CN113198473A - Transition metal oxide Fenton catalyst and preparation method and application thereof - Google Patents
Transition metal oxide Fenton catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113198473A CN113198473A CN202110476249.XA CN202110476249A CN113198473A CN 113198473 A CN113198473 A CN 113198473A CN 202110476249 A CN202110476249 A CN 202110476249A CN 113198473 A CN113198473 A CN 113198473A
- Authority
- CN
- China
- Prior art keywords
- carbon
- solution
- transition metal
- metal oxide
- catalyst
- 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.)
- Granted
Links
Images
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
- B01J23/75—Cobalt
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- 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
- B01J23/755—Nickel
-
- 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
- B01J23/76—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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- 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
Abstract
The invention belongs to the technical field of industrial catalysts, and particularly relates to a transition metal oxide Fenton catalyst, and a preparation method and application thereof. The invention pretreats and dries a carbon-based carrier for later use, and then loads transition metal salt on the carrier by a one-step hydrothermal method to obtain the transition metal oxide Fenton catalyst. The catalyst prepared by the method is filled in a fixed bed reactor, persulfate is used as an oxidant to degrade organic wastewater, and the degradation rate of the organic wastewater can reach more than 85% under the conditions of normal temperature and normal pressure and no need of regulating the pH value. Has great industrial popularization value.
Description
Technical Field
The invention belongs to the technical field of industrial catalysts, and particularly relates to a transition metal oxide Fenton catalyst, and a preparation method and application thereof.
Background
With the continuous development of global economy, the treatment of various industrial wastewater and domestic sewage becomes one of the problems which are difficult to solve internationally at present. Water is vital to human health. In the art of degrading sewage to the emission standard, researchers have done much work and have developed innovative solutions for effectively removing organic pollutants to reduce the content of organic pollutants to an acceptable level, but the technology for industrialization has not yet matured.
The advanced oxidation technology adopts an oxidant with strong oxidizability, such as potassium permanganate, a Fenton reagent, ozone, persulfate and the like, and quickly oxidizes organic pollutants which are difficult to biodegrade into small molecular compounds which are nontoxic or easy to biodegrade without selectivity. However, the oxidation of potassium permanganate is not selective, the pH application range of the Fenton reagent is narrow, and the longitudinal transmission distance of ozone is short. In recent years, persulfate has appeared in related studies as a novel oxidizing agent, SO4Standard redox potential (2.5-3.1V) of.OH is similar (2.8V), SO4The redox potential of (A) is higher than that of (OH), and most organic pollutants can be treated by SO4Complete degradation. SO (SO)4Life span of (3X 10)-5-4×10-5s) longer than OH (2X 10)-8s), persulfate remains in the environment for a longer period of time than hydrogen peroxide, increasing its chance of reaction in contact with contaminants.
The patent CN 111420665A utilizes catalyst Fe2O3-CoAl2O4/TiO2The carrier is titanium oxide, active component Fe salt is loaded on the carrier by an impregnation method to treat the organic wastewater, the whole preparation process is very complex, and the pH value needs to be adjusted when the wastewater is treated. In patent CN105268487A, basalt fiber is used as a carrier to load an iron oxide catalyst to purify sewage, the carrier is expensive and not easy to obtain, and the carrier is complicated in pretreatment and not beneficial to industrial production.
The invention takes a carbon-based material as a carrier, and the transition metal salt is loaded on the carbon-based carrier through a one-step hydrothermal synthesis method to obtain the transition metal oxide Fenton catalyst. The catalyst can efficiently treat various organic wastewater under the conditions of normal temperature and normal pressure and no pH limitation, is renewable, and has very important industrial application value.
Disclosure of Invention
The invention aims to provide a transition metal oxide Fenton catalyst and a preparation method and application thereof based on the defects in the prior art, wherein the transition metal oxide Fenton catalyst treats various organic wastewater by using persulfate as an oxidant under the conditions of normal temperature and normal pressure and no pH limitation, and has the advantages of simple and continuous process, long service life and reproducibility when being used for treating wastewater.
In order to realize the purpose, the invention is realized by the following technical scheme:
a transition metal oxide Fenton catalyst is prepared by loading transition metal salt on a pretreated carbon-based carrier and performing one-step hydrothermal synthesis.
Further, the carbon-based carrier is one or a mixture of a plurality of coal-based activated carbon, coconut shell activated carbon, carbon felt, carbon paper, carbon fiber, carbon rods, carbon nano tubes or carbon cloth in any proportion.
The invention provides a preparation method of the transition metal oxide Fenton catalyst, which comprises the following steps:
and 5, filtering out the carbon-based carrier loaded with the catalyst, drying the catalyst, and introducing protective gas for high-temperature calcination.
Further, the carbon-based carrier in the step 1 is one or a mixture of a plurality of coal-based activated carbon, coconut shell activated carbon, carbon felt, carbon paper, carbon fiber, carbon rod, carbon nanotube or carbon cloth in any proportion; the pretreatment of the carbon-based carrier comprises the following specific steps:
step 1.1, soaking in a dilute acid solution for two hours, and then washing with deionized water;
step 1.2, soaking in a dilute alkali solution for two hours, and then washing with deionized water;
and step 1.3, soaking in deionized water for two hours, and then drying in an oven for later use.
Further, the dilute acid solution in the step 1.1 is one or a combination of hydrochloric acid, sulfuric acid, nitric acid, citric acid and acetic acid; the concentration of the dilute acid is 0.01-1mol/L, and the preferable concentration is 0.3-0.6 mol/L; the dilute alkali solution is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide and ammonia water, and the concentration of the dilute alkali is 0.01-1mol/L, preferably 0.3-0.6 mol/L.
Further, the specific operation of the active ingredient solution in the step 2 is as follows: preparing a solution according to a conventional method, and dripping a PVP solution and a NaOH solution into a transition metal salt solution to be fully dissolved to obtain an active component solution; the concentration of the transition metal salt solution is 0.01-0.1 mol/L; the transition metal salt is one or a combination of iron salt, cobalt salt, nickel salt, copper salt and zinc salt.
Further, the constant-temperature stirring temperature in the step 3 is 40-80 ℃, and the stirring time is 0.5-4 h; the proportion of the carbon-based carrier added into the active component solution is 100-500 g/L; the reaction temperature of the high-temperature hydrothermal reaction in the step 4 is 100-180 ℃, and the heat preservation time is 6-12 h.
Further, in the step 5, the drying time of the catalyst is 6-12h, the high-temperature calcination temperature is 300-.
The invention also provides application of the transition metal oxide Fenton catalyst in degrading organic wastewater by activating persulfate.
Further, in a fixed bed reactor, under normal temperature and pressure, introducing 200-20000mg/L organic wastewater and 10-1000mg/L persulfate solution from the lower end of the reactor, wherein the organic wastewater stays in the bed for 0.5-100h, sampling at the upper end of the reactor, and testing the COD value and the persulfate concentration of the treated water sample for 1-4 h/time.
Further, the organic wastewater is coking wastewater, power plant wastewater, printing and dyeing wastewater, pharmaceutical factory wastewater, brewery wastewater or paper mill wastewater; the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the catalyst synthesis process, the substances are simple and easy to obtain, and the preparation process is simple and clear;
(2) the carbon-based carrier adopted by the invention is cheap and easy to obtain, has no pollution, large specific surface area and is easy to recycle;
(3) the invention has little loss of metal content of the catalyst before and after reaction, simple regeneration and easy popularization;
(4) the invention has continuous effect in treating wastewater, and is simple in manual operation and improves the efficiency;
(5) the persulfate is adopted, so that the service life is longer, and the effect is better;
(6) the catalyst has high active site, promotes the rapid decomposition of organic wastewater pollutants, and ensures that the removal rate of the wastewater after passing through the reactor reaches more than 85 percent;
(7) the sewage treated by the method can be directly discharged;
(8) the invention has simple process, easily obtained materials, long service life of the catalyst and easy regeneration, and is beneficial to industrialization.
Drawings
FIG. 1 is a schematic view of the structure of a fixed bed reactor used in the present invention;
FIG. 2 is a diagram showing the COD removal rate of the transition metal oxide-based Fenton catalyst of the present invention.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of an iron oxide/cobalt oxide fenton-like catalyst, which comprises the following steps:
step 1: soaking in 0.05mol/L hydrochloric acid solution for 2h, and washing with deionized water to neutrality; then soaking the mixture in 0.05mol/L sodium hydroxide solution for 2 hours, and then washing the mixture to be neutral by using deionized water; finally soaking in deionized water for 2h, and drying in an oven;
step 2: weighing 0.5g of PVP and dissolving the PVP in 10mL of distilled water, weighing 0.2g of NaOH and dissolving the NaOH in 10mL of distilled water, weighing 0.6755g of ferric chloride and 0.595g of cobalt chloride and adding the ferric chloride and the cobalt chloride into 50mL of distilled water to fully dissolve the ferric chloride and the cobalt chloride, and then dripping the PVP solution and the NaOH solution into the solution of the ferric chloride and the cobalt chloride to fully dissolve the ferric chloride and the cobalt chloride to obtain an active component solution;
and step 3: adding 10g of coal-based activated carbon into the active component solution, and stirring for 2 hours at 40 ℃;
and 4, step 4: putting the solution into a polytetrafluoroethylene hydrothermal kettle, and reacting for 6 hours at 100 ℃;
and 5: filtering out the carbon-based carrier loaded with the catalyst, drying in a vacuum oven for 12h, transferring to a tubular furnace, calcining at high temperature for 6h at the temperature of 300 ℃ and the protective gas of hydrogen and nitrogen at the heating rate of 5 ℃/min, and cooling to obtain the iron oxide/cobalt oxide Fenton catalyst.
Example 2
The embodiment provides a preparation method of an iron oxide/nickel oxide fenton-like catalyst, which comprises the following steps:
step 1: soaking in 0.05mol/L sulfuric acid solution for 2h, and washing with deionized water to neutrality; then soaking the mixture in 0.05mol/L potassium hydroxide solution for 2 hours, and then washing the mixture to be neutral by using deionized water; finally soaking in deionized water for 2h, and drying in an oven;
step 2: weighing 0.5g of PVP and dissolving the PVP in 10mL of distilled water, weighing 0.2g of NaOH and dissolving the NaOH in 10mL of distilled water, weighing 0.6755g of ferric chloride and 0.713g of nickel chloride and adding the nickel chloride into 50mL of distilled water to fully dissolve the ferric chloride and the nickel chloride, and then dripping the PVP solution and the NaOH solution into the solution of the ferric chloride and the nickel chloride to fully dissolve the ferric chloride and the nickel chloride to obtain an active component solution;
and step 3: adding 10g of coconut shell activated carbon into the mixed solution, and stirring for 2 hours at 60 ℃;
and 4, step 4: putting the solution into a polytetrafluoroethylene hydrothermal kettle, and reacting for 4 hours at 120 ℃;
and 5: filtering out the carbon-based carrier loaded with the catalyst, drying the carbon-based carrier in a vacuum oven for 12 hours, transferring the carbon-based carrier into a tubular furnace, calcining the carbon-based carrier at the high temperature of 400 ℃ for 6 hours at the heating rate of 5 ℃/min under the protection of hydrogen and argon, and cooling to obtain the iron oxide/nickel oxide Fenton catalyst.
Example 3
The embodiment provides a preparation method of an iron oxide/copper oxide fenton-like catalyst, which comprises the following steps:
step 1: soaking in 0.3mol/L nitric acid solution for 2h, and washing with deionized water to neutrality; then soaking the mixture in 0.3mol/L barium hydroxide solution for 2 hours, and then washing the mixture to be neutral by using deionized water; finally soaking in deionized water for 2h, and drying in an oven;
step 2: weighing 0.5g of PVP and dissolving the PVP in 10mL of distilled water, weighing 0.2g of NaOH and dissolving the NaOH in 10mL of distilled water, weighing 0.6755g of ferric chloride and 0.152g of copper chloride and adding the copper chloride into 50mL of distilled water to fully dissolve the ferric chloride and the copper chloride, and then dripping the PVP solution and the NaOH solution into the solution of the ferric chloride and the copper chloride to fully dissolve the ferric chloride and the copper chloride to obtain an active component solution;
and step 3: adding 10g of carbon felt into the mixed solution, and stirring for 1h at 80 ℃;
and 4, step 4: putting the solution into a polytetrafluoroethylene hydrothermal kettle, and reacting for 12 hours at 140 ℃;
and 5: filtering out the carbon-based carrier loaded with the catalyst, drying the carbon-based carrier in a vacuum oven for 12h, transferring the carbon-based carrier into a tubular furnace at the temperature of 500 ℃, using hydrogen and argon as protective gas, calcining the carrier at high temperature for 6h at the heating rate of 5 ℃/min, and cooling the carrier to obtain the iron oxide/copper oxide Fenton catalyst.
Example 4
The embodiment provides a preparation method of an iron oxide/zinc oxide fenton-like catalyst, which comprises the following steps:
step 1: soaking in 0.6mol/L citric acid solution for 2h, and washing with deionized water to neutrality; then soaking the mixture in 0.6mol/L ammonia water solution for 2 hours, and then washing the mixture to be neutral by using deionized water; finally soaking in deionized water for 2h, and drying in an oven;
step 2: weighing 0.5g of PVP and dissolving the PVP in 10mL of distilled water, weighing 0.2g of NaOH and dissolving the NaOH in 10mL of distilled water, weighing 0.6755g of ferric chloride and 0.34g of zinc chloride and adding the ferric chloride and the zinc chloride into 50mL of distilled water to fully dissolve the ferric chloride and the zinc chloride, and then dripping the PVP solution and the NaOH solution into the solution of the ferric chloride and the zinc chloride to fully dissolve the ferric chloride and the zinc chloride to obtain an active component solution;
and step 3: adding 10g of carbon-based carrier into the mixed solution, stirring for 2h at 80 ℃,
and 4, step 4: transferring the solution into a polytetrafluoroethylene hydrothermal kettle, reacting for 6h at 160 ℃,
and 5: filtering out the carbon-based carrier loaded with the catalyst, drying the carbon-based carrier in a vacuum oven for 12h, transferring the carbon-based carrier into a tubular furnace at the temperature of 600 ℃, using hydrogen and helium as protective gas, calcining the carrier at high temperature for 5h at the heating rate of 7 ℃/min, and cooling the carrier to obtain the iron oxide/zinc oxide Fenton catalyst.
Example 5
The embodiment provides a preparation method of an iron oxide/cobalt oxide/copper oxide fenton-like catalyst, which comprises the following steps:
step 1: soaking in 0.05mol/L acetic acid solution for 2h, and washing with deionized water to neutrality; then soaking the mixture in 0.05mol/L sodium hydroxide solution for 2 hours, and then washing the mixture to be neutral by using deionized water; finally soaking in deionized water for 2h, and drying in an oven;
step 2: weighing 0.5g of PVP and dissolving into 10mL of distilled water, weighing 0.2g of NaOH and dissolving into 10mL of distilled water, weighing 0.6755g of ferric chloride, 0.595g of cobalt chloride and 0.152g of copper chloride, adding into 50mL of distilled water and adding into 50mL of distilled water to fully dissolve the ferric chloride, the cobalt chloride and the copper chloride, and then dripping the PVP solution and the NaOH solution into the solution of the ferric chloride, the cobalt chloride and the copper chloride to fully dissolve the ferric chloride, the cobalt chloride and the copper chloride to obtain an active component solution;
and step 3: adding 10g of one of carbon paper, carbon fiber, carbon rod, carbon nanotube or carbon cloth into the mixed solution, stirring at 80 deg.C for 4h,
and 4, step 4: putting the solution into a polytetrafluoroethylene hydrothermal kettle, reacting for 6h at 180 ℃,
and 5: filtering out the carbon-based carrier carrying the catalyst, drying in a vacuum oven for 12h, transferring to a tubular furnace at the temperature of 800 ℃, taking nitrogen as protective gas, calcining at high temperature for 4h at the heating rate of 10 ℃/min, and cooling to obtain the iron oxide/cobalt oxide/copper oxide Fenton catalyst.
Example 6
The iron oxide/cobalt oxide fenton catalyst prepared in the embodiment 1 is filled in a fixed bed reactor, coking wastewater of a certain coking plant in Shanxi is taken to flow from bottom to top, ammonium persulfate solution with the concentration of 50mg/L is taken to be introduced from bottom to top, the bed layer residence time is set to be 5 hours, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer and is reduced from 50ppm to about 5ppm, the COD value is tested by a rapid COD digestion instrument, the analysis result shows that the removal rate of the COD can reach 98% after 4 hours.
Example 7
The iron oxide/nickel oxide fenton catalyst prepared in the embodiment 2 is filled in a fixed bed reactor, wastewater of a certain power plant in Shanxi is taken to flow from bottom to top, a sodium persulfate solution with the concentration of 100mg/L is taken to be introduced from bottom to top, the bed layer retention time is set to be 2 hours, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer and is reduced from 100ppm to about 5ppm, the COD value is tested by a rapid COD digestion instrument, the analysis result shows that the removal rate of the COD after 4 hours can reach 90%.
Example 8
The iron oxide/copper oxide fenton catalyst prepared in the embodiment 3 is filled in a fixed bed reactor, the concentration of a certain domestic dyeing mill is taken as wastewater flowing from bottom to top, a potassium persulfate solution with the concentration of 200mg/L is introduced from bottom to top, the bed layer retention time is set to be 1h, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer, the persulfate content is reduced from 200ppm to about 5ppm, the COD value is tested by a rapid COD digestion instrument, the analysis result shows that the removal rate of COD after 4h can reach 100%.
Example 9
The iron oxide/zinc oxide fenton catalyst prepared in the embodiment 4 is filled in a fixed bed reactor, domestic pharmaceutical wastewater flows from bottom to top, a sodium persulfate solution with the concentration of 50mg/L is introduced from bottom to top, the bed layer retention time is set to be 0.5h, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer, the persulfate content is reduced from 50ppm to about 5ppm, a COD value is tested by a rapid COD digestion instrument, the analysis result shows that the removal rate of COD can reach 85% after 4 h.
Example 10
The iron oxide/cobalt oxide/copper oxide fenton catalyst prepared in the above example 5 is filled in a fixed bed reactor, wastewater from a brewery in Shanxi is taken to flow from bottom to top, a potassium persulfate solution with a concentration of 100mg/L is taken to be introduced from bottom to top, the bed layer retention time is set to be 100h, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer, the persulfate content is reduced from 100ppm to about 5ppm, the COD value is tested by a rapid COD digestion instrument, the analysis result shows that the removal rate of COD after 4h can reach 95%.
Example 11
The iron oxide/cobalt oxide/copper oxide fenton catalyst prepared in the above example 5 is filled in a fixed bed reactor, wastewater from a certain paper mill in Shanxi is taken to flow from bottom to top, a sodium persulfate solution with a concentration of 500mg/L is taken to be introduced from bottom to top, the bed layer retention time is set to be 60 hours, sampling is carried out at the upper end of the reactor, the persulfate content is tested by an ultraviolet spectrophotometer, the persulfate content is reduced from 500ppm to about 5ppm, the COD value is tested by a rapid COD digestion instrument, and the analysis result shows that the removal rate of COD can reach 98% after 4 hours.
Claims (10)
1. A transition metal oxide Fenton catalyst is characterized in that transition metal salt is loaded on a pretreated carbon-based carrier and is prepared through a one-step hydrothermal synthesis method.
2. A transition metal oxide Fenton's catalyst according to claim 1, wherein said carbon-based carrier is one or a mixture of several of coal-based activated carbon, coconut shell activated carbon, carbon felt, carbon paper, carbon fiber, carbon rod, carbon nanotube or carbon cloth in any proportion.
3. The method for preparing a transition metal oxide fenton-like catalyst according to claim 1 or 2, comprising the steps of:
step 1, pretreating a carbon-based carrier;
step 2, preparing an active component solution;
step 3, adding the carbon-based carrier into the active component solution, and stirring at constant temperature;
step 4, carrying out high-temperature hydrothermal reaction;
and 5, filtering out the carbon-based carrier loaded with the catalyst, drying the catalyst, and introducing protective gas for high-temperature calcination.
4. A method for preparing a transition metal oxide fenton catalyst according to claim 2, wherein the carbon-based carrier in step 1 is one or a mixture of several of coal-based activated carbon, coconut shell activated carbon, carbon felt, carbon paper, carbon fiber, carbon rod, carbon nanotube or carbon cloth in any proportion; the pretreatment of the carbon-based carrier comprises the following specific steps:
step 1.1, soaking in a dilute acid solution for two hours, and then washing with deionized water;
step 1.2, soaking in a dilute alkali solution for two hours, and then washing with deionized water;
and step 1.3, soaking in deionized water for two hours, and then drying in an oven for later use.
5. The method of claim 2, wherein the diluted acid solution in step 1.1 is one or more of hydrochloric acid, sulfuric acid, nitric acid, citric acid, and acetic acid; the concentration of the dilute acid is 0.01-1mol/L, and the preferable concentration is 0.3-0.6 mol/L; the dilute alkali solution is one or more of sodium hydroxide, potassium hydroxide, barium hydroxide and ammonia water, and the concentration of the dilute alkali is 0.01-1mol/L, preferably 0.3-0.6 mol/L.
6. The method for preparing a transition metal oxide fenton-like catalyst according to claim 2, wherein the specific operation of the active component solution in the step 2 is: preparing a solution according to a conventional method, and dripping a PVP solution and a NaOH solution into a transition metal salt solution to be fully dissolved to obtain an active component solution; the concentration of the transition metal salt solution is 0.01-0.1 mol/L; the transition metal salt is one or a combination of iron salt, cobalt salt, nickel salt, copper salt and zinc salt.
7. The method for preparing a transition metal oxide fenton catalyst according to claim 2, wherein the stirring temperature at constant temperature in step 3 is 40-80 ℃ and the stirring time is 0.5-4 h; the proportion of the carbon-based carrier added into the active component solution is 100-500 g/L; the reaction temperature of the high-temperature hydrothermal reaction in the step 4 is 100-180 ℃, and the heat preservation time is 4-12 h.
8. The method as claimed in claim 2, wherein the drying time of the catalyst in step 5 is 6-12h, the high-temperature calcination temperature is 300-800 ℃, the high-temperature calcination time is 3-6h, the temperature increase rate is 5-10 ℃/min, and the shielding gas is one or more of hydrogen, nitrogen, argon, or helium.
9. Use of the transition metal oxide Fenton's catalyst according to any one of claims 1 to 8 for activating persulfate to degrade organic waste water.
10. The use of a transition metal oxide Fenton's catalyst according to claim 9, wherein in a fixed bed reactor, at normal temperature and pressure, organic wastewater and persulfate solution are fed from the lower end of the reactor, the retention time of the organic wastewater in the bed is 0.5-100h, a sample is taken from the upper end of the reactor, and the COD value and persulfate concentration of the treated water sample are tested; the organic wastewater is coking wastewater, power plant wastewater, printing and dyeing wastewater, pharmaceutical factory wastewater, brewery wastewater or paper mill wastewater; the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110476249.XA CN113198473B (en) | 2021-04-29 | 2021-04-29 | Transition metal oxide Fenton catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110476249.XA CN113198473B (en) | 2021-04-29 | 2021-04-29 | Transition metal oxide Fenton catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113198473A true CN113198473A (en) | 2021-08-03 |
| CN113198473B CN113198473B (en) | 2023-02-17 |
Family
ID=77029544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110476249.XA Active CN113198473B (en) | 2021-04-29 | 2021-04-29 | Transition metal oxide Fenton catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113198473B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209970A (en) * | 2021-05-13 | 2021-08-06 | 哈尔滨工业大学 | Preparation method and application of carbon-based catalyst prepared from excess sludge |
| CN113842956A (en) * | 2021-10-29 | 2021-12-28 | 合肥工业大学 | Preparation method and application of carbon-based packaging cobalt oxide magnetic material |
| CN114293205A (en) * | 2021-12-17 | 2022-04-08 | 新疆新能源(集团)准东环境发展有限公司 | Device and method for recovering and treating PVC acetylene purification waste sulfuric acid |
| CN114307964A (en) * | 2022-01-17 | 2022-04-12 | 合肥学院 | Method for preparing iron-nitrogen-doped biochar functional material based on waste paper box and application |
| CN115888731A (en) * | 2022-10-08 | 2023-04-04 | 广州大学 | Hexagonal nanorod polymerization nanosphere Fenton water treatment catalyst, preparation method and application |
| CN116747890A (en) * | 2023-05-25 | 2023-09-15 | 太原理工大学 | Preparation and application of BN-supported modified metal oxide doped electrochemical catalyst |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090263314A1 (en) * | 2008-04-22 | 2009-10-22 | Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan | Method for producing catalyst for wastewater treatment |
| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
| CN102580746A (en) * | 2012-01-17 | 2012-07-18 | 武汉大学 | Activated carbon supported cobalt oxide catalyst and application of same in organic pollutant degradation |
| CN102989460A (en) * | 2011-09-13 | 2013-03-27 | 苏州科技学院 | Preparation method of heterogeneous Fenton catalyst, and method for visible photocatalytic degradation of organic pollutants |
| CN103521229A (en) * | 2013-10-31 | 2014-01-22 | 中国环境科学研究院 | Preparing method for iron-cobalt Fenton-like catalyst, products of iron cobalt Fenton-like catalyst and application of iron cobalt Fenton-like catalyst |
| CN104801351A (en) * | 2015-04-01 | 2015-07-29 | 万华化学集团股份有限公司 | Preparation method of coating catalyst and coating catalyst prepared by using method |
| CN106552628A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of porous Fe xCo3-xO4The preparation method and nanocages of nanocages and application |
| CN109894115A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of the modified active carbon catalyst for the processing of class Fenton |
| CN110420639A (en) * | 2019-08-08 | 2019-11-08 | 中南大学 | A kind of cobaltosic oxide material and its methods for making and using same |
| CN111111664A (en) * | 2019-12-22 | 2020-05-08 | 华东理工大学 | Catalyst for Fenton-like continuous treatment of low-concentration organic wastewater and preparation method and application thereof |
| CN111151251A (en) * | 2020-01-15 | 2020-05-15 | 清创人和生态工程技术有限公司 | Fe-Ni-Co composite Fenton-like catalyst and preparation method thereof |
| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| US20210023533A1 (en) * | 2019-07-23 | 2021-01-28 | King Fahd University Of Petroleum And Minerals | Magnetic composite containing polyethylenimine functionalized actived carbon and methods thereof |
-
2021
- 2021-04-29 CN CN202110476249.XA patent/CN113198473B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090263314A1 (en) * | 2008-04-22 | 2009-10-22 | Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan | Method for producing catalyst for wastewater treatment |
| CN102989460A (en) * | 2011-09-13 | 2013-03-27 | 苏州科技学院 | Preparation method of heterogeneous Fenton catalyst, and method for visible photocatalytic degradation of organic pollutants |
| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
| CN102580746A (en) * | 2012-01-17 | 2012-07-18 | 武汉大学 | Activated carbon supported cobalt oxide catalyst and application of same in organic pollutant degradation |
| CN103521229A (en) * | 2013-10-31 | 2014-01-22 | 中国环境科学研究院 | Preparing method for iron-cobalt Fenton-like catalyst, products of iron cobalt Fenton-like catalyst and application of iron cobalt Fenton-like catalyst |
| CN104801351A (en) * | 2015-04-01 | 2015-07-29 | 万华化学集团股份有限公司 | Preparation method of coating catalyst and coating catalyst prepared by using method |
| CN106552628A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of porous Fe xCo3-xO4The preparation method and nanocages of nanocages and application |
| CN109894115A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of the modified active carbon catalyst for the processing of class Fenton |
| US20210023533A1 (en) * | 2019-07-23 | 2021-01-28 | King Fahd University Of Petroleum And Minerals | Magnetic composite containing polyethylenimine functionalized actived carbon and methods thereof |
| CN110420639A (en) * | 2019-08-08 | 2019-11-08 | 中南大学 | A kind of cobaltosic oxide material and its methods for making and using same |
| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111111664A (en) * | 2019-12-22 | 2020-05-08 | 华东理工大学 | Catalyst for Fenton-like continuous treatment of low-concentration organic wastewater and preparation method and application thereof |
| CN111151251A (en) * | 2020-01-15 | 2020-05-15 | 清创人和生态工程技术有限公司 | Fe-Ni-Co composite Fenton-like catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| WANG F ET AL.: "synthesis,structure,magnetism and photocatalysis of alpha-Fe2O3 nanosnowflakes", 《RSC ADVANCES》 * |
| 冯连荣: "活性炭-铁酸镍磁性催化剂的光催化性能", 《催化学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209970A (en) * | 2021-05-13 | 2021-08-06 | 哈尔滨工业大学 | Preparation method and application of carbon-based catalyst prepared from excess sludge |
| CN113842956A (en) * | 2021-10-29 | 2021-12-28 | 合肥工业大学 | Preparation method and application of carbon-based packaging cobalt oxide magnetic material |
| CN113842956B (en) * | 2021-10-29 | 2024-04-02 | 合肥工业大学 | Preparation method and application of carbon-based encapsulated cobalt oxide magnetic material |
| CN114293205A (en) * | 2021-12-17 | 2022-04-08 | 新疆新能源(集团)准东环境发展有限公司 | Device and method for recovering and treating PVC acetylene purification waste sulfuric acid |
| CN114307964A (en) * | 2022-01-17 | 2022-04-12 | 合肥学院 | Method for preparing iron-nitrogen-doped biochar functional material based on waste paper box and application |
| CN115888731A (en) * | 2022-10-08 | 2023-04-04 | 广州大学 | Hexagonal nanorod polymerization nanosphere Fenton water treatment catalyst, preparation method and application |
| CN115888731B (en) * | 2022-10-08 | 2023-10-03 | 广州大学 | Hexagonal nanorod polymerization nanosphere Fenton water treatment catalyst, preparation method and application |
| CN116747890A (en) * | 2023-05-25 | 2023-09-15 | 太原理工大学 | Preparation and application of BN-supported modified metal oxide doped electrochemical catalyst |
| CN116747890B (en) * | 2023-05-25 | 2024-04-26 | 太原理工大学 | Preparation and application of BN-supported modified metal oxide doped electrochemical catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113198473B (en) | 2023-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113198473B (en) | Transition metal oxide Fenton catalyst and preparation method and application thereof | |
| CN109896598B (en) | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water | |
| CN109292883A (en) | A method of graphitization charcoal and its degradation Organic Pollutants In Water | |
| CN112169797B (en) | Preparation method of Cu-Fe bimetallic complex magnetic chitosan carbon aerogel catalyst applied to wet oxidation | |
| CN112374601A (en) | Method for degrading organic pollutants in water by using magnetic nitrogen-doped carbon activated persulfate | |
| CN114014412B (en) | Preparation method and application of cobalt-nitrogen co-doped porous carbon graphite felt electrode | |
| CN110152639A (en) | The preparation method of modified aluminium oxide supports and the preparation method and application of supported bi-metallic oxide catalyst | |
| CN106944091A (en) | A kind of photochemical catalyst Cu CuO MnO2And its preparation method and application | |
| CN102049253B (en) | Preparation method of special catalyst for waste water treatment by ozone oxidation | |
| CN103663609A (en) | Method for treating high-COD (chemical oxygen demand) organic wastewater through microwave catalytic oxidation | |
| CN111298821A (en) | Method for preparing novel iron-nitrogen-carbon catalyst by utilizing printing and dyeing wastewater flocculated sludge | |
| CN112892548A (en) | Preparation method of manganese-based catalyst for sewage treatment and manganese-based catalyst | |
| CN111569853A (en) | Preparation method of ozone catalyst | |
| CN110255697B (en) | Preparation of nitrogen-doped carbon anode and application of nitrogen-doped carbon anode in catalytic wet air oxidation | |
| CN110386692B (en) | Auxiliary agent wastewater treatment process | |
| CN108558084B (en) | Treatment method and device for electrolytic catalysis coupling advanced oxidation of organic matters in high-salt wastewater | |
| CN115715980B (en) | Mn3O4CNTs Fenton-like catalyst and preparation method and application thereof | |
| CN110801826A (en) | Photoelectrocatalysis graphite felt material and preparation method and application thereof | |
| CN109876816A (en) | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application | |
| CN109621975A (en) | A kind of support type ozone catalytic oxidation catalyst and its preparation method and application | |
| CN113398916B (en) | Method for preparing persulfate catalyst from waste chrome-containing leather scraps and application of persulfate catalyst | |
| CN105478118B (en) | A kind of Cu/TiO2Nanorods Catalyst and preparation method thereof and the application in waste water wet oxidation | |
| CN114225952A (en) | Magnetic nitrogen-doped carbon nanotube and preparation method and application thereof | |
| CN114628707A (en) | Modified carbon brush cathode material for microbial electro-Fenton fuel cell and preparation method and application thereof | |
| CN110302779B (en) | Composite catalyst for treating wastewater containing auxiliary agent |
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 |