CN113856692A - Preparation of perovskite catalyst and method for treating atrazine wastewater by activating persulfate through perovskite catalyst - Google Patents
Preparation of perovskite catalyst and method for treating atrazine wastewater by activating persulfate through perovskite catalyst Download PDFInfo
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- CN113856692A CN113856692A CN202111168638.2A CN202111168638A CN113856692A CN 113856692 A CN113856692 A CN 113856692A CN 202111168638 A CN202111168638 A CN 202111168638A CN 113856692 A CN113856692 A CN 113856692A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/83—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 with rare earths or actinides
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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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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- C02F2101/306—Pesticides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C02F2101/00—Nature of the contaminant
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Abstract
A method for preparing a perovskite catalyst and treating atrazine wastewater by activating persulfate, belonging to the technical field of water pollution control. Doping of LaFe by Sr0.5Cu0.5O3A perovskite catalyst prepared by LaxSr1‑ xFe0.5Cu0.5O3(x is more than or equal to 0.1 and less than or equal to 0.9). The step of treating atrazine wastewater by activating persulfate through the perovskite catalyst comprises the following steps: dispersing the perovskite catalyst into the atrazine wastewater, and fully stirring to obtain a mixed solution. Adding Peroxymonosulfate (PMS) into the mixed solution, and placing the solution in a constant temperature shaking table for reaction. Is suitable for use inAnd (4) treating various organic wastewater. Especially, 90 percent of the atrazine waste water can be removed in 20 min.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a preparation method of a perovskite catalyst and a method for treating atrazine wastewater by activating persulfate through the perovskite catalyst.
Background
Atrazine, also known as atrazine, is a herbicide widely used to control broadleaf weeds. However, surface and ground water contamination results from improper use. Atrazine has the characteristics of strong water solubility, stable structure and difficult biodegradation, has a very slow mineralization process in nature, and is listed in the list of endocrine disrupting compounds in the european union and the united states. Therefore, the method has important significance in treating the atrazine in the water body environment. The traditional water treatment technology has very limited atrazine removing capacity and poor degradation effect.
The persulfate advanced oxidation technology is a novel advanced oxidation technology developed in recent years and uses sulfate radical (SO)4 ·-) Is an active species. SO in contrast to hydroxyl radical (. OH)4 ·-Has higher oxidation-reduction potential and selectivity, thereby degrading most toxic and harmful organic pollutants more effectively and finally mineralizing into CO2、H2O and inorganic salts. SO (SO)4 ·-The method can be produced by activating persulfate through heat, alkali, ultraviolet light, nonmetal, ultrasound, transition metal and the like, wherein the transition metal activation has the advantages of mild reaction conditions, low cost, convenience for continuous operation and the like, and has good application prospect in the field of treating antibiotic wastewater.
Disclosure of Invention
The invention provides a preparation method of a persulfate activating catalyst, a method for catalyzing persulfate to treat atrazine wastewater and application thereof, which are efficient, stable and low in cost, aiming at solving the problem of high difficulty in the existing atrazine wastewater treatment.
In order to achieve the purpose, the technical scheme of the application is as follows:
the invention firstly provides a preparation method of a perovskite catalyst, and LaFe is doped with Sr0.5Cu0.5O3A perovskite catalyst prepared by LaxSr1-xFe0.5Cu0.5O3(x is more than or equal to 0.1 and less than or equal to 0.9), and is characterized by comprising the following steps:
(1) lanthanum nitrate hexahydrate (La (NO)3)3·6H2O), strontium nitrate hexahydrate (Sr(NO3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O), copper nitrate trihydrate (Cu (NO)3)2·3H2O), citric acid (C)6H8O7·H2O) to obtain a mixture A.
(2) And adding deionized water into the mixture A, continuously stirring to dissolve the mixture A, maintaining the temperature in a certain range, continuously adding ethanol, stirring and evaporating to dryness until the mixture is in a gel state to obtain a mixture B.
(3) And putting the mixture B into an oven for drying to obtain a mixture C.
(4) And placing the mixture C into a crucible, and placing the crucible into a muffle furnace for calcining.
(5) The calcined catalyst was ground to a uniform fine particle.
In the step (1), wherein La (NO)3)3·6H2O：Sr(NO3)3·6H2O： Fe(NO3)3·9H2O：Cu(NO3)2·3H2O：C6H8O7·H2The molar ratio of O is X: 1-X: 0.5: 0.5: 2 to 4.
The temperature in the step (2) is 60-80 ℃.
And (4) drying the oven in the step (3) at the drying temperature of 100-120 ℃ for 8-14 h.
And (4) heating the muffle furnace for calcination at a heating rate of 2-6 ℃/min, and heating to 700-900 ℃ for 4-6 h while keeping the temperature.
The invention also provides an application of the perovskite catalyst activated persulfate in treatment of atrazine wastewater, which is characterized by comprising the following steps:
(1) dispersing the perovskite catalyst into atrazine wastewater, and fully stirring to obtain a mixed solution.
(2) Adding Peroxymonosulfate (PMS) into the mixed solution, and placing the solution in a constant temperature shaking table for reaction, wherein the temperature is set to be room temperature, such as 25 ℃.
The adding amount of the catalyst in the step (1) is 0.1-1 g/L, and the concentration of the atrazine in the wastewater is 10-100 mg/L.
The persulfate in the step (2) is preferably potassium monopersulfate or sodium monopersulfate, the reaction time is 1-60 min, and the concentration of the monopersulfate is 0.1-0.3 g/L.
The whole reaction process in the step (2) is in a dark condition so as to avoid interference of illumination on persulfate activation.
The invention has the following beneficial effects:
(1) the invention adopts Sr to dope LaFe for the first time0.5Cu0.5O3The method for preparing the catalyst by the perovskite is simple and quick to operate;
(2) the catalyst has good stability, can be recycled, and reduces the wastewater treatment cost;
(3) the perovskite catalyst is used for activating persulfate to degrade pollutants, the reaction condition is mild, the pollutant degradation efficiency is high, and the method is economical and feasible and is suitable for treating various organic wastewater. Especially, 90 percent of the atrazine waste water can be removed in 20 min.
Drawings
FIG. 1 is a flow diagram of a process for preparing a perovskite catalyst.
FIG. 2 is a degradation diagram of atrazine wastewater treated by a perovskite catalyst activated persulfate.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments below:
example 1:
(1) lanthanum nitrate hexahydrate (La (NO)3)3·6H2O), strontium nitrate hexahydrate (Sr (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O), copper nitrate trihydrate (Cu (NO)3)2·3H2O), citric acid (C)6H8O7·H2O) to obtain a mixture A. Wherein, La (NO)3)3·6H2O：Sr(NO3)3·6H2O：Fe(NO3)3·9H2O： Cu(NO3)2·3H2O：C6H8O7·H2The molar ratio of O is 0.3: 0.7: 0.5: 0.5: 3.
(2) adding deionized water into the mixture A, continuously stirring to dissolve the mixture A, maintaining the temperature at 70 ℃, continuously adding ethanol, stirring and evaporating to dryness until the mixture is in a gel state to obtain a mixture B.
(3) And (5) putting the mixture B into an oven for drying at 100 ℃ for 10 hours to obtain a mixture C.
(4) And placing the mixture C into a crucible, placing the crucible into a muffle furnace for calcination, wherein the heating rate of the muffle furnace for calcination is 2 ℃/min, and heating to 800 ℃ for heat preservation for 6 h.
(5) The calcined catalyst was ground to a uniform fine particle.
Example 2:
(1) lanthanum nitrate hexahydrate (La (NO)3)3·6H2O), strontium nitrate hexahydrate (Sr (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O), copper nitrate trihydrate (Cu (NO)3)2·3H2O), citric acid (C)6H8O7·H2O) to obtain a mixture A. Wherein, La (NO)3)3·6H2O：Sr(NO3)3·6H2O：Fe(NO3)3·9H2O： Cu(NO3)2·3H2O：C6H8O7·H2The molar ratio of O is 0.5: 0.5: 0.5: 0.5: 3.
(2) adding deionized water into the mixture A, continuously stirring to dissolve the mixture A, maintaining the temperature at 70 ℃, continuously adding ethanol, stirring and evaporating to dryness until the mixture is in a gel state to obtain a mixture B.
(3) And (5) putting the mixture B into an oven for drying at 100 ℃ for 10 hours to obtain a mixture C.
(4) And placing the mixture C into a crucible, placing the crucible into a muffle furnace for calcination, wherein the heating rate of the muffle furnace for calcination is 2 ℃/min, and heating to 800 ℃ for heat preservation for 6 h.
(5) The calcined catalyst was ground to a uniform fine particle.
Example 3:
(1) lanthanum nitrate hexahydrate (La (NO)3)3·6H2O), strontium nitrate hexahydrate (Sr (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O), copper nitrate trihydrate (Cu (NO)3)2·3H2O), citric acid (C)6H8O7·H2O) to obtain a mixture A. Wherein, La (NO)3)3·6H2O：Sr(NO3)3·6H2O：Fe(NO3)3·9H2O： Cu(NO3)2·3H2O：C6H8O7·H2The molar ratio of O is 0.7: 0.3: 0.5: 0.5: 3.
(2) adding deionized water into the mixture A, continuously stirring to dissolve the mixture A, maintaining the temperature at 70 ℃, continuously adding ethanol, stirring and evaporating to dryness until the mixture is in a gel state to obtain a mixture B.
(3) And (5) putting the mixture B into an oven for drying at 100 ℃ for 10 hours to obtain a mixture C.
(4) And placing the mixture C into a crucible, placing the crucible into a muffle furnace for calcination, wherein the heating rate of the muffle furnace for calcination is 2 ℃/min, and heating to 800 ℃ for heat preservation for 6 h.
(5) The calcined catalyst was ground to a uniform fine particle.
Application example 1:
10mg of the perovskite catalyst prepared in the above example 1 was added to 100mL of atrazine wastewater having a concentration of 30 mg/L. And adding 20mg of peroxymonosulfate into the wastewater, reacting for 30min at normal temperature, wherein the degradation rate of the atrazine reaches 90% in about 20 min.
Application example 2:
10mg of the perovskite catalyst prepared in the above example 2 was added to 100mL of atrazine wastewater having a concentration of 30 mg/L. And adding 20mg of peroxymonosulfate into the wastewater, reacting for 30min at normal temperature, wherein the degradation rate of the atrazine reaches 90% in about 15 min.
Application example 3:
10mg of the perovskite catalyst prepared in the above example 3 was added to 100mL of atrazine wastewater having a concentration of 30 mg/L. And adding 20mg of peroxymonosulfate into the wastewater, reacting for 30min at normal temperature, wherein the degradation rate of the atrazine reaches 90% in about 20 min.
Degradation rate is (1-C/C)0)×100％
Residual concentration of atrazine in C-wastewater
C0Initial concentration of atrazine in the wastewater.
Claims (8)
1. A perovskite catalyst is characterized in that the perovskite catalyst has a chemical formula of LaxSr1-xFe0.5Cu0.5O3，0.1≤x≤0.9。
2. A process for preparing the perovskite catalyst as claimed in claim 1, comprising the steps of:
(1) lanthanum nitrate hexahydrate (La (NO)3)3·6H2O), strontium nitrate hexahydrate (Sr (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O), copper nitrate trihydrate (Cu (NO)3)2·3H2O), citric acid (C)6H8O7·H2O) mixing to obtain a mixture A;
(2) adding deionized water into the mixture A, continuously stirring to dissolve the mixture A, maintaining the temperature within a certain range, continuously adding ethanol, stirring and evaporating to dryness until the mixture is in a gel state to obtain a mixture B;
(3) putting the mixture B into an oven for drying to obtain a mixture C;
(4) placing the mixture C into a crucible, and placing the crucible in a muffle furnace for calcining;
(5) the calcined catalyst was ground to a uniform fine particle.
3. The method of claim 2,
in the step (1), wherein La (NO)3)3·6H2O：Sr(NO3)3·6H2O：Fe(NO3)3·9H2O：Cu(NO3)2·3H2O：C6H8O7·H2The molar ratio of O is X: 1-X: 0.5: 0.5: 2-4;
the temperature in the step (2) is 60-80 ℃;
the drying temperature of the drying oven in the step (3) is 100-120 ℃, and the drying time is 8-14 h;
and (4) heating the muffle furnace for calcination at a heating rate of 2-6 ℃/min, and heating to 700-900 ℃ for 4-6 h while keeping the temperature.
4. Use of the perovskite catalyst as defined in claim 1 for the treatment of organic pollutant waste water by persulfate activation.
5. Use according to claim 4, characterized in that the perovskite catalyst activates persulfate to treat atrazine wastewater, comprising the following steps:
(1) dispersing the perovskite catalyst into atrazine wastewater, and fully stirring to obtain a mixed solution;
(2) adding Peroxymonosulfate (PMS) into the mixed solution, placing the solution in a constant temperature shaking table for reaction, and setting the temperature to be room temperature.
6. The method as claimed in claim 4, wherein the catalyst is added in an amount of 0.1-1 g/L in step (1), and the concentration of atrazine in the wastewater is 10-100 mg/L.
7. The method according to claim 4, wherein the persulfate in step (2) is preferably potassium monopersulfate or sodium monopersulfate, the reaction time is 1-60 min, and the concentration of the monopersulfate is 0.1-0.3 g/L.
8. The use according to claim 4, wherein the reaction in step (2) is carried out under conditions protected from light to avoid interference of light with persulfate activation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433126A (en) * | 2022-01-26 | 2022-05-06 | 湖北拓扑来微科技有限公司 | A kind of high-entropy perovskite monolithic catalyst and its preparation method and application |
| CN115106091A (en) * | 2022-07-01 | 2022-09-27 | 长春理工大学 | Method for preparing perovskite persulfate catalyst by electrospinning process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015152613A1 (en) * | 2014-03-31 | 2015-10-08 | (주)써스텍 | Method for preparing mixed metal oxide catalyst |
| CN109095590A (en) * | 2018-08-31 | 2018-12-28 | 中国环境科学研究院 | LaFe1-xCuxO3The method for handling residue in water Atrazine |
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- 2021-09-30 CN CN202111168638.2A patent/CN113856692A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015152613A1 (en) * | 2014-03-31 | 2015-10-08 | (주)써스텍 | Method for preparing mixed metal oxide catalyst |
| CN109095590A (en) * | 2018-08-31 | 2018-12-28 | 中国环境科学研究院 | LaFe1-xCuxO3The method for handling residue in water Atrazine |
Non-Patent Citations (2)
| Title |
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| 徐劼等: "Sr掺杂强化LaCo0.5Cu0.5O3型钙钛矿活化过一硫酸盐的性能", 化工进展, vol. 39, no. 9, pages 3525 - 3534 * |
| 程成: "镧铁钙钛矿型材料活化过硫酸盐处理典型有机氯农药污染物", 中国优秀硕士学位论文全文数据库 工程科技I辑, pages 027 - 456 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433126A (en) * | 2022-01-26 | 2022-05-06 | 湖北拓扑来微科技有限公司 | A kind of high-entropy perovskite monolithic catalyst and its preparation method and application |
| CN114433126B (en) * | 2022-01-26 | 2023-11-28 | 湖北拓扑来微科技有限公司 | High-entropy perovskite monolithic catalyst and preparation method and application thereof |
| CN115106091A (en) * | 2022-07-01 | 2022-09-27 | 长春理工大学 | Method for preparing perovskite persulfate catalyst by electrospinning process |
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