CN115282964B - Fenton-like reaction catalyst and preparation method and application thereof - Google Patents
Fenton-like reaction catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115282964B CN115282964B CN202211077765.6A CN202211077765A CN115282964B CN 115282964 B CN115282964 B CN 115282964B CN 202211077765 A CN202211077765 A CN 202211077765A CN 115282964 B CN115282964 B CN 115282964B
- Authority
- CN
- China
- Prior art keywords
- reaction
- fenton
- catalyst
- reaction catalyst
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 19
- 239000004305 biphenyl Substances 0.000 claims abstract description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 13
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 19
- 239000004098 Tetracycline Substances 0.000 claims description 17
- 229960002180 tetracycline Drugs 0.000 claims description 17
- 229930101283 tetracycline Natural products 0.000 claims description 17
- 235000019364 tetracycline Nutrition 0.000 claims description 17
- 150000003522 tetracyclines Chemical class 0.000 claims description 17
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 30
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
- C02F2101/38—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
-
- 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
- C02F2305/10—Photocatalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalysts and wastewater treatment, and particularly discloses a Fenton-like reaction catalyst and a preparation method and application thereof. According to the invention, biphenyl, dimethoxy methane and ferric chloride are mixed according to a mole ratio of 1:1 to 3: 1-3, carrying out crosslinking reaction to obtain an iron-containing super-crosslinking precursor, and then carrying out high-temperature roasting on the iron-containing super-crosslinking precursor to obtain the Fenton-like reaction catalyst. The Fenton-like reaction catalyst prepared by the invention has the advantages of cheap and easily available raw materials, simple synthesis process, high catalytic activity, short catalytic reaction time and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts and wastewater treatment, in particular to a Fenton-like reaction catalyst and a preparation method and application thereof.
Background
Advanced oxidation processes (Advanced oxidationprocesses, AOPs) have been widely used as a main means for degrading organic pollutants in water, and conventional homogeneous Fenton reaction has the problems of narrow pH operating range (ph=2 to 4) of the catalyst, easiness in forming hydroxide precipitates, secondary pollution and the like, although the catalytic activity is very high. To overcome the above problems, fenton-like reaction catalysts (heterogeneous Fenton reaction catalysts) have been studied extensively.
For example, the Chinese patent application ZL201310442419.8 discloses a method for preparing an iron-carbon catalyst of a heterogeneous Fenton system by taking polytetrafluoroethylene as a precursor; the Chinese patent application ZL201610383476.7 discloses a method for preparing a high-activity heterogeneous Fenton-like reaction catalyst by loading magnetic nano-particles of ferroferric oxide with volcanic particles; the Chinese patent application ZL201710850683.3 discloses a method for preparing heterogeneous Fenton-like reaction catalyst by coating ferric oxide with silicon oxide; the Chinese patent application ZL201810227786.9 discloses a method for preparing a high-activity heterogeneous Fenton-like reaction catalyst by taking cellulose/graphene oxide hydrogel as a precursor; chinese patent No. CN201910443343.8 discloses a method for preparing heterogeneous fenton reaction nanocarbon material using saccharide compound as precursor; chinese patent No. CN202110379071.7 discloses a method for preparing heterogeneous Fenton-like reaction catalyst containing ZSM-5 molecular sieve, MXene loaded on ZSM-5 molecular sieve and metal oxide anchored on MXene nano-sheet.
However, the Fenton-like reaction catalysts disclosed by the above technology all have the problems of low reaction speed and poor catalytic degradation effect, and in practical application, the addition amount of the catalyst and hydrogen peroxide is increased to improve the catalytic effect, and the degradation reaction time is prolonged.
Therefore, how to provide a Fenton-like reaction catalyst, a preparation method and application thereof, so as to improve the catalytic activity of the catalyst, reduce the catalytic reaction time and reduce the addition amount of the catalyst and hydrogen peroxide is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a Fenton-like reaction catalyst, and a preparation method and application thereof, so as to solve the problems of low reaction speed, poor catalytic degradation effect and large dosage of the Fenton-like reaction catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing Fenton-like reaction catalyst, comprising the following steps: and mixing biphenyl, dimethoxymethane and ferric chloride, performing a crosslinking reaction to obtain an iron-containing super-crosslinking precursor, and then roasting to obtain the Fenton-like reaction catalyst.
Preferably, the molar ratio of biphenyl, dimethoxymethane and ferric chloride is 1:1 to 3:1 to 3.
Preferably, the cross-linking reaction is divided into a front section and a rear section, the temperature of the front section cross-linking reaction is 55-65 ℃, and the reaction time is 4-6 hours; the temperature of the later reaction is 70-80 ℃ and the reaction time is 18-24 h.
Preferably, the roasting temperature is 450-650 ℃, and the roasting time is 3-5 h.
Preferably, the crosslinking reaction is carried out in a solvent which is 1, 2-dichloroethane.
Preferably, the volume mole ratio of the addition amount of the solvent to the ferric chloride is 30-50 mL:0.1 to 0.3mol.
The invention also aims to provide the Fenton-like reaction catalyst prepared by the preparation method of the Fenton-like reaction catalyst, and the Fenton-like reaction catalyst has a structure of carbon-coated ferric oxide.
It is a further object of the present invention to provide the use of a Fenton-like reaction catalyst for the degradation of tetracycline organic pollutants.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method comprises the steps of preparing the super-crosslinked polymer by taking ferric chloride as a catalyst, uniformly dispersing the ferric chloride in the super-crosslinked polymer after reaction, further taking the super-crosslinked polymer containing the ferric chloride as a precursor, roasting to prepare the Fenton-like reaction catalyst of carbon-coated supported ferric oxide, wherein the prepared super-crosslinked polymer has larger specific surface area, and the ferric oxide is uniformly dispersed in the super-crosslinked polymer and tightly coated by a carbon material and is not easy to run off.
Detailed Description
The invention provides a preparation method of Fenton-like reaction catalyst, which comprises the following steps: and mixing biphenyl, dimethoxymethane and ferric chloride, performing a crosslinking reaction to obtain an iron-containing super-crosslinking precursor, and then roasting to obtain the Fenton-like reaction catalyst.
In the invention, the molar ratio of biphenyl, dimethoxymethane and ferric chloride is 1:1 to 3:1 to 3, preferably 1:1.5 to 2.5:1.5 to 2.5, more preferably 1:2:2.
in the invention, the crosslinking reaction is divided into a front section and a rear section, and the temperature of the front section crosslinking reaction is 55-65 ℃, preferably 58-62 ℃, and more preferably 60 ℃; the reaction time is 4 to 6 hours, preferably 4.5 to 5.5 hours, and more preferably 5 hours; the temperature of the subsequent reaction is 70-80 ℃, preferably 72-78 ℃, and more preferably 75 ℃; the reaction time is 18 to 24 hours, preferably 19 to 22 hours, and more preferably 20 hours.
In the present invention, the baking temperature is 450 to 650 ℃, preferably 500 to 600 ℃, and more preferably 550 ℃; the calcination time is 3 to 5 hours, preferably 3.5 to 4.5 hours, and more preferably 4 hours.
In the present invention, the crosslinking reaction is performed in a solvent, which is 1, 2-dichloroethane.
In the invention, the volume mole ratio of the addition amount of the solvent to the ferric chloride is 30-50 mL:0.1 to 0.3mol, preferably 35 to 45mL:0.15 to 0.25mol, more preferably 40mL:0.2mol.
The invention also aims to provide the Fenton-like reaction catalyst prepared by the preparation method of the Fenton-like reaction catalyst.
It is a further object of the present invention to provide the use of a Fenton-like reaction catalyst having the structure of carbon-coated ferric oxide for the degradation of tetracycline organic pollutants.
In the invention, the treatment object of the Fenton-like reaction catalyst is preferably organic pollutants in organic wastewater, and the specific method for degrading the organic pollutants in the organic wastewater by the Fenton-like reaction catalyst comprises the following steps of: and adding the Fenton-like reaction catalyst and hydrogen peroxide into the organic wastewater to perform Fenton-like reaction, so as to degrade organic matters in the organic wastewater.
In the invention, the addition amount of the Fenton-like reaction catalyst is 60-120 mg/L, preferably 80-110 mg/L, and more preferably 100mg/L; the volume ratio of the hydrogen peroxide to the organic wastewater is 0.03-0.15: 100, preferably 0.05 to 0.12:100, more preferably 0.1:100.
in the present invention, the reaction time is preferably 15 to 30 minutes, more preferably 20 to 25 minutes, and still more preferably 22 minutes.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added and stirred until the biphenyl is dissolved, 0.01mol of dimethoxymethane (FDA) and 0.01mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 55 ℃ and stirred for reaction for 4 hours, and then the temperature is raised to 70 ℃ and the reaction is continued for 18 hours until the reaction is completed. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 450 ℃ for 3 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like reaction catalyst, which is prepared in this exampleThe specific surface area of the catalyst is 120m 2 /g
In a 250mL glass beaker, 100mL of a tetracycline solution at a concentration of 10mg/L was added, and 6mg of catalyst was added at room temperature and stirred on a magnetic stirrer. To the mixture was added 0.05mL of H 2 O 2 The reaction is carried out for 15min, and the degradation rate of the tetracycline is 96%.
Example 2
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added, stirring is carried out until the biphenyl is dissolved, 0.02mol of dimethoxymethane (FDA) and 0.02mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 60 ℃ and stirring is carried out for 5 hours, and then the temperature is raised to 80 ℃ and the reaction is continued for 21 hours until the reaction is complete. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 550 ℃ for 4 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like catalyst, wherein the specific surface area of Fenton-like catalyst prepared in this example is 140m 2 /g。
In a 250mL glass beaker, 100mL of a 50mg/L tetracycline solution was added, 9mg of catalyst was added at room temperature, and stirred on a magnetic stirrer. To the mixture was added 0.1mL of H 2 O 2 The reaction is carried out for 20min, and the degradation rate of the tetracycline is 97%.
Example 3
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added and stirred until the biphenyl is dissolved, 0.03mol of dimethoxymethane (FDA) and 0.03mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 65 ℃ and stirred for reaction for 6 hours, and then the temperature is raised to 80 ℃ and the reaction is continued for 24 hours until the reaction is complete. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 650 ℃ for 5 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like catalyst, wherein the specific surface area of Fenton-like catalyst prepared in this example is 158m 2 /g。
In a 250mL glass beaker, 100mL of a 90mg/L tetracycline solution was added, 12mg of catalyst was added at room temperature, and stirred on a magnetic stirrer. To the mixture was added 0.15mL of H 2 O 2 The reaction is carried out for 25min, and the degradation rate of the tetracycline is 98%.
Example 4
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added and stirred until the biphenyl is dissolved, 0.01mol of dimethoxymethane (FDA) and 0.01mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 55 ℃ and stirred for 4 hours, and then the temperature is raised to 80 ℃ and the reaction is continued for 18 hours until the reaction is complete. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 450 ℃ for 3 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like catalyst, wherein the specific surface area of Fenton-like catalyst prepared in this example is 117m 2 /g。
In a 250mL glass beaker, 100mL of a tetracycline solution at a concentration of 130mg/L was added, 6mg of catalyst was added at room temperature, and stirred on a magnetic stirrer. To the mixture was added 0.05mL of H 2 O 2 The reaction is carried out for 30min, and the degradation rate of the tetracycline is 95%.
Example 5
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added, stirring is carried out until the biphenyl is dissolved, 0.02mol of dimethoxymethane (FDA) and 0.02mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 55 ℃ for stirring reaction for 5 hours, and then the temperature is raised to 80 ℃ for continuous reaction for 21 hours until the reaction is complete. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 450 ℃ for 3 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like catalyst, wherein the specific surface area of Fenton-like catalyst prepared in this example is 142m 2 /g。
At 250mLIn a glass beaker, 100mL of 170mg/L tetracycline solution was added, 9mg of catalyst was added at room temperature, and stirred on a magnetic stirrer. To the mixture was added 0.1mL of H 2 O 2 The reaction is carried out for 20min, and the degradation rate of the tetracycline is 96%.
Example 6
Into a 250mL three-neck flask, 0.01mol of biphenyl is added, 40mL of 1, 2-Dichloroethane (DCE) solvent is added and stirred until the biphenyl is dissolved, 0.03mol of dimethoxymethane (FDA) and 0.03mol of anhydrous ferric trichloride are sequentially added, the temperature is raised to 65 ℃ and stirred for reaction for 6 hours, and then the temperature is raised to 80 ℃ and the reaction is continued for 24 hours until the reaction is complete. The solvent was spin-dried using a rotary evaporator and the solid residue was dried under vacuum at 80 ℃ for 24h to give a dark gray solid. The dark gray solid was placed in a muffle furnace and calcined at 650 ℃ for 4 hours, and cooled to room temperature to obtain a black solid. Washing the black solid with deionized water, and drying at 80deg.C under vacuum for 24 hr to obtain Fenton-like catalyst, wherein the specific surface area of Fenton-like catalyst prepared in this example is 161m 2 /g。
In a 250mL glass beaker, 100mL of 200mg/L tetracycline solution was added, 12mg of catalyst was added at room temperature, and stirred on a magnetic stirrer. To the mixture was added 0.15mL of H 2 O 2 The reaction is carried out for 25min, and the degradation rate of the tetracycline is 96%.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. The application of the Fenton-like reaction catalyst in degrading tetracycline organic pollutants is characterized in that the preparation method of the Fenton-like reaction catalyst comprises the following steps: mixing biphenyl, dimethoxymethane and ferric chloride, performing a crosslinking reaction to obtain an iron-containing super-crosslinking precursor, and then roasting to obtain a Fenton-like reaction catalyst;
the molar ratio of the biphenyl to the dimethoxymethane to the ferric chloride is 1: 1-3: 1-3;
the crosslinking reaction is divided into a front section and a rear section, the temperature of the front section crosslinking reaction is 55-65 ℃, and the reaction time is 4-6 hours; the temperature of the subsequent reaction is 70-80 ℃, and the reaction time is 18-24 hours;
the crosslinking reaction is carried out in a solvent;
the volume mole ratio of the addition amount of the solvent to the ferric chloride is 30-50 mL:0.1 to 0.3mol;
the Fenton-like reaction catalyst has a structure of carbon-coated ferric oxide.
2. The application of Fenton-like reaction catalyst in degrading tetracycline organic pollutants according to claim 1, wherein the roasting temperature is 450-650 ℃ and the roasting time is 3-5 h in the preparation method.
3. Use of a Fenton-like reaction catalyst according to claim 2 for degrading tetracycline organic pollutants, wherein said solvent is 1, 2-dichloroethane during the preparation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211077765.6A CN115282964B (en) | 2022-09-05 | 2022-09-05 | Fenton-like reaction catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211077765.6A CN115282964B (en) | 2022-09-05 | 2022-09-05 | Fenton-like reaction catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115282964A CN115282964A (en) | 2022-11-04 |
| CN115282964B true CN115282964B (en) | 2023-05-23 |
Family
ID=83834208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211077765.6A Active CN115282964B (en) | 2022-09-05 | 2022-09-05 | Fenton-like reaction catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115282964B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020492B (en) * | 2022-12-15 | 2024-06-25 | 贵州大学 | Fenton-like catalyst preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505101A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | Organic dye degradation catalyst based on heterogeneous Fenton-like reaction, and preparation and application thereof |
| CN114700097A (en) * | 2022-05-17 | 2022-07-05 | 南京大学 | Fe2O3-MXenes composite catalyst and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836727B (en) * | 2016-03-21 | 2018-10-23 | 陕西师范大学 | A kind of method that low cost prepares multi-walled carbon nanotube |
| CN107723850A (en) * | 2017-10-31 | 2018-02-23 | 西北工业大学 | A kind of preparation method of high-ratio surface magnetic carbon nano-fiber |
| CN108559093B (en) * | 2018-03-22 | 2021-10-01 | 国家纳米科学中心 | Porous polymer material containing metallocene and preparation method thereof |
| AU2020100596A4 (en) * | 2020-04-17 | 2020-05-28 | Taiyuan City Vocational College | A Magnetic Catalyst For Bentonite Fenton And Its Preparation Method |
| CN112121843B (en) * | 2020-10-15 | 2022-04-22 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic-supported nitrogen-doped carbon nanotube coated iron nanoparticle Fenton-like catalyst |
| CN113893855B (en) * | 2021-10-28 | 2024-03-26 | 苏州大学 | Resin fibrous mesoporous SiO 2 Loaded with Fe 2 O 3 Catalyst, preparation method and application thereof |
-
2022
- 2022-09-05 CN CN202211077765.6A patent/CN115282964B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505101A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | Organic dye degradation catalyst based on heterogeneous Fenton-like reaction, and preparation and application thereof |
| CN114700097A (en) * | 2022-05-17 | 2022-07-05 | 南京大学 | Fe2O3-MXenes composite catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115282964A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113522317B (en) | Preparation method and application of cobalt-based bimetallic sulfur/carbon catalyst derived from MOFs (metal-organic frameworks) | |
| CN114534759A (en) | Monoatomic cobalt-supported tubular carbon nitride catalyst and preparation method and application thereof | |
| CN115282964B (en) | Fenton-like reaction catalyst and preparation method and application thereof | |
| CN111450871A (en) | Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material and the preparation method thereof | |
| CN113908878B (en) | Preparation method and application of bimetallic Prussian blue analogue catalyst | |
| CN113398944B (en) | Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof | |
| CN108212192A (en) | A kind of light-fenton catalyst and preparation method thereof | |
| CN113368905B (en) | Method for synthesizing Co monoatomic atom by using chitosan as substrate and application of Co monoatomic atom in efficient activation of persulfate to degrade organic pollutants | |
| CN109225325B (en) | Fe-PANI/zeolite catalyst and preparation method thereof | |
| CN115920895B (en) | photo-Fenton transition metal monoatomic catalyst and preparation method and application thereof | |
| CN115090287B (en) | Fe-CoO (Fe-CoO) ozone activation catalyst doped with iron and cobalt x Method for preparing the same | |
| CN114505101A (en) | Organic dye degradation catalyst based on heterogeneous Fenton-like reaction, and preparation and application thereof | |
| CN114768846A (en) | Preparation method and application of visible light catalytic material for efficiently degrading enoxacin | |
| CN111659468B (en) | MoS (MoS) 2 Composite catalyst of defective MIL-101 (Fe), preparation method and application | |
| CN114054053A (en) | Bismuth oxybromide/titanium dioxide composite photocatalyst and preparation method thereof | |
| CN113351202B (en) | Titanium dioxide/ruthenium monoatomic noble metal nano catalytic material for degrading pollutants and preparation method thereof | |
| CN111889143B (en) | Preparation method of tin dioxide/polyaniline nanowire composite photocatalyst | |
| CN106902828B (en) | A kind of processing method of acetyl spiramycin antibiotic waste water | |
| CN117582985B (en) | Quartz sand-based composite photocatalyst and preparation method and application thereof | |
| CN112403467A (en) | TiO2Co-doped composite photocatalyst, preparation method thereof and application thereof in treating phenol-containing wastewater | |
| CN112675896A (en) | Preparation method of nonmetal modified nickel-iron spinel Fenton catalyst | |
| CN114618594B (en) | Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof | |
| CN114247481B (en) | Photocatalysis treatment method for beta-aminopropionitrile refining kettle residues | |
| CN112371171B (en) | Preparation and application of bismuth ferrite loaded graphene composite material | |
| CN116764659A (en) | Cerium dioxide-nitrogen doped carbon nitride composite photocatalytic material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |