CN116212924A - Multi-site catalyst prepared from Fenton iron mud, and preparation method and application thereof - Google Patents

Multi-site catalyst prepared from Fenton iron mud, and preparation method and application thereof Download PDF

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CN116212924A
CN116212924A CN202310088084.8A CN202310088084A CN116212924A CN 116212924 A CN116212924 A CN 116212924A CN 202310088084 A CN202310088084 A CN 202310088084A CN 116212924 A CN116212924 A CN 116212924A
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site catalyst
iron mud
fenton iron
fenton
wastewater
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王俩
侯立安
陈冠益
李宁
程小双
吴霜
颜蓓蓓
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • 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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Abstract

The invention relates to the technical field of sewage treatment, in particular to a multi-site catalyst prepared from Fenton iron mud, and a preparation method and application thereof. According to the invention, fenton iron mud is directly pyrolyzed, and a multi-site catalyst prepared from Fenton iron mud is obtained by adjusting pyrolysis temperature and time. The surface of the catalyst contains multiple activation sites of metal and nonmetal, and can be used for effectively degrading and removing dye in water through the cooperation of free radical and non-free radical ways, so that the simple and safe integral utilization of Fenton iron mud is realized, and the recycling problem of Fenton iron mud is solved.

Description

Multi-site catalyst prepared from Fenton iron mud, and preparation method and application thereof
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a multi-site catalyst prepared from Fenton iron mud, and a preparation method and application thereof.
Background
The Fenton (Fenton) method is an advanced oxidation technology, and is particularly suitable for treating various waste water due to the advantages of strong oxidizing property, low cost, operation under normal temperature and normal pressure, and the like. However, a large amount of waste iron sludge, i.e., fenton iron sludge, is generated in the process of treating wastewater by the Fenton method. Fenton iron mud contains a large amount of heavy metals and refractory organic matters, and is extremely easy to cause secondary pollution to the environment due to improper treatment.
At present, the Fenton iron mud is mainly disposed in landfill, incineration, cement-based solidification and the like. However, direct landfill is easy to cause heavy metal pollution soil and underground water in waste iron mud, and organic matters contained in the iron mud also cause problems of putrefaction, malodor and the like in the landfill process. While the incineration method can effectively remove organic matters in the waste iron mud and reduce the solid waste volume, the flue gas and fly ash generated in the incineration process are easy to cause atmospheric pollution, and heavy metals in the iron mud also have the risk of further pollution along with the atmospheric transmission. Although harmless treatment of the waste iron mud can be achieved by cement-based solidification, the waste iron mud still contains a large amount of metal resources, so that resource waste is caused.
In order to reasonably treat Fenton iron mud and recycle the Fenton iron mud, the prior art of Fenton iron mud component analysis and the influence of Fenton iron mud on anaerobic treatment of papermaking wastewater is mentioned, and the Fenton iron mud is used for strengthening the microbial anaerobic digestion process according to the characteristic that the Fenton iron mud has conductivity and contains a large amount of iron, so that the methane ratio in methane is improved. However, in the technology, the Fenton iron mud can be used for strengthening the anaerobic digestion process, and mainly comprises iron elements in the Fenton iron mud, but the Fenton iron mud is amorphous, has more impurities, and cannot play a role except iron in the Fenton iron mud, and finally can still be deposited.
In the prior art CN105836987, industrial ferrous sulfate is recovered and prepared from iron mud; in the prior art of Fenton iron mud for preparing ferrous sulfate and polymeric ferric sulfate and application research thereof, extracting ferrous sulfate and polymeric ferric sulfate from Fenton iron mud, and recycling the ferrous sulfate to a Fenton oxidation system for continuous wastewater treatment; in the prior art CN112723520, the iron mud is recovered and treated to obtain a new Fenton reagent suitable for Fenton reaction. The essence of the three recovery processes is to recycle the iron in the iron mud only. In the prior art CN114349296, fenton iron mud is integrally treated, and then substances are separated to obtain a catalyst Fe-SAC/NC, and the catalyst Fe-SAC/NC is catalyzed by fire coal. Although it carries out the integral treatment to Fenton iron mud, follow-up separation and continuous treatment process are comparatively complicated. Moreover, the four recovery treatment modes of Fenton iron mud all need to use acid or even strong acid in the treatment process, so that the safety of operators is easily influenced, and meanwhile, the pollution is also easily caused in the recovery treatment process. In the prior art CN115254110, fenton iron mud and titanium dioxide sol are treated together to obtain the Fenton iron mud-based suspension photocatalyst, but more additional materials are required to be added in the process of preparing the catalyst by the technology.
In view of the above, the art lacks a simple and safe way of integrally recycling Fenton iron mud.
Disclosure of Invention
The invention aims to provide a method for preparing a multi-site catalyst from Fenton iron mud, which is a simple and safe integral Fenton iron mud recycling mode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a multi-site catalyst from Fenton iron mud, which comprises the following steps:
under the protective atmosphere, the Fenton iron mud is heated to 650-800 ℃ at a heating rate of 2-10 ℃/min, and is kept for 1-5 h, so as to obtain the multi-site catalyst.
Optionally, the Fenton iron mud comprises the following elements in parts by weight:
Figure BDA0004069624110000021
optionally, the protective atmosphere comprises nitrogen, helium or argon, and the gas flow rate of the protective atmosphere is 50-150 mL/min.
The invention also provides a multi-site catalyst prepared by the method.
The invention also provides the multi-site catalyst for activating H 2 O 2 An application for removing dye in wastewater, comprising the following steps:
mixing the multi-site catalyst and the wastewater until adsorption balance is achieved, so as to obtain a mixture system;
the resulting mixture system and H 2 O 2 Mixing and reacting to remove dye in the wastewater.
Optionally, the dye in the wastewater comprises at least one of methylene blue, rhodamine B, congo red, methyl orange, and acid scarlet GR.
Optionally, the concentration of the multi-site catalyst in the mixture system is 0.05-0.5 g/L, and the concentration of the dye is 10-100 mg/L;
adding H to a mixture system 2 O 2 After that, H 2 O 2 The concentration of (C) is 20-80 mmol/L.
Optionally, before reaching adsorption equilibrium, when the multi-site catalyst is mixed with the wastewater, ultrasonic treatment is carried out for 1-3 min under the ultrasonic power of 80-300W, and then stirring is carried out for 50-70 min continuously; adding H 2 O 2 And (3) finishing the removal of the dye in the wastewater after the post reaction for 80-120 min.
The invention provides a method for preparing a multi-site catalyst from Fenton iron mud, which can simply and efficiently carry out integral recovery treatment on Fenton iron mud, and solves the problems that only iron in Fenton iron mud is recovered in the existing Fenton iron mud recovery treatment mode, and recovery and utilization of substances except iron in Fenton iron mud are not completed. After the Fenton iron mud is pyrolyzed at high temperature,the crystallinity is greatly improved, a rich pore structure is formed, a plurality of active sites are exposed, and the obtained catalyst can effectively activate H 2 O 2 The active species are generated to oxidize and remove the organic dye in the water.
In Fenton iron mud used in the invention, C and Si mainly come from natural organic matters and colloidal particle suspended matters in raw water, fe and S mainly come from introduction of a catalyst in a Fenton treatment process of wastewater, N mainly comes from addition of PAM in a mud storage tank, and Ca mainly comes from addition of alkali after Fenton reaction is finished. On the basis of the composition, the optimization of the composition of the catalyst crystal structure can be completed through the regulation and control of the temperature time in the Fenton iron mud pyrolysis process, so that nonmetallic active sites are formed on the surface of the catalyst besides metal active sites, and the problem that the existing iron mud-based catalyst is single in component and active site type is solved.
Surface Fe in multi-site catalyst Cat-700 prepared by the invention 0 The content of c=c/C-C and c=o active sites was 0.64%, 44.79% and 12.18%, respectively, for H 2 O 2 Plays an important role in the activation of (a). H using the multi-site catalyst prepared according to the present invention 2 O 2 Upon activation, catalyst/H 2 O 2 The system generates Fenton-like reaction, has rich active species, mainly generates various active species such as hydroxyl free radicals, singlet oxygen, superoxide free radicals and the like, and efficiently degrades and removes dye in water through the cooperation of free radical and non-free radical paths.
Drawings
FIG. 1 is an SEM image of the multi-site catalysts Cat-400, cat-500, cat-600 prepared in comparative examples 1 to 3 and of the multi-site catalyst Cat-700 prepared in example 1, where (a) is an SEM image of Cat-400, (b) is an SEM image of Cat-500, (c) is an SEM image of Cat-600, and (d) is an SEM image of Cat-700;
FIG. 2 is a plot of the ratio of the residual methylene blue content in water to the original methylene blue content in water over time for the multi-site catalysts Cat-400, cat-500, cat-600 prepared in comparative examples 1 to 3 and the multi-site catalyst Cat-700 prepared in example 1 under the same conditions to remove methylene blue dye in water.
Detailed Description
The invention provides a method for preparing a multi-site catalyst from Fenton iron mud, which comprises the following steps:
under the protective atmosphere, the Fenton iron mud is heated to 650-800 ℃ at a heating rate of 2-10 ℃/min, and is kept for 1-5 h, so as to obtain the multi-site catalyst.
In the present invention, the heating rate of the Fenton iron mud is 2 to 10 ℃/min, preferably 4 to 10 ℃/min, more preferably 6 to 10 ℃/min, still more preferably 8 to 10 ℃/min.
In the present invention, the Fenton iron mud is heated at 650 to 800 ℃, preferably 690 to 750 ℃, and more preferably 700 ℃.
In the present invention, the heating time is 1 to 5 hours, preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, still more preferably 2 to 3 hours.
In the invention, the Fenton iron mud comprises the following elements in parts by weight:
Figure BDA0004069624110000041
preferably 49.70 parts of carbon, 35.40 parts of iron, 3.43 parts of nitrogen, 3.33 parts of calcium, 2.98 parts of silicon, 1.45 parts of sulfur, 1.03 parts of aluminum, 0.88 part of phosphorus and 0.61 part of sodium.
In the present invention, the protective atmosphere includes nitrogen, helium or argon, and the gas flow rate of the protective atmosphere is 50 to 150mL/min, preferably 80 to 150mL/min, more preferably 110 to 150mL/min, and even more preferably 130 to 150mL/min.
The invention also provides a multi-site catalyst prepared by the method.
The invention also provides the multi-site catalyst for activating H 2 O 2 An application for removing dye in wastewater, comprising the following steps:
mixing the multi-site catalyst and the wastewater until adsorption balance is achieved, so as to obtain a mixture system;
the resulting mixture system and H 2 O 2 Mixing and reacting to remove dye in the wastewater.
In the present invention, the dye in the wastewater includes at least one of methylene blue, rhodamine B, congo red, methyl orange, and acid scarlet GR.
In the present invention, the concentration of the multi-site catalyst in the mixture system is 0.05 to 0.5g/L, preferably 0.1 to 0.5g/L; the concentration of the dye is 10-100 mg/L, preferably 15-100 mg/L, and more preferably 20-100 mg/L;
adding H to a mixture system 2 O 2 After that, H 2 O 2 The concentration of (C) is 20 to 80mmol/L, preferably 25 to 80mmol/L, more preferably 35 to 80mmol/L, still more preferably 45 to 80mmol/L.
In the invention, before reaching adsorption equilibrium, when the multi-site catalyst is mixed with the wastewater, ultrasonic treatment is carried out for 1 to 3 minutes under ultrasonic power of 80 to 300W, preferably 90 to 200W, more preferably 95 to 150W, and stirring is carried out for 50 to 70 minutes, preferably 55 to 65 minutes, more preferably 60 minutes; adding H 2 O 2 The post-reaction is carried out for 80 to 120 minutes, preferably 85 to 115 minutes, more preferably 90 to 110 minutes, still more preferably 85 to 105 minutes, to complete the removal of the dye in the wastewater.
The mass percentage of each element in the Fenton iron mud is measured by an X-ray fluorescence spectrometer.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Loading waste Fenton iron mud from a sewage treatment plant into a quartz boat and conveying the quartz boat into a tube furnace, wherein the Fenton iron mud mainly comprises the following elements in percentage by mass: 49.70% of carbon, 35.40% of iron, 3.43% of nitrogen, 3.33% of calcium, 2.98% of silicon, 1.45% of sulfur, 1.03% of aluminum, 0.88% of phosphorus and 0.61% of sodium, and the balance of the composition contains other elements such as titanium, magnesium, potassium, chlorine, zinc, manganese, chromium, copper, antimony, nickel, gadolinium, terbium, vanadium, bromine, barium, strontium, silver and zirconium. Continuously introducing nitrogen into the tube furnace at a flow rate of 150mL/min, heating the tube furnace to 700 ℃ at a heating rate of 10 ℃/min, maintaining for 2h, and cooling the quartz tube to room temperature to obtain the multi-site catalyst Cat-700.
At room temperature, the initial pH value of the methylene blue solution is regulated to 3.61 by using a sulfuric acid solution with the concentration of 0.1mol/L, the multi-site catalyst is mixed with the methylene blue solution in a 200mL beaker, the concentration of the multi-site catalyst in the mixed system is 0.4g/L, the concentration of the methylene blue is 100mg/L, and the mixed solution is subjected to ultrasonic treatment for 2min with the concentration of 100W to ensure that the mixed solution is uniformly mixed, and the mixed solution is continuously stirred for 60min to achieve adsorption balance. Adding H 2 O 2 To make H in the system 2 O 2 The concentration of (2) reached 50mmol/L and stirring was continued.
Respectively adding H 2 O 2 Taking 2.5mL of supernatant by a syringe at the time of 5min, 10min, 20min, 30min, 60min and 100min, filtering by a filter head with the aperture of 0.22 mu m, and adding into a centrifuge tube containing an excessive terminator, wherein the terminator is methanol. The ratio of the residual methylene blue content to the methylene blue content in the original solution at each time node was calculated by measuring the residual methylene blue content at 664nm with an ultraviolet-visible spectrophotometer, as shown in fig. 2.
Example 2
Loading waste Fenton iron mud from a sewage treatment plant into a quartz boat and conveying the quartz boat into a tube furnace, wherein the Fenton iron mud mainly comprises the following elements in percentage by mass: 49.70% of carbon, 35.40% of iron, 3.43% of nitrogen, 3.33% of calcium, 2.98% of silicon, 1.45% of sulfur, 1.03% of aluminum, 0.88% of phosphorus and 0.61% of sodium, and the balance of the composition contains other elements such as titanium, magnesium, potassium, chlorine, zinc, manganese, chromium, copper, antimony, nickel, gadolinium, terbium, vanadium, bromine, barium, strontium, silver and zirconium. Continuously introducing nitrogen into the tube furnace at a flow rate of 150mL/min, heating the tube furnace to 700 ℃ at a heating rate of 10 ℃/min, maintaining for 2h, and cooling the quartz tube to room temperature to obtain the multi-site catalyst Cat-700.
At room temperature, regulating the initial pH value of methylene blue solution to 3.61 by using 0.1mol/L sulfuric acid solution, mixing the multi-site catalyst with the methylene blue solution in a 200mL beaker, wherein the concentration of the multi-site catalyst in the mixed system is 0.3g/L, the concentration of the methylene blue is 30mg/L, and performing ultrasonic treatment for 2m at 100Win, uniformly mixing the materials, and continuously stirring the mixed solution for 60min to reach adsorption equilibrium. Adding H 2 O 2 To make H in the system 2 O 2 After 100min, 2.5mL of the supernatant was removed by syringe, filtered through a filter head having a pore size of 0.22. Mu.m, and added to a centrifuge tube containing an excess of a terminating agent, which was methanol. The residual methylene blue content was measured at 664nm by an ultraviolet-visible spectrophotometer, and the methylene blue degradation rate was 87.4%.
Example 3
Loading waste Fenton iron mud from a sewage treatment plant into a quartz boat and conveying the quartz boat into a tube furnace, wherein the Fenton iron mud mainly comprises the following elements in percentage by mass: 49.70% of carbon, 35.40% of iron, 3.43% of nitrogen, 3.33% of calcium, 2.98% of silicon, 1.45% of sulfur, 1.03% of aluminum, 0.88% of phosphorus and 0.61% of sodium, and the balance of the composition contains other elements such as titanium, magnesium, potassium, chlorine, zinc, manganese, chromium, copper, antimony, nickel, gadolinium, terbium, vanadium, bromine, barium, strontium, silver and zirconium. Continuously introducing nitrogen into the tube furnace at a flow rate of 150mL/min, heating the tube furnace to 700 ℃ at a heating rate of 10 ℃/min, maintaining for 2h, and cooling the quartz tube to room temperature to obtain the multi-site catalyst Cat-700.
At room temperature, the initial pH value of the methylene blue solution is regulated to 3.61 by using a sulfuric acid solution with the concentration of 0.1mol/L, the multi-site catalyst is mixed with the methylene blue solution in a 200mL beaker, the concentration of the multi-site catalyst in the mixed system is 0.2g/L, the concentration of the methylene blue is 30mg/L, and the mixed solution is subjected to ultrasonic treatment for 2min with the concentration of 100W to ensure that the mixed solution is uniformly mixed, and the mixed solution is continuously stirred for 60min to achieve adsorption balance. Adding H 2 O 2 To make H in the system 2 O 2 After 100min, 2.5mL of the supernatant was removed by syringe, filtered through a filter head having a pore size of 0.22. Mu.m, and added to a centrifuge tube containing an excess of a terminating agent, which was methanol. The residual methylene blue content was measured at 664nm by means of an ultraviolet-visible spectrophotometer, and the methylene blue degradation rate was 85%.
Example 4
Loading waste Fenton iron mud from a sewage treatment plant into a quartz boat and conveying the quartz boat into a tube furnace, wherein the Fenton iron mud mainly comprises the following elements in percentage by mass: 49.70% of carbon, 35.40% of iron, 3.43% of nitrogen, 3.33% of calcium, 2.98% of silicon, 1.45% of sulfur, 1.03% of aluminum, 0.88% of phosphorus and 0.61% of sodium, and the balance of the composition contains other elements such as titanium, magnesium, potassium, chlorine, zinc, manganese, chromium, copper, antimony, nickel, gadolinium, terbium, vanadium, bromine, barium, strontium, silver and zirconium. Continuously introducing nitrogen into the tube furnace at a flow rate of 150mL/min, heating the tube furnace to 700 ℃ at a heating rate of 10 ℃/min, maintaining for 3 hours, and cooling the quartz tube to room temperature to obtain the multi-site catalyst Cat-700-3.
At room temperature, the initial pH value of the methylene blue solution is regulated to 3.61 by using a sulfuric acid solution with the concentration of 0.1mol/L, the multi-site catalyst is mixed with the methylene blue solution in a 200mL beaker, the concentration of the multi-site catalyst in the mixed system is 0.5g/L, the concentration of the methylene blue is 100mg/L, and the mixed solution is subjected to ultrasonic treatment for 2min to ensure that the mixed solution is uniformly mixed, and the mixed solution is continuously stirred for 60min to achieve adsorption balance. Adding H 2 O 2 To make H in the system 2 O 2 After 100min, 2.5mL of the supernatant was removed by syringe, filtered through a filter head having a pore size of 0.22. Mu.m, and added to a centrifuge tube containing an excess of a terminating agent, which was methanol. The residual methylene blue content was measured by UV-visible spectrophotometry at 664nm to give a methylene blue degradation of 96.2%.
Comparative examples 1 to 3
Comparative examples 1 to 3 were different from example 1 in that the heating temperatures were 400℃and 500℃and 600℃respectively, and Cat-400, cat-500 and Cat-600 were obtained respectively, based on example 1, and the remainder was the same as in example 1.
SEM images of Cat-400, cat-500, cat-600 prepared in comparative examples 1 to 3 and Cat-700 prepared in example 1 were obtained by analyzing them with a scanning electron microscope, the surfaces of Cat-400 were smoother, a small amount of crystal particles were adhered, the pore structures were small, and the specific surface area was 49.94m 2 /g; the particle aggregate on the Cat-500 surface is obviously increased, the number of pore channels is increased to a certain extent, and the specific surface area is 48.48m 2 /g; with further increase of pyrolysis temperature, cat-600 has fluffy surface and specific surface area of 55.76m 2 /g; the roughness of Cat-700 surface is aggravated, and the specific surface area is obviously increased to 83.87m 2 /g。
Experimental example
Four sets of experiments for removing methylene blue from water were performed using Cat-700 prepared in example 1, based on example 1, except that Cat-700/H was used in each of the three sets of experiments 2 O 2 Tertiary butanol, chloroform and furfuryl alcohol were added to the system and the supernatant was taken only at 100min of reaction time.
Using a pseudo first order kinetic model, the methylene blue degradation reaction rate constant (k) is calculated by formula (1):
ln(C t /C 0 )＝-kt (1)
wherein C is t Represents the methylene blue concentration (mg/L) after a specific degradation time;
C 0 represents that the multi-site catalyst and methylene blue reach adsorption balance, and H is not added 2 O 2 Methylene blue concentration (mg/L);
t represents the oxidation reaction time (min).
Respectively calculating k according to the formula (1) 0 、k 1 、k 2 、k 3 Wherein k is 0 To add only H 2 O 2 The methylene blue degradation reaction rate constant;
k 1 a methylene blue degradation reaction rate constant for the additional addition of t-butanol;
k 2 the methylene blue degradation reaction rate constant when chloroform is additionally added;
k 3 the methylene blue degradation reaction rate constant for the additional addition of furfuryl alcohol.
Tert-butanol can capture Cat-700/H 2 O 2 In the system · OH, chloroform can capture Cat-700/H 2 O 2 O in the system 2 ·- Furfuryl alcohol can capture Cat-700/H 2 O 2 In the system 1 O 2 。
Calculating Cat-700/H by the formulas (2) to (4) 2 O 2 In the system · OH、O 2 ·- And 1 O 2 contribution degree of (2):
Figure BDA0004069624110000091
Figure BDA0004069624110000092
Figure BDA0004069624110000093
it was calculated that in example 1, the contribution degree of the hydroxyl radical and the singlet oxygen was 80.0% and 63.8%, respectively, which are the main active species, and the contribution degree of the superoxide radical was 8.1%, and the effect was small.
From the above embodiments, the present invention provides a multi-site catalyst made of Fenton iron mud, which realizes an integral, simple and safe recycling mode of Fenton iron mud. The catalyst has a plurality of activation sites, and can be used for effectively degrading and removing dye in water through the cooperation of free radical and non-free radical paths.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. A method for preparing a multi-site catalyst from Fenton iron mud, comprising the steps of:
under the protective atmosphere, the Fenton iron mud is heated to 650-800 ℃ at a heating rate of 2-10 ℃/min, and is kept for 1-5 h, so as to obtain the multi-site catalyst.
2. The method according to claim 1, wherein the Fenton iron mud comprises the following elements in parts by weight:
Figure FDA0004069624100000011
3. the method of claim 1 or 2, wherein the protective atmosphere comprises nitrogen, helium or argon, and the gas flow rate of the protective atmosphere is 50-150 mL/min.
4. A multi-site catalyst made by the process of any one of claims 1-3.
5. The multi-site catalyst of claim 4 in activating H 2 O 2 The application of removing the dye in the wastewater is characterized by comprising the following steps:
mixing the multi-site catalyst and the wastewater until adsorption balance is achieved, so as to obtain a mixture system;
the resulting mixture system and H 2 O 2 Mixing and reacting to remove dye in the wastewater.
6. The use according to claim 5, wherein the dye in the wastewater comprises at least one of methylene blue, rhodamine B, congo red, methyl orange and acid scarlet GR.
7. The use according to claim 5 or 6, characterized in that the concentration of the multi-site catalyst in the mixture system is 0.05-0.5 g/L and the concentration of the dye is 10-100 mg/L;
adding H to a mixture system 2 O 2 After that, H 2 O 2 The concentration of (C) is 20-80 mmol/L.
8. The use according to claim 5 or 6, wherein before reaching adsorption equilibrium, the multi-site catalyst is mixed with the wastewater, and is subjected to ultrasonic treatment for 1-3 min under ultrasonic power of 80-300W, and then is continuously stirred for 50-70 min; adding H 2 O 2 And (3) finishing the removal of the dye in the wastewater after the post reaction for 80-120 min.
CN202310088084.8A 2023-02-07 2023-02-07 Multi-site catalyst prepared from Fenton iron mud, and preparation method and application thereof Pending CN116212924A (en)

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