-; grinding, and sieving with 60-200 mesh sieve.
3. The preparation method of the sludge biochar containing ferrous sulfate and ferromagnetic chloride, which is applied to the efficient degradation of sulfamethoxazole by activated peroxymonosulfate, according to claim 1, is characterized by comprising the following steps: in the step (2), the sludge biochar SBC: FeSO 4 ·7H 2 0：FeCl 3 ·6H 2 O ═ 6.32-10.32 g: 1.66-3.66 g: 4.66-6.66g, the volume of water is 150-; the reaction conditions are as follows: continuously stirring and heating the mixed solution to 55-60 ℃, cooling the solution to 35-40 ℃, dropwise adding NaOH solution until the pH value reaches 10-12, stirring for 60-120min, drying at 60-90 ℃, calcining at 300-700 ℃, grinding, and sieving with a 60-200 mesh sieve.
4. The utility model provides a ferrous sulfate and ferromagnetism chloride mud biochar which characterized in that: the ferrous sulfate and the ferric chloride magnetic sludge biochar are prepared by any method of claims 1-3.
5. The application of the ferrous sulfate and the ferromagnetic chloride sludge biochar in activating the peroxymonosulfate to efficiently degrade sulfamethoxazole is characterized by comprising the following steps of: the prepared magnetic sludge biochar ASBC is used as a catalyst for activating peroxymonosulfate to degrade sulfamethoxazole, and after the degradation process is finished, the solution after the sulfamethoxazole is removed and the ASBC which achieves the degradation balance are obtained by filtering.
6. The application of the sludge biochar based on ferrous sulfate and iron chloride in the efficient degradation of sulfamethoxazole by activated peroxymonosulfate, as claimed in claim 5, is characterized in that: the concentration of sulfamethoxazole in the sulfamethoxazole solution is 2-6mg/L, pH and is 3-11; the adding amount of the ferrous sulfate and the ferric chloride magnetic sludge biochar ASBC is 0.05-0.2 g/L; the concentration of the peroxymonosulfate is 0.1 to 5 mmol/L.
7. The method for regenerating sludge biochar based on ferrous sulfate and iron chloride magnetism as claimed in any one of claims 5 to 6, characterized by comprising the following steps: and (3) performing magnetic separation on the ASBC which reaches the degradation balance, performing regeneration treatment for 20min by using ethanol, cleaning for 5-6 times by using ultrapure water, and drying the ASBC in an oven at the temperature of 50 ℃ to obtain the regenerated ASBC.
8. The method for regenerating sludge biochar based on ferrous sulfate and iron chloride magnetism as claimed in claim 7, wherein: the regenerated ASBC has continuous and stable degradation capability in subsequent cycle use, and the removal rate of the binary system to sulfamethoxazole is still more than 83.3 percent after 5 cycles.
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