CN112403465A - Preparation of biochar-based catalyst and method for repairing biochar-based catalyst in antibiotics - Google Patents
Preparation of biochar-based catalyst and method for repairing biochar-based catalyst in antibiotics Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 18
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 17
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 59
- 239000004098 Tetracycline Substances 0.000 claims abstract description 58
- 229960002180 tetracycline Drugs 0.000 claims abstract description 58
- 229930101283 tetracycline Natural products 0.000 claims abstract description 58
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 58
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
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- 230000035484 reaction time Effects 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 229910052785 arsenic Inorganic materials 0.000 claims description 8
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- 239000007787 solid Substances 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 claims description 6
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- 238000005067 remediation Methods 0.000 claims 2
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- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- -1 aluminum ions Chemical class 0.000 abstract description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000001035 drying Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
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- 238000004140 cleaning Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- 239000010457 zeolite Substances 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
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/16—Reducing
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
本发明公开了一种生物炭基催化剂的制备及其在抗生素的修复方法，首先采用预处理后的硫铁矿酸性矿山废水作为农业废弃物柚子皮生物炭的改性剂。随后，生物炭质上的铁铜铝离子在柚子皮提取液的还原作用下，形成高活性生物炭基零价铁铜铝三元金属复合催化剂材料，与过硫酸盐构建出一种新型Fenton氧化技术体系，并用于水体抗生素四环素和诺氟沙星的单一和同步高效降解去除。在反应时间为60 min内，四环素和诺氟沙星的单一去除率分别高达98.85%和96.52%；在同步去除时，去除率也能达到80%以上。并且，此种高活性生物炭基Fenton催化剂具有良好的稳定性。本发明既实现了酸性矿山废水和农业废弃物柚子皮的处置和资源化，又实现了多种抗生素的单一和同步降解去除。
The invention discloses a preparation method of a biochar-based catalyst and a method for repairing it in antibiotics. First, the pretreated pyrite acid mine wastewater is used as a modifier of agricultural waste grapefruit peel biochar. Subsequently, the iron, copper and aluminum ions on the biochar were reduced by the grapefruit peel extract to form a highly active biochar-based zero-valent iron-copper-aluminum ternary metal composite catalyst material, and a new type of Fenton oxidation was constructed with persulfate. Technology system, and used for single and simultaneous efficient degradation and removal of water antibiotics tetracycline and norfloxacin. Within 60 min of reaction time, the single removal rates of tetracycline and norfloxacin were as high as 98.85% and 96.52%, respectively; the removal rates could also reach more than 80% during simultaneous removal. Moreover, this highly active biochar-based Fenton catalyst has good stability. The invention not only realizes the disposal and resource utilization of acid mine wastewater and agricultural waste pomelo peels, but also realizes the single and simultaneous degradation and removal of multiple antibiotics.
Description
Technical Field
The invention relates to the technical field of resource utilization of solid waste and waste water and water pollution treatment in environmental engineering, in particular to a preparation method of a charcoal-based catalyst and a repair method of the charcoal-based catalyst in antibiotics.
Background
The adsorption method is widely applied to the high-efficiency removal of antibiotics in water, and common adsorbents comprise active carbon, kaolin, zeolite, biochar and the like. Among these adsorbents, the most pertinent research on biochar is popular, biochar is a product formed by high-temperature oxygen-limited pyrolysis of a biomass raw material, and has the advantages of wide source and low cost, but the original biochar is poor in pollutant adsorption performance, and needs to be modified to improve the adsorption performance. Among them, the modification of iron salts which are environment-friendly is the most studied, however, iron salts used at present are basically commercialized and have high cost, and iron-rich cheap raw materials are urgently sought to replace the commercialized iron salts as iron modifiers.
In recent years, attention has been paid to environmental pollution caused by pyrite acid mine wastewater, which is mine wastewater with a pH value of 2-3, a high concentration of iron ions and some heavy metal ions such as copper, manganese and the like. The waste water has two characteristics of high acidity and high iron content, which are required for modifying acid and iron salt in a common modification method of the biochar. Therefore, if the modified biological charcoal is used as a modifier of agricultural waste shaddock peel biological charcoal, a novel biological charcoal preparation method is formed, and resource utilization of acid mine wastewater is realized. However, the adsorption of antibiotics by the iron-modified biochar has a limitation, and the iron-modified biochar only transfers the antibiotics in the water phase to the surface of the carbon and is not really degraded and removed. The high-reactivity nano zero-valent iron is considered to be the most promising environment repairing material at present, has very strong reactivity, can remove most pollutants, and is widely applied to the repairing of water and soil pollutants. However, in the process of preparing the nano zero-valent iron, highly toxic sodium borohydride is used as a reducing agent, so that an environment-friendly reducing agent is urgently needed to replace the sodium borohydride to prepare the nano zero-valent iron. In recent years, researches report that phenolic substances in some plants have strong reducibility, can be used for replacing sodium borohydride to prepare nano zero-valent iron, is considered to be a green preparation method of nano zero-valent iron, and solves the problem of secondary environmental pollution caused by sodium borohydride.
At present, the Fenton method in the advanced oxidation technology is considered as a treatment process capable of degrading antibiotic pollution most efficiently, in particular to a Fenton technology based on sulfate radicals, and the technology can realize efficient degradation of antibiotics in a wide pH range and under mild conditions. Biochar and an iron-containing substance are usually used as a Fenton catalyst to activate persulfate so as to generate high-activity sulfate radicals for degrading and removing organic pollutants.
However, a preparation method of a biochar-based catalyst and a patent technology for constructing a Fenton oxidation technology system with persulfate in an antibiotic repair method have not been reported so far.
Disclosure of Invention
The invention provides a preparation method of a biochar-based catalyst and a repair method of the biochar-based catalyst in antibiotics, which can effectively solve the problems in the background art.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a preparation method of a biochar-based catalyst and a repair method of the biochar-based catalyst in antibiotics comprise the following steps:
s1: placing agricultural waste shaddock peel in deionized water, repeatedly cleaning surface impurities for 2-3 times, drying at 75-100 deg.C to constant weight, grinding, and sieving with 80 mesh sieve;
s2: then, under the protection of nitrogen, the temperature is raised to 600 ℃ in a tube furnace at the speed of 5 ℃/min, and the pyrolysis is kept for 120 min;
s3: naturally cooling, grinding the obtained solid, and sieving with a 80-mesh sieve to obtain the shaddock peel biochar;
s4: in a three-neck flask, mixing 200 mL of acidic mine wastewater with the iron mass concentration of 0.89-1.02 g/L after filtration pretreatment and 10-20 g of shaddock peel biochar, stirring for 300-;
s5: then under the protection of nitrogen, slowly adding the newly prepared shaddock peel extracting solution with a certain concentration into the mixed solution for continuous reaction, and keeping stirring for 60-120 min;
s6: finally, drying the solid in vacuum at 70-90 ℃ for 100-120 min, grinding the obtained solid and sieving the ground solid by a sieve of 80 meshes to obtain the high-activity biochar-based Fenton catalyst material;
s7: and (2) in a stirring reactor, adding a biochar material into the polluted water containing tetracycline and/or norfloxacin, reacting for 60 min, and removing the tetracycline and norfloxacin singly or synchronously.
As a further preferable scheme of the invention, in the step S7, the mass concentrations of tetracycline and norfloxacin in the polluted water body are both 0-60 mg/L; the dosage of the biochar-based catalyst material is 0-2.0 g/L; the dosage of the persulfate or the hydrogen peroxide is 0-2.0 mM; the mass concentration of the heavy metal arsenic is 0-20 mg/L.
As a further preferred embodiment of the present invention, in step S7, before adding the biochar-based catalyst material, it must be ground and sieved to ensure that its particles are within the range of less than 178 μm.
As a further preferable scheme of the invention, in step S7, before adding the biochar-based catalyst material, the pH value of the water body is adjusted to 3.0-8.0.
As a further preferable scheme of the invention, the dosage of the biochar iron source material added into the water body containing tetracycline and norfloxacin is 1.5 g/L.
As a further preferable scheme of the invention, the dosage of the persulfate or the hydrogen peroxide added into the water body containing the tetracycline and the norfloxacin is 1.0 mM.
As a further preferable scheme of the invention, the mass concentration of the tetracycline in the polluted water body is 15 mg/L; the mass concentration of norfloxacin is 30 mg/L.
As a further preferable scheme of the invention, the mass concentration of heavy metal arsenic in the polluted water body is adjusted to be 0-20 mg/L when the polluted water body coexists with tetracycline or norfloxacin.
As a further preferable scheme of the invention, in the mixed solution, the mass concentration of the tetracycline in the polluted water body is 15 mg/L; the mass concentration of norfloxacin is 5-60 mg/L.
As a further preferable scheme of the invention, the biochar-based Fenton catalyst material is repeatedly used for 5 times.
Compared with the prior art, the invention provides a preparation method of a biochar-based catalyst and a repair method of the biochar-based catalyst in antibiotics, and the method has the following beneficial effects:
1. according to the invention, agricultural waste shaddock peel is used as a biochar raw material, and shaddock peel extracting solution is used as a reducing agent to replace toxic sodium borohydride so as to convert various metal ions of the acidic mine wastewater into high-activity zero-valent metal catalyst particles, so that the recycling of the agricultural waste shaddock peel and the acidic mine wastewater is realized to the maximum extent.
2. The high-activity biochar-based Fenton catalyst has the catalytic characteristics of multi-metal, and a novel Fenton oxidation technology system constructed by the high-activity biochar-based Fenton catalyst and persulfate (potassium persulfate) presents high-efficiency performance of single and synchronous removal of antibiotics tetracycline and norfloxacin in a water body.
3. The novel Fenton oxidation technology system can effectively remove organic matters such as antibiotics, dyes and polycyclic aromatic hydrocarbon substances in water and soil in most scenes.
Drawings
Fig. 1 is a scanning electron microscope image of the high activity biochar-based Fenton catalyst of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the following examples, the biochar-based Fenton catalyst particles were isolated by filtration and then measured by HPLC before the tetracycline and norfloxacin concentrations in the water were measured.
Example 1:
the preparation method using the high activity biochar-based Fenton catalyst is described in detail in this example. In this example, the preparation procedure was as follows:
firstly, placing agricultural waste shaddock peel in deionized water, repeatedly cleaning surface impurities for 2-3 times, drying at 75-100 ℃ to constant weight, grinding and sieving with an 80-mesh sieve, then heating to 600 ℃ at the speed of 5 ℃/min in a tubular furnace under the protection of nitrogen, keeping pyrolysis for 120 min, naturally cooling, grinding the obtained solid and sieving with an 80-mesh sieve to obtain the shaddock peel biochar. Then, in a three-mouth flask, mixing 200 mL of acidic mine wastewater with the iron mass concentration of 0.89-1.02 g/L after filtration pretreatment and 10-20 g of shaddock peel biochar, stirring for 300-360 min, then slowly adding a newly prepared shaddock peel extracting solution with a certain concentration into the mixed solution under the protection of nitrogen, continuing to react for 60-120 min, finally drying for 120 min under vacuum at 70-90 ℃ for 100-120 min, grinding the obtained solid, and sieving with a 80-mesh sieve to obtain the high-activity biochar-based Fenton catalyst material.
Example 2:
in this example, comparing the single removal and degradation effects of different biochar-based Fenton catalyst materials on tetracycline and norfloxacin, the steps are as follows: respectively adding the following five combined materials or reagent combinations into a water body polluted by tetracycline or norfloxacin: persulfate, biochar-based Fenton catalyst, biochar/persulfate, and biochar-based Fenton catalyst/persulfate. A200 mL beaker is used as a reactor, a treatment object is a water body with the concentration of 100 mL tetracycline being 15 mg/L or norfloxacin being 30 mg/L, the pH of the water body is 4.0, the dosage of the catalyst material is 1.5 g/L, and the beaker is placed on a stirrer, the rotating speed is 150 rpm, and the reaction time is 60 min. Example 2 the results are shown in table 1. As can be seen from the table, the removal rate of the tetracycline and the norfloxacin by the persulfate and the biochar is low, and the removal rate of the biochar and the persulfate is improved to a certain extent by combining the biochar and the persulfate, but the effect is not obvious. Compared with biochar, the removal of tetracycline and norfloxacin by the biochar-based Fenton catalyst is improved to a certain extent, but under the biochar-based Fenton catalyst/persulfate system, tetracycline and norfloxacin are remarkably improved, and the removal rates can reach 98.85% and 96.52% respectively. The result shows that the novel biochar-based Fenton catalyst/persulfate technical system can efficiently degrade and remove tetracycline and norfloxacin.
Example 3:
the difference from example 2 is that the pH is adjusted to 3.0, 4.0, 5.0, 6.0, 7.0 and 8.0, and the tetracycline or norfloxacin is degraded and removed by using a biochar-based Fenton catalyst/persulfate system. Other conditions were the same as in example 2, and changes in tetracycline or norfloxacin in the water before and after the reaction were measured. Example 3 the results are shown in table 2. As can be seen from the table, the removal rates of tetracycline and norfloxacin decreased with increasing pH, and the removal rates under acidic conditions were greater than those under neutral and basic conditions, but both removal rates reached higher levels at pH =3.0 and 4.0, and therefore, pH =4.0 was selected as the optimum pH condition.
Example 4:
the difference from the example 3 is that the dosage of the biochar-based Fenton catalyst is adjusted to be 0.5-2.0 g/L, other conditions are the same as the example 3, and the change of tetracycline or norfloxacin in the water body before and after the reaction is measured. Example 4 the results are shown in table 3. The table shows that the removal rates of tetracycline and norfloxacin are increased along with the increase of the dosage of the biochar-based Fenton catalyst, when the dosage is 1.5 g/L, the removal rates of tetracycline and norfloxacin reach higher levels, and when the dosage is further increased, the removal rates of tetracycline and norfloxacin are not obviously improved. Therefore, 1.5 g/L is the optimum amount of catalyst.
Example 5:
except for the difference from example 3 in that the persulfate concentration was adjusted in the range of 0.5 to 2.0 mM and the other conditions were the same as in example 3, the change in tetracycline or norfloxacin in the water before and after the reaction was measured. The results of example 5 are shown in Table 4. As can be seen from the table, the removal rates of tetracycline and norfloxacin both increased with the increase of the persulfate concentration, and when the dosage was 1.0 mM, the removal rates of tetracycline and norfloxacin both reached higher levels, and when the persulfate concentration was further increased, the removal rates of both were not changed much. Therefore, 1.0 mM is the optimum persulfate concentration.
Example 6:
except for the difference from example 3 in that the concentration of hydrogen peroxide was adjusted to the range of 0.5 to 2.0 mM and the other conditions were the same as in example 3, the change in tetracycline or norfloxacin in the water body before and after the reaction was measured. Example 6 the results are shown in table 5. As shown in the table, the removal rate of tetracycline and norfloxacin increases with the increase of the hydrogen peroxide concentration, and the removal rate of tetracycline and norfloxacin only reaches about 90% when the dosage is 2.0 mM.
Compared with a biochar-based Fenton catalyst/persulfate technical system, the biochar-based Fenton catalyst/hydrogen peroxide technical system has low degradation and removal effects on tetracycline or norfloxacin. Therefore, the persulfate is more suitable for being used for constructing a novel Fenton oxidation technical system together with the biochar-based Fenton catalyst to be applied to degradation and removal of tetracycline or norfloxacin.
Example 7:
the difference from example 3 is that the concentration of the contaminant was adjusted to a range of 5 to 60 mg/L, and the change in tetracycline or norfloxacin in the water before and after the reaction was measured under the same conditions as in example 3. The results of example 7 are shown in Table 6. As shown in the table, the removal rates of tetracycline and norfloxacin decrease with the increase of the concentration of tetracycline and norfloxacin, and both the removal rates reach more than 98% when the concentration of tetracycline is less than or equal to 15 mg/L, and both the removal rates reach more than 96% when the concentration of norfloxacin is less than or equal to 30 mg/L, so that the optimal concentrations of tetracycline and norfloxacin are respectively 15 mg/L and 30 mg/L.
Example 8:
the difference from example 3 is that the concentration of coexisting heavy metal arsenic was adjusted to 0 to 20 mg/L, and the change in tetracycline or norfloxacin in the water before and after the reaction was measured under the same conditions as in example 3. The results of example 8 are shown in Table 7. As can be seen from the table, the removal rates of tetracycline and norfloxacin are reduced along with the increase of the arsenic concentration, and when the arsenic is less than or equal to 5 mg/L, the removal rates are all up to over 86 percent, and the results show that the tetracycline or norfloxacin can be degraded and removed better under the coexistence of arsenic with a certain concentration.
Example 9:
the difference from the example 3 is that the biochar-based Fenton catalyst material is reused for 5 times, other conditions are the same as the example 3, and the change of tetracycline or norfloxacin in the water body before and after the reaction is measured. The results of example 9 are shown in Table 8. As can be seen from the table, the reaction activity of the biochar-based Fenton catalyst is reduced along with the increase of the repeated use times, the removal rate of tetracycline and norfloxacin can still reach more than 91% when the biochar-based Fenton catalyst is used for the 3 rd time, and even when the biochar-based Fenton catalyst is used for the 5 th time, the removal rate of tetracycline and norfloxacin can also reach more than 73%. The result shows that the biochar-based Fenton catalyst has better repeated stability.
Example 10:
the difference from the example 3 is that the polluted water body is a mixed solution of tetracycline and norfloxacin, the fixed tetracycline concentration is 15 mg/L, the norfloxacin concentration is adjusted to be 5-60 mg/L, other conditions are the same as the example 3, and the change of the tetracycline or norfloxacin in the water body before and after the reaction is measured. Example 10 the results are shown in table 9. As can be seen from the table, in the synchronous removal process, the removal rate of tetracycline is reduced along with the increase of the concentration of the added norfloxacin, and when the norfloxacin is less than or equal to 10 mg/L, the removal rates of tetracycline and norfloxacin can reach more than 80 percent, so that a higher synchronous removal effect can be realized.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
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