CN115518658A - Preparation method and application of cluster spherical multiphase Fenton catalyst - Google Patents
Preparation method and application of cluster spherical multiphase Fenton catalyst Download PDFInfo
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- CN115518658A CN115518658A CN202211141681.4A CN202211141681A CN115518658A CN 115518658 A CN115518658 A CN 115518658A CN 202211141681 A CN202211141681 A CN 202211141681A CN 115518658 A CN115518658 A CN 115518658A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 14
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 14
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 14
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 12
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to the technical field of sewage treatment, and discloses a preparation method and application of a cluster spherical multiphase Fenton catalyst, wherein the preparation method comprises the following steps: weighing a copper source and a zinc source, dissolving the copper source and the zinc source in ultrapure water, and uniformly stirring to obtain a solution A; adding a mixture of a sulfur source and sodium hydroxide into the solution A, continuously stirring, and waiting for the completion of precipitation to obtain a suspension B; dissolving 3-mercaptopropyltriethoxysilane in absolute ethyl alcohol in batches to obtain a solution C; adding the solution C into the suspension B, and keeping stirring to obtain a suspension D; centrifuging, and washing with ultrapure water for three times to obtain a wet solid E; and transferring the solid E onto a porcelain boat, placing the porcelain boat in a muffle furnace, heating to a set temperature, preserving the heat for a certain time, and cooling to room temperature to obtain the cluster spherical multiphase Fenton catalyst. The method for preparing the multiphase Fenton catalyst has short time-consuming process, the needed raw materials are cheap and easy to obtain, and the prepared catalyst has high degradation rate on pollutants which are difficult to degrade in water.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a preparation method and application of a cluster spherical multiphase Fenton catalyst.
Background
Persistent organic pollutants are discharged into the environment along with the production and living of human beings, and the pollutants have long-distance mobility, difficult biodegradability and bioaccumulation. In recent years, there has been an increasing interest in human health and aquatic ecology due to its potential adverse effects. Fenton technology is a promising technology for the treatment of toxic and persistent organic pollutants in wastewater. The Fenton technology can utilize hydroxyl free radicals (OH) generated in the reaction process to attack pollutants, so that macromolecular pollutants are degraded into small molecules and even mineralized into CO 2 And H 2 And O. However, in the classical Fenton reaction, due to its pair with H 2 O 2 Low utilization rate, large amount of H 2 O 2 The ineffective decomposition causes energy waste; and Fe in the reaction 2+ Is continuously consumed and converted into Fe 3+ And a large amount of iron mud is generated to cause secondary pollution of the water body.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method and application of a cluster ball-shaped heterogeneous Fenton catalyst. On the basis of the classical Fenton reaction, the degradation rate of the pollutants difficult to degrade in the water body is accelerated, the time consumption of the preparation process is short, the needed raw materials are cheap and easy to obtain, and the problem of Fe is solved 3+ The secondary pollution of the water body is caused.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention discloses a preparation method of a cluster ball-shaped multiphase Fenton catalyst, which comprises the following steps:
s1, weighing a copper source and a zinc source, dissolving the copper source and the zinc source in ultrapure water, and uniformly stirring to obtain a solution A.
S2, adding a mixture of a sulfur source and sodium hydroxide into the solution A, continuously stirring, and waiting for the completion of precipitation to obtain a suspension B;
s3, dissolving 3-mercaptopropyltriethoxysilane in absolute ethanol in batches to obtain a solution C;
s4, adding the solution C into the suspension B, and keeping stirring to obtain a suspension D;
s5, transferring the suspension D into a centrifugal tube for centrifugation, and washing the suspension D with ultrapure water for three times to obtain a wet solid E;
s6, transferring the solid E to a porcelain boat, placing the porcelain boat in a muffle furnace, heating to a set temperature, preserving heat for a certain time, and cooling to room temperature to obtain the cluster spherical multiphase Fenton catalyst.
Preferably, in the step S1, the copper source is copper chloride dihydrate, and the zinc source is zinc sulfate heptahydrate, wherein the molar ratio of the copper chloride dihydrate to the zinc sulfate heptahydrate is (1-5): (5-10).
Preferably, in the step S1, the stirring temperature is 30-35 ℃, and the stirring time is 10-30min.
Preferably, in the step S2, the sulfur source is sodium sulfide nonahydrate, wherein the molar ratio of sodium sulfide nonahydrate to sodium hydroxide is (0-1): (1-5).
Preferably, in the step S2, the stirring temperature is 30-35 ℃, and the stirring time is 10-30min.
Preferably, in the step S3, the stirring temperature is 30-35 ℃, and the stirring time is 10-30min.
Preferably, in the step S4, the stirring temperature is 30-35 ℃, and the stirring time is 5-10h.
Preferably, in the step S5, the centrifugation times are 4-5 times, and the single centrifugation time is 8-9min.
Preferably, in the step S6, the heating speed of the muffle furnace is (5-10) ° C/min, the set temperature is (600-800) ° C, and the heat preservation time is (1-3) h.
In a second aspect, the invention discloses an application of the cluster ball-shaped heterogeneous Fenton catalyst prepared by the method in pollutant degradation.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the heterogeneous Fenton-like catalyst has the advantages of short time-consuming preparation process, cheap and easily-obtained raw materials, high degradation rate of the catalyst on pollutants difficult to degrade in water, and greatly shortened reaction time compared with the traditional Fenton technology.
2. The preparation method of the heterogeneous Fenton catalyst does not need to adjust the pH value (pH value) of a system to 2-3 in the reaction process, has good removal effect on degradation of organic pollutants difficult to biodegrade under neutral or even alkaline room temperature conditions, does not have copper source dissolution in the reaction process, does not generate solid foreign matters, and does not need a foreign matter removing device.
3. The preparation method of the multiphase Fenton catalyst does not need input of external energy in the process of degrading pollutants, greatly reduces resource waste, and has good stability in the process of removing organic pollutants.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a scanning electron micrograph of a heterogeneous Fenton catalyst according to the present invention at low resolution;
FIG. 2 is a high resolution transmission electron micrograph of a heterogeneous Fenton catalyst according to the present invention;
FIG. 3 is an X-ray diffraction pattern of LL-GTT-3 prepared in example 2 according to the present invention;
FIG. 4 is a graph showing the degradation profile of LL-GTT-3 prepared in example 2 of the present invention and LL-GTT-prepared in comparative example 1 with respect to ciprofloxacin;
FIG. 5 is a graph showing the degradation profiles of LL-GTT-3 prepared in example 2 of the present invention for various contaminants.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The invention is further described with reference to the following examples.
Example 1
A preparation method of a cluster spherical heterogeneous Fenton catalyst comprises the following steps:
s1, weighing a certain amount of copper chloride dihydrate and zinc sulfate heptahydrate, wherein the molar ratio of the copper chloride dihydrate to the zinc sulfate heptahydrate is as follows: copper chloride dihydrate: zinc sulfate heptahydrate =1: and 5, dissolving the mixture in ultrapure water, stirring at the temperature of 30 ℃ for 10min, and uniformly stirring to obtain a solution A.
S2, adding a mixture of sodium sulfide nonahydrate and sodium hydroxide according to a certain proportion, wherein the molar ratio of the sodium sulfide nonahydrate to the sodium hydroxide is as follows: sodium sulfide nonahydrate: sodium hydroxide =0.1:1, stirring at the temperature of 30 ℃ for 10min, and waiting for the precipitation to be finished to obtain a suspension B.
S3, dissolving 3-mercaptopropyltriethoxysilane in anhydrous ethanol in batches, stirring at the temperature of 30 ℃ for 10min to obtain a solution C,
and S4, adding the solution C obtained in the step S3 into the suspension B obtained in the step S2, and stirring at the temperature of 30 ℃ for 5 hours to obtain a suspension D.
S5, transferring the obtained suspension D into a centrifuge tube for centrifugation for 4 times, wherein the single centrifugation time is 8min, and washing the suspension D with ultrapure water for three times to obtain a wet solid E.
And S6, transferring the solid E onto a porcelain boat, placing the porcelain boat in a muffle furnace, heating the muffle furnace to 700 ℃ at a heating speed of 5K/min, and preserving heat for 1h to obtain the solid catalyst after the temperature is reduced to room temperature.
Example 2:
a preparation method of a cluster ball-shaped heterogeneous Fenton catalyst comprises the following steps:
s1, weighing a certain amount of copper chloride dihydrate and zinc sulfate heptahydrate, wherein the molar ratio of the copper chloride dihydrate to the zinc sulfate heptahydrate is as follows: copper chloride dihydrate: zinc sulfate heptahydrate =1:6.25, dissolving in ultrapure water, stirring at 30 ℃ for 30min, and uniformly stirring to obtain a solution A.
S2, adding a mixture of sodium sulfide nonahydrate and sodium hydroxide according to a certain proportion, wherein the molar ratio of the sodium sulfide nonahydrate to the sodium hydroxide is as follows: sodium sulfide nonahydrate: sodium hydroxide =1: and 4, stirring at the temperature of 30 ℃ for 30min, and waiting for the precipitation to be finished to obtain a suspension B.
S3, dissolving 3-mercaptopropyltriethoxysilane in anhydrous ethanol in batches, stirring at the temperature of 30 ℃ for 10min to obtain a solution C,
and S4, adding the solution C obtained in the step S3 into the suspension B obtained in the step S2, and stirring at the temperature of 30 ℃ for 5 hours to obtain a suspension D.
S5, transferring the obtained suspension D into a centrifuge tube for centrifugation for 4 times, wherein the single centrifugation time is 8min, and washing with ultrapure water for three times to obtain a wet solid E.
S6, transferring the solid E to a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature of the muffle furnace to 600 ℃ at the speed of 5K/min, preserving the temperature for 1h, and obtaining a solid catalyst LL-GTT-3 after the temperature is reduced to room temperature.
Example 3:
a preparation method of a cluster ball-shaped heterogeneous Fenton catalyst comprises the following steps:
s1, weighing a certain amount of copper chloride dihydrate and zinc sulfate heptahydrate, wherein the molar ratio of the copper chloride dihydrate to the zinc sulfate heptahydrate is as follows: copper chloride dihydrate: zinc sulfate heptahydrate =5:10, dissolving in ultrapure water, stirring at 35 ℃ for 30min, and uniformly stirring to obtain a solution A.
S2, adding a mixture of sodium sulfide nonahydrate and sodium hydroxide according to a certain proportion, wherein the molar ratio of the sodium sulfide nonahydrate to the sodium hydroxide is as follows: sodium sulfide nonahydrate: sodium hydroxide =1: and 5, stirring at the temperature of 35 ℃ for 30min, and waiting for the precipitation to be finished to obtain a suspension B.
S3, dissolving 3-mercaptopropyltriethoxysilane in anhydrous ethanol in batches, stirring at 35 ℃ for 30min to obtain a solution C,
and S4, adding the solution C obtained in the step S3 into the suspension B obtained in the step S2, and stirring at the temperature of 35 ℃ for 10 hours to obtain a suspension D.
S5, transferring the obtained suspension D into a centrifuge tube for centrifugation for 5 times and 9min for single centrifugation, and washing with ultrapure water for three times to obtain a wet solid E.
S6, transferring the solid E to a porcelain boat, placing the porcelain boat in a muffle furnace, heating the muffle furnace to 800 ℃ at a heating speed of 10K/min, and preserving heat for 3 hours to obtain a solid catalyst after the temperature is reduced to room temperature.
Comparative example 1:
compared with the example 2, only copper chloride dihydrate and sodium sulfide nonahydrate are not added, and the rest components, the parts by weight and the preparation method are completely the same as the example 2, so that the catalyst LL-GTT-contrast is finally prepared.
The preparation method of the heterogeneous Fenton-like catalyst disclosed by the invention is short in time-consuming preparation process, and the required raw materials are cheap and easy to obtain. As can be seen from the graphs of FIGS. 3-5, the catalyst prepared by the invention has a high degradation rate on the pollutants which are difficult to be degraded in water, greatly shortens the reaction time compared with the traditional Fenton technology, simultaneously does not need to adjust the pH value (pH value) of the system to 2-3 in the reaction process, and has a good removal effect on the degradation of the organic pollutants which are difficult to be biologically degraded under the neutral or even alkaline room temperature condition. Secondly, no copper source is dissolved out in the reaction process, no solid foreign matter is generated, no foreign matter removing device is needed, no external energy is input in the process of degrading pollutants, the resource waste is greatly reduced, and the catalyst has good stability in the process of removing organic pollutants.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a cluster ball-shaped multiphase Fenton catalyst is characterized by comprising the following steps:
s1, weighing a copper source and a zinc source, dissolving the copper source and the zinc source in ultrapure water, and uniformly stirring to obtain a solution A;
s2, adding a mixture of a sulfur source and sodium hydroxide into the solution A, continuously stirring, and waiting for the completion of precipitation to obtain a suspension B;
s3, dissolving 3-mercaptopropyltriethoxysilane in absolute ethanol in batches to obtain a solution C;
s4, adding the solution C into the suspension B, and keeping stirring to obtain a suspension D;
s5, transferring the suspension D into a centrifugal tube for centrifugation, and washing the suspension D with ultrapure water for three times to obtain a wet solid E;
s6, transferring the solid E to a porcelain boat, placing the porcelain boat in a muffle furnace, heating to a set temperature, preserving heat for a certain time, and cooling to room temperature to obtain the cluster spherical multiphase Fenton catalyst.
2. The method for preparing a floral ball-shaped heterogeneous Fenton catalyst according to claim 1, wherein in the step S1, the copper source is copper chloride dihydrate and the zinc source is zinc sulfate heptahydrate, wherein the molar ratio of the copper chloride dihydrate to the zinc sulfate heptahydrate is (1-5): (5-10).
3. The method for preparing a floral ball-shaped multiphase Fenton' S catalyst according to claim 1, wherein in the step S1, the stirring temperature is 30-35 ℃ and the stirring time is 10-30min.
4. The method for preparing a floral cluster spherical heterogeneous fenton catalyst according to claim 1, wherein in step S2, the sulfur source is sodium sulfide nonahydrate, wherein the molar ratio of sodium sulfide nonahydrate to sodium hydroxide is (0-1): (1-5).
5. The method for preparing a floral ball-shaped multiphase Fenton' S catalyst according to claim 1, wherein in the step S2, the stirring temperature is 30-35 ℃ and the stirring time is 10-30min.
6. The method for preparing a floral ball-shaped multiphase Fenton' S catalyst according to claim 1, wherein in the step S3, the stirring temperature is 30-35 ℃ and the stirring time is 10-30min.
7. The method for preparing a floral ball-shaped multiphase Fenton' S catalyst in accordance with claim 1, wherein in said step S4, the stirring temperature is 30-35 ℃ and the stirring time is 5-10h.
8. The method for preparing a floral cluster spherical heterogeneous Fenton' S catalyst according to claim 1, wherein in step S5, the centrifugation time is 4-5 times and the single centrifugation time is 8-9min.
9. The method of claim 1, wherein in step S6, the muffle furnace heating rate is (5-10) ° c/min, the set temperature is (600-800) ° c, and the holding time is (1-3) hours.
10. Use of a floral bouquet shaped heterogeneous fenton catalyst prepared by the method according to any one of claims 1 to 9 for degrading pollutants.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759226A (en) * | 2009-12-04 | 2010-06-30 | 郑州大学 | Binary sulfide CuXZn1-XS particle with efflorescent structure and preparation method thereof |
| CN110342568A (en) * | 2019-08-09 | 2019-10-18 | 陕西科技大学 | A kind of silk ball flower shape zinc oxide copper sulfide and preparation method thereof |
| CN111111697A (en) * | 2020-01-10 | 2020-05-08 | 新疆大学 | Method for preparing copper sulfide/zinc oxide nano composite photocatalytic material by room-temperature solid-phase chemical method |
| CN111330577A (en) * | 2020-04-15 | 2020-06-26 | 广州大学 | Fenton catalyst with zero-valent copper coated on carbonized organic framework and preparation method and application thereof |
| CN112717954A (en) * | 2020-12-24 | 2021-04-30 | 广州大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN113231082A (en) * | 2021-06-02 | 2021-08-10 | 南京泽佑环保科技有限公司 | High-activity iron-based-sulfide heterogeneous Fenton composite material and method for removing organic pollutants by using same |
-
2022
- 2022-09-20 CN CN202211141681.4A patent/CN115518658B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759226A (en) * | 2009-12-04 | 2010-06-30 | 郑州大学 | Binary sulfide CuXZn1-XS particle with efflorescent structure and preparation method thereof |
| CN110342568A (en) * | 2019-08-09 | 2019-10-18 | 陕西科技大学 | A kind of silk ball flower shape zinc oxide copper sulfide and preparation method thereof |
| CN111111697A (en) * | 2020-01-10 | 2020-05-08 | 新疆大学 | Method for preparing copper sulfide/zinc oxide nano composite photocatalytic material by room-temperature solid-phase chemical method |
| CN111330577A (en) * | 2020-04-15 | 2020-06-26 | 广州大学 | Fenton catalyst with zero-valent copper coated on carbonized organic framework and preparation method and application thereof |
| CN112717954A (en) * | 2020-12-24 | 2021-04-30 | 广州大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN113231082A (en) * | 2021-06-02 | 2021-08-10 | 南京泽佑环保科技有限公司 | High-activity iron-based-sulfide heterogeneous Fenton composite material and method for removing organic pollutants by using same |
Non-Patent Citations (2)
| Title |
|---|
| HAMID REZA POURETEDAL ET AL.: "Nanoparticles of zinc sulfide doped with manganese, nickel and copper as nanophotocatalyst in the degradation of organic dyes", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 162, pages 674 - 681, XP025805044, DOI: 10.1016/j.jhazmat.2008.05.128 * |
| JIA-HUI JI ET AL.: "Magnetic separation of metal sulfides/oxides by Fe3O4 at room temperature and atmospheric pressure", 《RARE MET.》, vol. 38, no. 5, pages 379 - 389, XP036767404, DOI: 10.1007/s12598-019-01232-3 * |
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