CN113877579A - Preparation method and application of catalyst for degrading endocrine disruptors - Google Patents
Preparation method and application of catalyst for degrading endocrine disruptors Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000000598 endocrine disruptor Substances 0.000 title claims abstract description 26
- 231100000049 endocrine disruptor Toxicity 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000000593 degrading effect Effects 0.000 title claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
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- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229920005610 lignin Polymers 0.000 claims abstract description 11
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
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- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
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- 238000001704 evaporation Methods 0.000 claims abstract 2
- 239000002351 wastewater Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
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- 230000002452 interceptive effect Effects 0.000 claims description 5
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- -1 Cl- Chemical class 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
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- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 238000013019 agitation Methods 0.000 claims 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
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- 229910052742 iron Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 239000007832 Na2SO4 Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—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
- 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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a preparation method and application of a catalyst for treating endocrine disruptors. Stirring lignin and dicyandiamide in water at the temperature of 60-75 ℃, evaporating to dryness, calcining, grinding, cleaning and drying the obtained solid in a protective atmosphere at the temperature of 600-800 ℃ to obtain nitrogen-doped biochar; then the FeSO is dissolved by a liquid phase reduction method4Mixing the solution with absolute ethyl alcohol, adding nitrogen-doped biochar, stirring uniformly, and adding KBH4And standing and aging the solution, separating, washing and drying the solid in the mixed solution to prepare the nitrogen-doped biochar loaded with the nano zero-valent iron. The catalyst enriches the active sites of the carrier by modifying the carrier biochar loaded with nano zero-valent ironThe synergistic effect of the carrier and zero-valent iron is realized, and the persulfate is activated by combining free radicals and non-free radical ways in the oxidation process, so that the adaptability of the system to pH change and various inorganic ion interferences is enhanced. The catalyst can effectively activate persulfate so as to remove the endocrine disrupter bisphenol A with a removal rate of 100% in a short time.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a catalyst for treating endocrine disruptors in wastewater and application thereof.
Background
Endocrine disruptors, also known as environmental hormones, can be absorbed by the body by enriching the food chain. Bisphenol A (BPA) is widely applied to industrial materials, is often applied to the fields of manufacturing can coatings, polycarbonate plastics, combustion improvers, medical instruments and the like, has biological toxicity, can cause endocrine dyscrasia, reproductive capacity reduction or immune diseases of people or animals at an extremely low concentration, and is a typical refractory endocrine disrupter.
The conventional physical adsorption method and biological treatment method hardly achieve efficient removal of bisphenol a, and the advanced oxidation method in chemical remediation is concerned because of its characteristics of effectiveness, low toxicity and low cost. The advanced oxidation method is mainly classified into a Fenton method, a photocatalytic oxidation method, and a persulfate oxidation method. Although the traditional Fenton method is efficient, the reaction has low adaptability to the pH change of a system, and a large amount of iron mud is generated in the process of the method, so that the method is not beneficial to the reutilization of the treated wastewater; the photocatalytic oxidation method requires a large amount of light energy input from an external source, the cost is too high when an artificial light source is used, the efficiency of utilizing natural light is not high, and the implementation has certain difficulty.
In recent years, techniques for degrading or mineralizing refractory organics by generating active oxygen through Persulfate (PS) activation have received increasing attention. Sodium Persulfate (PDS) is an environmentally friendly oxidant that is soluble in water. PDS dissolves in water to produce persulfate ions (S)2O8 2-) The PDS has good chemical stability in water and very low reactivity with organic pollutants, and requires additional energy or catalyst to activate PDS, thereby degrading organic pollutants by generating active oxygen.
Catalysts commonly used to activate PDS are transition metals, metal oxides and carbon-based materials. The nano Zero-valent iron (nZVI) refers to Zero-valent iron particles with the particle size of 1-100nm, has small particle size and high reactivity, and can activate PDS, but the nZVI has magnetism and high surface energy, and is easy to aggregate into micron particles, so that the reactivity is reduced. In order to solve the problem, research is carried out on the method that the nZVI is loaded on the carrier, the nZVI is dispersed on the carrier, the agglomeration of the nZVI is reduced, and higher catalytic capability is realized. Biochar is regarded as a suitable nZVI carrier material because it has a porous structure and is low in cost. However, the activation ability of the biochar on PDS is not strong, and the biochar is more of the function of dispersing nZVI and is not a direct influence factor of the catalytic ability. The original biochar loaded nZVI material still has the problems of single catalytic path, metal ion dissolution, poor reusability of the material, large interference of original substances of water and the like in practical application. Through modification of the biochar serving as the carrier, the nZVI loading capacity of the carrier is improved, the catalytic capacity of the biochar carrier is enhanced, and PDS is activated by the carrier and the nZVI in a synergistic manner, so that BPA is degraded and mineralized more efficiently.
The Chinese patent document "a method for catalytic oxidative degradation of bisphenol A in wastewater" (application No. CN 101456618A) discloses a method for removing bisphenol A in water, namely, a proper amount of tungstate and hydrogen peroxide are added into a system, the method can effectively degrade bisphenol A in water, but the pH range applicable to the method is only 9-11, and the degradation efficiency is greatly influenced by the change of the pH value. The Chinese invention patent document 'method for degrading bisphenol A by activating sodium persulfate through nano zero-valent iron' (application number CN 201810536144.7) discloses a method for preparing the bisphenol A by catalyzing and activating the sodium persulfate through the nano zero-valent iron, wherein the nano zero-valent iron is used as a catalyst to catalyze and activate the persulfate, the method can effectively degrade BPA in simulated wastewater, but the influence of actual environmental water on a reaction system is not considered, and the removal efficiency of the BPA is reduced because the nano zero-valent iron is easy to agglomerate in the water.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses a preparation method of modified biochar carrier loaded with nano zero-valent iron, the catalyst enriches the active sites of the biochar carrier, realizes the synergistic effect of the carrier and the zero-valent iron, and activates persulfate through free radical and non-free radical ways in the oxidation process, so that the adaptability of the system to pH and the anti-interference capability of various inorganic ions are enhanced. The persulfate activated by the catalyst shows good degradation activity and mineralization capability on bisphenol A which is a typical endocrine disrupter.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst for degrading endocrine disruptors, wherein the catalyst is nitrogen-doped biochar loaded with nano zero-valent iron, and comprises the following steps:
s1, weighing lignin (pure lignin can be adopted, and industrial lignin and waste lignin can also be adopted) and dicyandiamide, adding the lignin and dicyandiamide into water, hermetically stirring at 70-75 ℃, then stirring the mixture in an open way until the water is evaporated to dryness, calcining the mixture at 600-700 ℃ in a protective atmosphere, washing the calcined solid with water to remove impurities, drying, grinding and sieving the calcined solid to obtain nitrogen-doped biochar;
s2, adding the nitrogen-doped biochar obtained in the step S1 into absolute ethyl alcohol, uniformly stirring, and adding FeSO4Introducing inert gas into the solution and continuously stirring to fully mix the nitrogen-doped biochar with the solution;
s3, keeping the introduction and the stirring of the inert gas, and dropwise adding KBH into the mixed solution obtained in the step S24A solution;
s4, standing and aging the mixed solution obtained in the step S3 at room temperature, and washing and drying to obtain the nitrogen-doped biochar catalyst loaded with the nano zero-valent iron;
preferably, the mass ratio of the lignin to the dicyandiamide in the step S1 is 1: (2-6); the stirring speed is 100-120 rpm, and the stirring time is 4-5 hours; the temperature rise rate of the calcination is 5-10 ℃/min.
Preferably, the volume ratio of the mass of the nitrogen-doped biochar to the absolute ethyl alcohol in the step S2 is (0.1-0.7): 40 g/mL, mass of the nitrogen-doped biochar and FeSO4·7H2The mass ratio of O is (1-7): 5; and the stirring speed is that the mixing time of the nitrogen-doped biochar and the solution is 1-2 h.
Preferably, the inert gas in step S3 is nitrogen, argon or ammonia.
Preferably, the standing and aging time in the step S4 is 3-4 h.
The present invention further provides a catalyst for degrading endocrine disruptors, which is obtained by the above preparation method.
Further provides application of the catalyst for degrading endocrine disruptors in treating endocrine disruptors.
In particular embodiments, the endocrine disruptor wastewater also contains interfering ions, such as Cl-、NO3 -、SO4 2-
In a preferred embodiment, the initial pH of the wastewater containing the endocrine disruptors is 3-9; the concentration of the endocrine disruptor is 10-20 ppm; the interfering ions are Cl with the concentration adjusted to be 8-12mmol/L-、NO3 -、SO4 2-(ii) a The concentration of the nitrogen-doped biochar loaded with the nano zero-valent iron in the wastewater containing the endocrine disruptors is 0.1-0.5 g/L; the adding concentration of sodium persulfate in the endocrine disrupter wastewater is 1-3 mmol/L.
In the nitrogen-doped biological carbon catalyst loaded with the nano zero-valent iron, the biological carbon modified by nitrogen doping is used as a carrier to load and disperse the nano zero-valent iron, compared with the original unmodified biological carbon, the nitrogen-doped biological carbon is used as the carrier of the nano zero-valent iron, the electron density of ortho-position carbon is changed by the nitrogen doping, the activity of the ortho-position carbon is enhanced, graphite nitrogen, pyridine nitrogen and other structures are introduced into a graphite carbon network to be used as persulfate active sites, the nano zero-valent iron is dispersed and prevented from being aggregated, the nitrogen-doped biological carbon catalyst has certain capacity of activating persulfate and adsorbing organic matters, a non-free radical activation path can be provided for a system, and the activation path is cooperated with a free radical path provided by the nano zero-valent iron, so the nitrogen-doped biological carbon catalyst loaded with the nano zero-valent iron has strong anti-interference capacity on coexisting ions, and can keep high bisphenol A degradation, Mineralization ability.
Compared with the prior art, the invention has the following beneficial effects: the nitrogen-doped biological carbon catalyst loaded with the nano zero-valent iron realizes the cooperative activation of persulfate by free radicals and non-free radicals through the cooperative action of the nitrogen-doped modified biological carbon carrier and the loaded nano zero-valent iron, the adaptability of the catalyst to different environments is enhanced, and higher degradation efficiency can be kept. In addition, due to the modification of the carrier, the protection capability of the nano zero-valent iron is improved, the metal dissolution is reduced, and the actual application capability of the catalyst is improved. The nitrogen-doped biochar catalyst loaded with nano zero-valent iron obtained by the preparation method has richer active sites, can effectively activate persulfate to remove bisphenol A in water, and has stronger bisphenol A mineralization capability.
Drawings
FIG. 1 is a graph showing the effect of sodium persulfate addition on bisphenol A degradation in example 5.
FIG. 2 is a graph showing the effect of pH on bisphenol A degradation in example 6.
FIG. 3 is a graph showing the effect of inorganic anions on the degradation of bisphenol A in example 7.
FIG. 4 is an infrared spectrum of nitrogen-doped biochar loaded with nano zero-valent iron in a material characterization example.
Detailed Description
The following further illustrates the invention in connection with specific examples which should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Preparing nitrogen-doped biochar loaded with nano zero-valent iron:
1. 2g of lignin and 8g of dicyandiamide were dissolved in 200mL of water, and stirred at 75 ℃ in a water bath until the water was evaporated. The obtained dry solid was calcined at 700 ℃ for 1h under nitrogen atmosphere. Cooling to room temperature, cleaning the obtained material until the pH value is not changed, drying, grinding, and sieving with a 60-mesh sieve to obtain nitrogen-doped biochar;
2. weighing 1g of nitrogen-doped biochar, adding the nitrogen-doped biochar into 80mL of absolute ethanol, and adding 20mL of FeSO with the concentration of 0.18 mol/L4Solution, introducing nitrogen into the mixed solution as protective gas,simultaneously mechanically stirring at 350 rpm for 40min to ensure that the solution is fully mixed with the nitrogen-doped biochar;
3. keeping introducing nitrogen and mechanically stirring, and dropwise adding 50 mLKBH into the mixed solution at the speed of 2 mL/min4The solution was stirred for 20 min. Standing and aging the mixed solution for 3 hours to obtain a mixture with the mass ratio of iron to the carbon material of 1: 5, and sealing and storing the nitrogen-doped biological carbon catalyst loaded with the nano zero-valent iron for later use.
Identification of nitrogen-doped biochar loaded with nano zero-valent iron:
detecting the surface functional group of the catalyst by Fourier transform infrared spectroscopy (Samerfei, USA), wherein the detection wavelength range is 400cm-1To 4000cm-1. And (3) comparing active functional groups on the surfaces of the nitrogen-doped biochar (nZVI @ NBC) loaded with nano zero-valent iron with unmodified original Biochar (BC). As shown in FIG. 4, the infrared spectrum of the nitrogen-doped biochar loaded with nano zero-valent iron prepared in this example can be seen at a wavelength of 565cm-1、1250 cm-1、1605 cm-1、1694 cm-1And 2200 cm-1New functional group signals appear, C-C = O, C-N, N-H, C = O and C ≡ N, respectively. Compared with the original biochar, the nitrogen-doped biochar surface loaded with the nano zero-valent iron shows more abundant surface functional groups, and provides more active sites for catalytic oxidation reaction.
The application of the nitrogen-doped biochar loaded with nano zero-valent iron comprises the following steps:
and (3) adding 1mmol/L PDS and 0.3g/L nitrogen-doped biochar loaded with nano zero-valent iron prepared in the step (3) into BPA wastewater with the concentration of 20ppm to start an oxidation reaction, and carrying out the reaction on a reciprocating shaking table at room temperature. Sampling is carried out at the time points of 2, 5, 10, 15, 30, 60, 90 and 120min, and the oxidation reaction of the samples sampled at each time point is stopped by taking ethanol as a quenching agent. Wherein, BPA in the sample is detected by high performance liquid chromatography: the mobile phase is acetonitrile and water with equal volume, the flow rate is 0.6 mL/min, the column temperature is 30 ℃, and the detection wavelength is 277 nm. The results show that the reaction systems have BPA removal rates of 42.4%, 61.4%, 69.7%, 75.0%, 89.1%, 95.2% and 96.8% at the time of 2, 5, 10, 15, 30, 60 and 90min respectively, and the removal rate reaches 99.5% at the time of 120 min.
Example 2
Different from the embodiment 1, 2g of lignin and 4g of dicyandiamide are dissolved in 200mL of water, the temperature of the water bath is 60 ℃, and the obtained dry solid is calcined for 1h at 800 ℃ under the nitrogen atmosphere; 20mL of FeSO with a concentration of 0.13 mol/L was added in step 24And (3) obtaining a solution, wherein the mass ratio of the iron to the carbon material obtained in the step (3) is 1: 7, and the nitrogen-doped biological carbon catalyst loaded with nano zero-valent iron.
Referring to the application of example 1, the results show that the reaction systems have BPA removal rates of 37.3%, 47.6%, 52.3%, 64.3%, 80.7%, 92.5%, 97.1% at 2, 5, 10, 15, 30, 60, 90min, respectively, and 99.2% at 120 min.
EXAMPLE 3 Effect of sodium persulfate addition on bisphenol A degradation
Different from the example 1, the PDS in the step 4 is added into BPA wastewater (0.1 mmol/L) according to the concentration of 1.0, 1.5, 2.0 and 3.0mmol/L, and 0.2g/L of nitrogen-doped biochar loaded with nano zero-valent iron is added. Taking out water samples at the time of 2, 5, 10, 15, 30, 60, 90 and 120min, detecting the BPA concentration of the water samples, and simultaneously measuring the total organic carbon of the solution with the PDS addition amount of 1.0 mmol/L.
The result shows that the PDS dosage is 1mmol/L solution, and the total organic carbon removal rate is 73.3% after the reaction is carried out for 40 min; BPA was completely removed at 120min at various sodium persulfate concentrations.
FIG. 1 is a graph showing the effect of sodium persulfate head metering on bisphenol A degradation. As can be seen from FIG. 1, the optimal concentration ratio of PDS to the nitrogen-doped biochar loaded with nano zero-valent iron is 2mmol/L: 0.2 g/L.
Example 4 Effect of pH on bisphenol A degradation
In contrast to example 1, during the application process, 5 parts of BPA wastewater (20 ppm) with initial pH values of 3, 5, 7 and 9 were prepared, and after adding PDS at a concentration of 2mmol/L to each part of wastewater, 0.2g/L of nitrogen-doped biochar loaded with nano zero-valent iron was added. And taking out water samples at the moments of 2, 5, 10, 15, 30, 60, 90 and 120min, and detecting the BPA concentration of the water samples.
The result shows that the BPA removal rate is inhibited to a certain extent only when the pH is 9, and the catalytic system can efficiently degrade BPA within the pH range of 3-7.
FIG. 2 is a graph showing the effect of pH on bisphenol A. As can be seen from FIG. 2, the BPA removal rate at 120min still reached 84.1% at pH 9. BPA was completely removed within 120min at pH 3, 5, 7.
EXAMPLE 5 Effect of inorganic anions on bisphenol A degradation
In contrast to example 1, 4 parts of BPA wastewater (0.1 mmol/L) were prepared during the application, and NaCl and NaNO were added to the wastewater at a concentration of 10mmol/L, respectively3、Na2SO4And the concentrations of PDS and nitrogen-doped biochar loaded with nano zero-valent iron in each part of BPA wastewater are respectively controlled to be 2mmol/L and 0.2 g/L. And taking out water samples at the moments of 2, 5, 10, 15, 30, 60, 90 and 120min, and detecting the BPA concentration of the water samples.
FIG. 3 is a graph showing the effect of inorganic anions on bisphenol A degradation. As can be seen from FIG. 3, the concentration of NaCl in 10mmol/L and NaNO in 10mmol/L3、10mmol/L Na2SO4Under the coexistence condition, BPA is completely removed within 120 min. The results show that the material is capable of adapting to bodies of water containing interfering ions.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for degrading endocrine disruptors is characterized by comprising the following steps,
1) dissolving lignin and dicyandiamide in water, repeatedly stirring and evaporating in a water bath, calcining, grinding, cleaning and drying the obtained solid at 600-800 ℃ to obtain nitrogen-doped biochar;
2) will dissolve FeSO4After mixing the water and the absolute ethyl alcohol, adding nitrogen-doped biochar, and fully and uniformly stirring;
3) dropping KBH while maintaining agitation and aeration4And (3) solution dropwise adding, standing and aging the solution, separating, washing and drying the solid in the mixed solution to prepare the nitrogen-doped biochar loaded with the nano zero-valent iron.
2. The preparation method according to claim 1, wherein the mass ratio of the lignin to the dicyandiamide in the step 1) is 1: 2 to 6.
3. The method according to claim 1, wherein the FeSO is used in step 2)4The mass ratio of the nitrogen-doped biochar to the nitrogen-doped biochar is 5: 1 to 7.
4. The method according to claim 1, wherein the aeration in step 3) is performed under a protective gas such as nitrogen, argon or ammonia; standing and aging for 3-4 h.
5. The preparation method according to claim 1, wherein the temperature increase rate of the calcination in the step 1) is 5 to 10 ℃/min.
6. The catalyst for degrading endocrine disruptors obtained by the production method according to any one of claims 1 to 5.
7. Use of the catalyst of claim 6 for treating wastewater containing endocrine disruptors.
8. The use according to claim 7, wherein the endocrine disruptor wastewater also contains interfering ions, such as Cl-、NO3 -、SO4 2-。
9. The use according to claim 5, wherein the initial pH of the wastewater containing endocrine disruptors is 3 to 9; the concentration of the endocrine disruptor is 10-20 ppm; the interfering ions are Cl with the concentration adjusted to be 8-12mmol/L-、NO3 -、SO4 2-(ii) a The concentration of the nitrogen-doped biochar loaded with the nano zero-valent iron in the wastewater containing the endocrine disruptors is 0.1-0.5 g/L; the adding concentration of sodium persulfate in the endocrine disrupter wastewater is 1-3 mmol/L.
10. The use of claim 9, wherein the endocrine disruptor is bisphenol a.
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