CN111545212A - Double perovskite La2NiFeO6Method for catalytic degradation of antibiotic wastewater - Google Patents
Double perovskite La2NiFeO6Method for catalytic degradation of antibiotic wastewater Download PDFInfo
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- CN111545212A CN111545212A CN202010356672.1A CN202010356672A CN111545212A CN 111545212 A CN111545212 A CN 111545212A CN 202010356672 A CN202010356672 A CN 202010356672A CN 111545212 A CN111545212 A CN 111545212A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 86
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 42
- 230000015556 catabolic process Effects 0.000 title abstract description 7
- 238000006731 degradation reaction Methods 0.000 title abstract description 7
- 230000003197 catalytic effect Effects 0.000 title description 5
- 238000009987 spinning Methods 0.000 claims abstract description 96
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 13
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000011272 standard treatment Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NVIAYEIXYQCDAN-MHTLYPKNSA-N (6r,7s)-7-azaniumyl-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound S1CC(C)=C(C([O-])=O)N2C(=O)[C@H]([NH3+])[C@@H]12 NVIAYEIXYQCDAN-MHTLYPKNSA-N 0.000 description 1
- HSHGZXNAXBPPDL-HZGVNTEJSA-N 7beta-aminocephalosporanic acid Chemical compound S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H]([NH3+])[C@@H]12 HSHGZXNAXBPPDL-HZGVNTEJSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229960003022 amoxicillin Drugs 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940106164 cephalexin Drugs 0.000 description 1
- ZAIPMKNFIOOWCQ-UEKVPHQBSA-N cephalexin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)C(=C(CS3)C)C(O)=O)=CC=CC=C1 ZAIPMKNFIOOWCQ-UEKVPHQBSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 235000013613 poultry product Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B01J35/39—Photocatalytic properties
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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Abstract
The invention relates to a double perovskite La2NiFeO6The method for catalytically degrading the antibiotic wastewater comprises the following steps: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, adding nickel acetate, stirring to obtain a spinning solution, and preparing La through electrostatic spinning, oxidation and calcination2NiFeO6A catalyst; filtering antibiotic waste water, adding La2NiFeO6The catalyst is stirred to carry out photocatalytic reaction, and the wastewater after the reaction is settled and then is discharged; the invention discloses a double perovskite La2NiFeO6A method for catalyzing and degrading antibiotic wastewater, namely synthesizing double perovskite La2NiFeO6The nano material catalyst realizes the efficient degradation of the antibiotic wastewater under photocatalysis.
Description
Technical Field
The invention relates to an antibiotic wastewater treatment process, in particular to a method for treating antibiotic wastewater by using double perovskite La2NiFeO6A method for catalyzing and degrading antibiotic wastewater by using a catalyst.
Background
The source of antibiotic wastewater is very wide, the antibiotic wastewater is from life, the discharge of industrial sewage, the discharge of hospital and pharmaceutical factory wastewater, aquaculture wastewater and refuse landfill sites and the like also contain a large amount of antibiotic drugs, the antibiotics remained in the environment can enter into a biological chain through drinking water, livestock and poultry products and the like, so that corresponding antibiotic drug resistance is generated in human bodies, microorganisms in the environment generate drug resistance genes due to the use of the antibiotics and are transmitted to human beings through various ways, great harm is caused to the human health and the environment for a long time, and the discharge of pharmaceutical wastewater is the main source of the antibiotic wastewater.
The environmental protection of China is increasingly emphasized, with the continuous perfection of national environmental laws and regulations, the discharge standard of industrial wastewater is increasingly strict, as antibiotic wastewater has the characteristics of high biotoxicity, containing bacteriostatic substances, complex components and the like, a single process hardly meets the national discharge standard due to the technical limitation, so that multiple processes are adopted to be combined for use to effectively degrade organic matters so as to ensure that the wastewater reaches the standard for discharge, the treatment of pharmaceutical wastewater is roughly divided into three steps, namely pretreatment, secondary treatment and advanced treatment, and the treatment technology of the wastewater can be divided into physicochemical technology, biotechnology and advanced catalytic oxidation technology according to different technical characteristics.
The physicochemical technology and the biological technology have the defects of incomplete degradation and the like, and although the high-grade catalytic oxidation method such as Fenton can treat some waste water which is difficult to degrade, the existence of ferrous iron causes secondary pollution; the ozone catalysis technology has no problems of secondary pollution and the like, but has higher cost and is difficult to realize large-scale application. Therefore, it is urgent to find a cheap and efficient method for degrading antibiotic wastewater.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a double perovskite La2NiFeO6A method for catalyzing and degrading antibiotic wastewater, which aims to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
double perovskite La2NiFeO6The preparation process of the catalyst comprises the following steps:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring, adding nickel acetate, and stirring to obtain a spinning solution;
step 2: extracting spinning solution by using a spinning needle tube, spinning the spinning solution on a spinning carrier by using an electrostatic spinning instrument, detaching the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 250-280 ℃ at a heating rate of 1 ℃/min for pre-oxidation for 1-1.5 h, and heating to 650-700 ℃ at a heating rate of 2 ℃/min for oxidation for 1-2 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 1-3 h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
As an improvement of the invention, in the step 1, the molar ratio of lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone, nickel acetate and N, N-dimethylformamide is 6:5:2:1: 10-15.
As an improvement of the invention, in the step 2, the spinning speed of the electrostatic spinning instrument is 0.1-0.2 mm/min, the spinning positive voltage is 14-16V, the spinning negative voltage is-5-6V, and the spinning distance is 20-25 mm.
As a modification of the invention, in the step 2, the spinning carrier is tin foil paper.
As an improvement of the invention, the drying temperature in the step 3 is 100-110 ℃, and the drying time is 4-6 h.
As an improvement of the invention, the reaction temperature of the constant-temperature magnetic stirrer in the step 1 is 60-70 ℃.
La prepared by using double perovskite2NiFeO6The application of the catalyst in catalyzing and degrading antibiotic wastewater comprises the following steps:
(1) filtering the antibiotic wastewater;
(2) adding double perovskite La into the filtered wastewater2NiFeO6Stirring the catalyst;
(3) carrying out photocatalytic reaction on the wastewater for 1-2 hours;
(4) and introducing the wastewater after the reaction into a settling pond for settling, and then discharging the settled wastewater.
As an improvement of the invention, the wastewater in the step (2) is mixed with La2NiFeO6The volume-mass ratio of the catalyst is 100: 1-6.
As an improvement of the invention, the stirring speed in the step (2) is 50-100 r/min, the stirring time is 5-10 min, and the reaction temperature is 35-45 ℃.
As an improvement of the invention, the method is characterized in that: and (4) the pH value of the wastewater discharged in the step (4) is 7-8.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
the invention discloses a double perovskite La2NiFeO6A method for catalyzing and degrading antibiotic wastewater, namely synthesizing double perovskite La2NiFeO6The nano material catalyst realizes the high-efficiency and high-standard treatment of the antibiotic wastewater under photocatalysis;
the double perovskite catalyst prepared by the electrostatic spinning method has a nanofiber material structure, increases the specific surface area, and has better photocatalytic performance than the traditional perovskite;
the double perovskite catalyst prepared by the invention has higher crystallinity and unique one-dimensional structure, thus having excellent photocatalytic stability.
The invention discloses a double perovskite La2NiFeO6Method for catalytic degradation of antibiotic wastewater by using the double perovskite La2NiFeO6The nano material catalyst can degrade antibiotic wastewater, and has high degradation rate and no secondary pollution.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
The wastewater antibiotic comprehensive wastewater used in the experiment mainly contains penicillin industrial salt, 7-ACA, 7-ADCA, amoxicillin, cefalexin and the like. Therefore, the antibiotic wastewater has very complex components, various organic pollutants, high content, high salinity, deep chromaticity and many difficultly-degraded substances, wherein many of the organic pollutants have biological inhibition or toxicity, poor biodegradability and high wastewater treatment difficulty.
Example 1:
La2NiFeO6the preparation steps of the catalyst are as follows:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring at 65 ℃, adding nickel acetate, and stirring to obtain a spinning solution; the molar ratio of the lanthanum nitrate to the ferric nitrate to the polyvinylpyrrolidone to the nickel acetate to the N, N-dimethylformamide is 6:5:2:1: 12.
Step 2: the spinning solution was extracted with a spinning needle and passed through an electrospinning apparatus (the spinning speed of the electrospinning apparatus was 0.18mm min)-1Spinning solution on a spinning carrier (tin foil paper) with spinning positive voltage of 15.11V, spinning negative voltage of-4.98V and spinning distance of 23mm), detaching the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying, wherein the drying temperature is 105 ℃, and the drying time is 5 h;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 280 ℃ at the heating rate of 1 ℃/min for pre-oxidation for 1h, and heating to 700 ℃ at the heating rate of 2 ℃/min for oxidation for 2 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 1h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
Example 2:
La2NiFeO6the preparation steps of the catalyst are as follows:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring at 60 ℃, adding nickel acetate, and stirring to obtain a spinning solution; the molar ratio of the lanthanum nitrate to the ferric nitrate to the polyvinylpyrrolidone to the nickel acetate to the N, N-dimethylformamide is 6:5:2:1: 10.
Step 2: the spinning solution was extracted with a spinning needle tube and passed through an electrospinning apparatus (the spinning speed of the electrospinning apparatus was 0.1mm min)-1Spinning solution on a spinning carrier (tinfoil paper) at spinning positive voltage of 14V, spinning negative voltage of-5V and spinning distance of 20mm, and removing the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying at the temperature of 100 ℃ for 4 h;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 250 ℃ at the heating rate of 1 ℃/min for pre-oxidation for 1.5h, and heating to 650 ℃ at the heating rate of 2 ℃/min for oxidation for 1 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 3h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
Example 3:
La2NiFeO6the preparation steps of the catalyst are as follows:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring at 70 ℃, adding nickel acetate, and stirring to obtain a spinning solution; the molar ratio of the lanthanum nitrate to the ferric nitrate to the polyvinylpyrrolidone to the nickel acetate to the N, N-dimethylformamide is 6:5:2:1: 15.
Step 2: the spinning solution was extracted with a spinning needle tube and passed through an electrospinning apparatus (the spinning speed of the electrospinning apparatus was 0.2mm min)-1Spinning the spinning solution on a spinning carrier (tin foil paper) with a spinning positive voltage of 16V, a spinning negative voltage of-6V and a spinning distance of 25mm), detaching the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying at the temperature of 110 ℃ for 6 h;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 270 ℃ at the heating rate of 1 ℃/min for pre-oxidation for 1.3h, and heating to 680 ℃ at the heating rate of 2 ℃/min for oxidation for 2 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 2h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
Example 4: la2NiFeO6Preparation of the catalyst
La2NiFeO6The preparation steps of the catalyst are as follows:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring at 80 ℃, adding nickel acetate, and stirring to obtain a spinning solution; the molar ratio of the lanthanum nitrate to the ferric nitrate to the polyvinylpyrrolidone to the nickel acetate to the N, N-dimethylformamide is 6:5:2:1: 30.
Step 2: the spinning solution was extracted with a spinning needle and passed through an electrospinning apparatus (the spinning speed of the electrospinning apparatus was 0.18mm min)-1Spinning solution on a spinning carrier (tin foil paper) with spinning positive voltage of 15.11V, spinning negative voltage of-4.98V and spinning distance of 23mm), detaching the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying at the temperature of 150 ℃ for 2 h;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 500 ℃ and oxidizing for 1 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 2h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
Example 5: la2NiFeO6Catalytic degradation of antibiotic wastewater
La double perovskite prepared in example 12NiFeO6The method for catalytically degrading the antibiotic wastewater comprises the following steps:
(1) filtering the antibiotic wastewater;
(2) adding La into the filtered wastewater2NiFeO6The catalyst was stirred (wastewater with La)2NiFeO6The volume mass ratio of the catalyst is 100: 5; stirring at 70r/min for 8min at 40 deg.C);
(3) carrying out photocatalytic reaction on the wastewater for 1 hour;
(4) introducing the wastewater after the reaction into a settling pond for settling, and then discharging the settled wastewater; the pH value of the discharged wastewater is 7-8.
The water quality indexes of the antibiotic wastewater at different stages are as follows:
| water quality index at different stages | BOD5(mg/L) | COD(mg/L) | Ammonia nitrogen (mg/L) | SS(mg/L) |
| Initial antibiotic wastewater | 319.5 | 617.5 | 26.7 | 60.4 |
| The wastewater treated in the step (1) | 319.4 | 616.9 | 26.7 | 58.1 |
| The wastewater treated in the step (2) | 124.7 | 385.6 | 24.4 | 53.5 |
| The wastewater treated in the step (3) | 25.1 | 15.1 | 19.2 | 48.9 |
| The wastewater treated in the step (4) | 24.7 | 14.8 | 19.1 | 48.1 |
The technical problem to be solved by the invention is to provide a solution for antibiotic wastewater, namely synthesizing double perovskite La2NiFeO6The nano material catalyst realizes high-efficiency and high-standard treatment of antibiotic wastewater under photocatalysis. Double perovskite PVP-La2NiFeO6The nano-fiber is a photocatalyst with better photocatalytic oxidation performanceHas wide application prospect.
The antibiotic wastewater treated by the method has BOD5 less than or equal to 25mg/L, COD less than or equal to 15mg/L, ammonia nitrogen less than or equal to 20mg/L and SS less than or equal to 50mg/L, and meets the national wastewater discharge standard.
Example 6:
la double perovskite prepared in example 42NiFeO6The method for catalytically degrading the antibiotic wastewater comprises the following steps:
(1) filtering the antibiotic wastewater;
(2) adding La into the filtered wastewater2NiFeO6The catalyst was stirred (wastewater with La)2NiFeO6The volume mass ratio of the catalyst is 100: 5; stirring at 70r/min for 8min at 40 deg.C);
(3) carrying out photocatalytic reaction on the wastewater for 2 hours;
(4) introducing the wastewater after the reaction into a settling pond for settling, and then discharging the settled wastewater; the pH value of the discharged wastewater is 7-8.
The water quality indexes of the antibiotic wastewater at different stages are as follows:
| water quality index at different stages | BOD5(mg/L) | COD(mg/L) | Ammonia nitrogen (mg/L) | SS(mg/L) |
| Initial antibiotic wastewater | 319.5 | 617.5 | 26.7 | 60.4 |
| The wastewater treated in the step (1) | 318.5 | 617.3 | 26.4 | 58.1 |
| The wastewater treated in the step (2) | 298.3 | 591.7 | 25.0 | 57.5 |
| The wastewater treated in the step (3) | 239.6 | 507.3 | 23.2 | 54.9 |
| The wastewater treated in the step (4) | 153.1 | 208.2 | 20.7 | 50.6 |
Example 8:
the method for degrading the antibiotic wastewater by photocatalysis comprises the following steps:
filtering the antibiotic wastewater, and carrying out photocatalytic reaction on the wastewater for 1.5 hours; introducing the wastewater after the reaction into a settling pond for settling, and then discharging the settled wastewater; the pH value of the discharged wastewater is 7-8.
| Water quality index at different stages | BOD5(mg/L) | COD(mg/L) | Ammonia nitrogen (mg/L) | SS(mg/L) |
| Initial antibiotic wastewater | 319.5 | 617.5 | 26.7 | 60.4 |
| Treated wastewater | 318.1 | 613.5 | 25.8 | 59.4 |
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. Double perovskite La2NiFeO6The preparation process of the catalyst is characterized by comprising the following steps:
step 1: mixing lanthanum nitrate, ferric nitrate, polyvinylpyrrolidone and N, N-dimethylformamide, introducing into a constant-temperature magnetic stirrer, uniformly stirring, adding nickel acetate, and stirring to obtain a spinning solution;
step 2: extracting spinning solution by using a spinning needle tube, spinning the spinning solution on a spinning carrier by using an electrostatic spinning instrument, detaching the spinning carrier and scraping spinning fibers after spinning is finished;
and step 3: transferring the spinning fiber into a vacuum oven for drying;
and 4, step 4: putting the spinning fiber into a tube furnace, heating to 250-280 ℃ at a heating rate of 1 ℃/min for pre-oxidation for 1-1.5 h, and heating to 650-700 ℃ at a heating rate of 2 ℃/min for oxidation for 1-2 h;
and 5: taking the spinning fiber out of the tube furnace, calcining for 1-3 h, and cooling to room temperature to obtain La2NiFeO6A catalyst.
2. A double perovskite La of claim 12NiFeO6The preparation process of the catalyst is characterized by comprising the following steps: in the step 1, the molar ratio of lanthanum nitrate to ferric nitrate to polyvinylpyrrolidone to nickel acetate to N, N-dimethylformamide is 6:5:2:1: 10-15.
3. A double perovskite La of claim 12NiFeO6The preparation process of the catalyst is characterized by comprising the following steps: the reaction temperature of the constant-temperature magnetic stirrer in the step 1 is 60-70 ℃.
4. A double perovskite La of claim 12NiFeO6The preparation process of the catalyst is characterized by comprising the following steps: in the step 2, the spinning speed of the electrostatic spinning instrument is 0.1-0.2 mm/min, the spinning positive voltage is 14-16V, the spinning negative voltage is-5-6V, and the spinning distance is 20-25 mm.
5. A double perovskite La of claim 12NiFeO6Preparation process of catalystThe method is characterized in that: and the spinning carrier in the step 2 is tin foil paper.
6. A double perovskite La of claim 12NiFeO6The preparation process of the catalyst is characterized by comprising the following steps: and the drying temperature in the step 3 is 100-110 ℃, and the drying time is 4-6 h.
7. La using the double perovskite of any one of claims 1 to 62NiFeO6The application of the catalyst in catalyzing and degrading antibiotic wastewater is characterized by comprising the following steps:
(1) filtering the antibiotic wastewater;
(2) adding La into the filtered wastewater2NiFeO6Stirring the catalyst;
(3) carrying out photocatalytic reaction on the wastewater for 1-2 hours;
(4) and introducing the wastewater after the reaction into a settling pond for settling, and then discharging the settled wastewater.
8. Use according to claim 7, characterized in that: the wastewater and La in the step (2)2NiFeO6The volume-mass ratio of the catalyst is 100: 1-6.
9. Use according to claim 7, characterized in that: the stirring speed in the step (2) is 50-100 r/min, the stirring time is 5-10 min, and the reaction temperature is 35-45 ℃.
10. Use according to claim 7, characterized in that: and (4) the pH value of the wastewater discharged in the step (4) is 7-8.
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