CN113522290A - Hollow magnetic composite carbon material derived based on metal-organic framework material, method thereof and wastewater treatment method - Google Patents
Hollow magnetic composite carbon material derived based on metal-organic framework material, method thereof and wastewater treatment method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
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- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 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
- 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
- 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
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention relates to a hollow magnetic composite carbon material derived based on a metal-organic framework material, a method thereof and a wastewater treatment method. The derivation method of the hollow magnetic composite carbon material comprises the following steps: dissolving cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid in N, N-dimethyl amide, uniformly mixing, and carrying out solvothermal reaction at the temperature of 150 ℃; cooling, washing and drying to obtain a precursor; roasting the prepared precursor in a tubular furnace filled with inert gas at a certain flow rate at the temperature of 600-900 ℃; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material. The highly dispersed cobalt-iron alloy in the hollow magnetic composite carbon material can react with monoperoxybisulfate to generate active substances such as sulfate radicals, hydroxyl radicals, singlet oxygen and the like with strong oxidizing property, so that organic pollutants which are difficult to degrade in wastewater are removed.
Description
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a hollow magnetic composite carbon material derived based on a metal-organic framework material, a deriving method of the hollow magnetic composite carbon material, and a method for applying the hollow magnetic composite carbon material to wastewater treatment.
Background
With the rapid development of industry, the treatment of water pollution environment becomes a worldwide problem, and the wide existence of refractory organic pollutants makes the water treatment more and more concerned by people. The persistent organic pollutants are difficult to remove by traditional biological, physical and chemical methods due to complex components, stable structure and long half-life. And most of the organic pollutants which are difficult to degrade have certain toxicity and are easy to be retained in organisms, so that people and animals are cancerated, distorted, feminized and the like. The advanced oxidation technology has the characteristics of rapidness, no selectivity, thorough oxidation and the like, has better treatment effect on trace refractory organic pollutants, high-concentration organic wastewater and the like in the environment, and improves an effective solution for solving the environmental problem. Therefore, advanced oxidation technology is becoming the first choice for treating refractory organic pollutants.
In recent years, advanced oxidation technology based on monoperoxybisulfate has attracted more and more researchers' attention and research due to the advantages of strong oxidation capability, wide applicable pH range, simple operation and the like. The use of transition metals is a very effective way of activating monoperoxybisulfate. The decomposition of monoperoxybisulfate (PMS) produces SO with very strong oxidizing power4 －·And hydroxyl radical (. OH), so that the system has better treatment effect on the organic wastewater under the acidic to near-alkaline condition. Metal-Organic Framework Materials (MOFs) are prepared by passing inorganic Metal nodes and Organic bridging ligands throughThe novel material with a periodic structure is obtained by coordination self-assembly. Recent research shows that MOFs as a heterogeneous catalyst shows outstanding performance in the aspect of pollution environment treatment, and particularly shows great application prospect in the aspect of removing water pollutants.
However, in the prior art, unstable precipitation of metal ions such as cobalt ions in a reaction system of metal organic framework material activated hydrogen monoperoxysulfate causes secondary pollution to the environment, and treatment processes such as ion exchange, adsorption, precipitation separation and the like need to be further added, so that the treatment cost is increased. In order to solve the problem, chinese patent application No. 2019109886078 discloses an iron-cobalt bimetallic-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand, its preparation method and application, although the technical scheme has its advantages, it also has the following disadvantages: the stability is insufficient, the TOC concentration in a system is increased due to collapse of an organic ligand in a catalyst framework in the recycling process, the concentration of the precipitated metal ions is over-standard due to increase of the concentration of the catalyst, and particularly the catalytic performance of the catalyst is greatly reduced due to precipitation of the metal ions when the catalyst is used under an acidic condition.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a hollow magnetic composite carbon material derived from a metal-organic framework material, a derivation method of the hollow magnetic composite carbon material, and application of the hollow magnetic composite carbon material in the field of wastewater treatment.
The invention adopts the technical scheme that:
a method for deriving a hollow magnetic composite carbon material based on a metal-organic framework material comprises the following steps:
(1) preparation of a reaction precursor: dissolving cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxyterephthalic acid in an N, N-dimethylformamide solvent, uniformly mixing, carrying out solvothermal reaction (preferably for 24 hours) at the temperature of 150 ℃, cooling, washing and drying to obtain a precursor;
(2) roasting the precursor prepared in the step (1) at the temperature of 600-900 ℃ in a tubular furnace filled with inert gas at a certain flow rate for a certain time; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material.
Preferably, in step (1), the molar ratio of cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxyterephthalic acid is 4: 1: 2.5-1: 4: 2.5.
preferably, in the step (2), the inert gas is nitrogen or argon, and the flow rate of the inert gas is 20-40mL min-1。
Preferably, in the step (2), the roasting reaction time is 1.5-4.0 h
The invention also provides a hollow magnetic composite carbon material, which is derived by the method for deriving the hollow magnetic composite carbon material based on the metal-organic framework material.
Preferably, the form of the hollow magnetic composite carbon material is a regular hollow polyhedral structure.
The invention also provides an application of the hollow magnetic composite carbon material in the field of wastewater treatment, namely a wastewater treatment method, which comprises the following steps: adding monoperoxybisulfate serving as an oxidant and a hollow magnetic composite carbon material derived from a metal-organic framework material serving as a catalyst into wastewater to perform wastewater treatment reaction. The hollow magnetic composite carbon material derived based on the metal-organic framework material can efficiently catalyze and activate the monoperoxybisulfate, and quickly and effectively remove toxic, harmful and nonbiodegradable organic matters in the wastewater.
Preferably, the hydrogen monoperoxysulfate is sodium monoperoxysulfate or potassium monoperoxysulfate.
Preferably, the molar ratio of the monoperoxybisulfate to the organic pollutants in the wastewater is 1-300: 1, the addition amount of the metal-organic framework material-based derived hollow magnetic composite carbon material is 20-1000 mg/L. The adding amount of the monoperoxybisulfate is determined according to the concentration of organic pollutants in the wastewater, and the larger the concentration of the organic pollutants is, the more monoperoxybisulfate is added.
Preferably, the temperature of the wastewater treatment reaction is 20-60 ℃, and the time is 2-180 min; the wastewater treatment reaction is carried out under the condition of stirring or oscillation, and the rotating speed of the stirring or oscillation is 50-200 rpm; the wastewater is organic wastewater, and the pH value of the organic wastewater is 3.0-11.0.
The principle of the invention is as follows: the invention provides a water treatment technology for efficiently activating monoperoxy hydrogen sulfate based on a metal-organic framework material derived hollow magnetic composite carbon material, which is characterized in that the metal-organic framework material derived hollow magnetic composite carbon material is used as a heterogeneous catalyst of monoperoxy hydrogen sulfate, the metal-organic framework material derived hollow magnetic composite carbon material and the monoperoxy hydrogen sulfate are reacted with organic wastewater to be treated in the presence of the metal-organic framework material derived hollow magnetic composite carbon material and the monoperoxy hydrogen sulfate, and uniformly dispersed iron and cobalt in the metal-organic framework material derived hollow magnetic composite carbon material can efficiently activate the monoperoxy hydrogen sulfate to generate SO with strong oxidizing property4 -·OH and1O2and the like, so that the aim of efficiently removing the organic pollutants difficult to degrade can be fulfilled. The reaction can be carried out in a wider pH value range, and the method has the advantages of less catalyst consumption, short reaction time, good cycle performance, high catalytic oxidation rate, simple equipment, convenient operation, environmental friendliness, easy recycling of the catalyst due to magnetism and the like, and has a great application prospect in the technical field of advanced wastewater treatment.
Compared with the prior art, the invention has the following technical effects:
(1) the preparation method of the metal-organic framework material derived hollow magnetic composite carbon material provided by the invention has the advantages of mild reaction conditions, no special requirements on external environmental conditions, simple operation, strong repeatability and easy realization.
(2) The metal-organic framework material derived hollow magnetic composite carbon material as the heterogeneous catalyst for activating the monoperoxybisulfate can be applied to wastewater treatment, and the metal-organic framework material derived hollow magnetic composite carbon material is applied to the reaction for treating organic pollutants by an advanced oxidation method based on the monoperoxybisulfate for the first time; the hollow magnetic composite carbon material derived based on the metal-organic framework material has the advantages that iron and cobalt are uniformly dispersed in the framework material, so that the catalytic activity can be obviously improved. The invention fully utilizes highly dispersed cobalt and iron active central ions in the hollow magnetic composite carbon material derived based on the metal-organic framework material, enhances the effective contact of transition metal ions and monoperoxybisulfate to enhance the generation of active free radicals with strong oxidizing property, thereby accelerating the oxidative degradation of refractory organic pollutants in wastewater; the high catalytic activity hollow magnetic composite carbon material derived based on the metal-organic framework material enables the monoperoxybisulfate to be effectively decomposed to generate active free radicals, and the method has the advantages of high utilization rate of the free radicals, short reaction time and good removal effect on pollutants.
(3) According to the invention, the hollow magnetic composite carbon material derived based on the metal-organic framework material is used as a heterogeneous phase catalyst to catalyze the hydrogen monoperoxysulfate, and has high catalytic activity within the pH range of 3.0-11.0, so that the pH value of the wastewater suitable for treatment is greatly widened, and the acid-base regulation cost is effectively reduced.
(4) The hollow magnetic composite carbon material derived based on the metal-organic framework material is used as a heterogeneous catalyst, so that the activity is high, the dosage is small, the monoperoxy hydrogen sulfate can be efficiently catalyzed at normal temperature without illumination and other conditions, the cost of sewage treatment is reduced, the catalyst with magnetism after reaction is easier to recycle from a solution, and no secondary pollution is caused.
(5) The hollow magnetic composite carbon material derived based on the metal-organic framework material is adopted as a heterogeneous catalyst, so that the stability is good, and the precipitation rate of metal ions is far higher than that of a precursor of the metal-organic framework material; the material catalyst has better recycling performance under neutral and near-alkaline conditions, and the catalytic performance of the material catalyst is hardly reduced after being used for many times.
(6) The method has the advantages of simple operation, easily controlled conditions, high catalytic efficiency, economy and feasibility, and is suitable for the advanced treatment of various organic wastewater.
(7) The method still keeps higher pollutant removal rate under the condition of higher pH, is suitable for treating various organic wastewater, has high efficiency, good durability, convenient operation and environmental protection, can efficiently remove toxic and harmful pollutants in the wastewater within a wider pH range, and provides wide prospects for treating the toxic, harmful and nonbiodegradable organic wastewater.
Compared with an application number 2019109886078 of an iron-cobalt bimetallic-organic framework material based on a 2, 5-dihydroxy terephthalic acid ligand and a preparation method and application thereof, the technical scheme of the invention has the following advantages: the catalyst has higher catalytic activity and longer durability of catalytic capability, and tests show that the catalyst can be circularly reacted for 5 times when the pH value is 7 and the pH value is 9, the catalytic performance of the catalyst is hardly reduced, the stability of the catalyst is greatly improved, and the precipitation rate of metal ions is greatly reduced. In addition, the roasted and modified catalyst has strong magnetism, and can be separated from the reaction liquid directly through a magnet, so that the treatment cost for separating the catalyst after reaction is reduced, and the environmental threat to a water environment ecosystem caused by incomplete residual water environment after separation of the catalyst and the reaction liquid is also reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a metal-organic framework material-based derived hollow magnetic composite carbon material prepared by the invention with a magnification of 500 ten thousand times.
FIG. 2 is a scanning electron microscope image of 2000 ten thousand times magnification of the hollow magnetic composite carbon material derived based on the metal-organic framework material prepared by the invention.
FIG. 3 is a transmission electron microscope image of a hollow magnetic composite carbon material derived based on a metal-organic framework material prepared by the invention.
FIG. 4 is an X-ray crystal diffraction diagram of a hollow magnetic composite carbon material derived based on a metal-organic framework material prepared by the present invention.
FIG. 5 is a Raman spectrum of a metal-organic framework material-based derivatized hollow magnetic composite carbon material prepared according to the present invention.
Detailed Description
The invention will be further described with reference to the drawings and preferred embodiments, but the scope of protection of the invention is not limited thereto.
Cobalt nitrate hexahydrate (Co (NO) used in examples of the present invention3)2·6H2O), chlorine tetrahydrateFerrous sulfide (FeCl)2·4H2O), 2, 5-dihydroxyterephthalic acid (C)8H6O6) N, N-dimethylformamide (DMF, C)3H7NO), potassium monoperoxysulfate, etc. are analytically pure, acid orange G is chromatographically pure, and the water used is deionized water.
According to statistics, the variety of the dyes for commercial use exceeds 100000, the annual output of the dyes in the world is about 80 ten thousand to 90 ten thousand tons, while the annual output of the dyes in China is about 15 ten thousand tons, and the dye output in the world is in the forefront. Wherein 10-15% of the dye is released into the environment during production and use. Most dyes are extremely stable and are difficult to naturally degrade after entering a water body, so that the chromaticity of a polluted water area is increased, the quantity of incident light is influenced, the normal life activities of aquatic animals and plants in the water body are further influenced, and the ecological balance of the water environment is damaged. More seriously, most dyes have carcinogenic and teratogenic effects and are discharged into aqueous environments causing significant harm to humans and other organisms. The invention considers that the dye is widely applied to industries such as medicine, food, printing and dyeing, cosmetic manufacturing and the like. Therefore, the invention selects and uses wider acid Orange G (OG) as a representative of pollutants, and researches on decolorization and degradation of OG can represent degradation of organic wastewater difficult to biochemically degrade to a certain extent. The organic wastewater in the following examples is OG solution.
The method is adopted to treat the organic wastewater containing acid Orange G (OG).
Example 1
A method for deriving a hollow magnetic composite carbon material based on a metal-organic framework material comprises the following steps:
(1) preparing a precursor: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2Dissolving O and 0.498g (3mM) of 2, 5-dihydroxyterephthalic acid in 60mL of N, N-Dimethylformamide (DMF), stirring the mixed solution until the mixed solution is completely dissolved, transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24 hours at 150 ℃; cooling, naturally cooling to room temperature, filtering with vacuum pump, and adding anhydrous ethyl acetateRepeatedly washing alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the precursor based on the metal-organic framework material.
(2) Filling the precursor prepared in the step (1) with N at the temperature of 600 DEG C2Roasting for 2.0 hours in a tubular furnace with the flow rate of 20 mL/min; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material.
The hollow magnetic composite carbon material derived based on the metal-organic framework material is characterized by adopting a scanning electron microscope, X-ray crystal diffraction and infrared rays, wherein, FIG. 1 is a scanning electron microscope image with a magnification of 500 ten thousand times based on the metal-organic framework material derived hollow magnetic composite carbon material in this example, FIG. 2 is a scanning electron microscope image of 2000 ten thousand times magnification of the hollow magnetic composite carbon material derived based on the metal-organic framework material in this example, FIG. 3 is a transmission electron microscope image of a hollow magnetic composite carbon material derived based on a metal-organic framework material in the present example, FIG. 4 is an X-ray crystal diffraction pattern of the hollow magnetic composite carbon material derived based on the metal-organic framework material, a material X-ray crystal diffraction pattern, fig. 5 is a raman spectrum of the hollow magnetic composite carbon material derived based on the metal-organic framework material in this example. From the above illustration, the present invention indeed produces a hollow magnetic composite carbon material derived from a metal-organic framework material, which is in the form of a hollow regular polyhedral crystal and strongly attracted by a magnet. ICP-MS detection results show that the molar ratio of cobalt element to iron element in the material obtained by the preparation method is close to 1: 1, indicating that the hollow magnetic composite carbon material derived based on the metal-organic framework material is successfully prepared.
Example 2
A method for deriving a hollow magnetic composite carbon material based on a metal-organic framework material comprises the following steps:
(1) preparing a precursor: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2O and 0.498g (3mM)2, 5-dihydroxyterephthalic acid were dissolved in 60mL N, N-dimethylStirring the mixed solution until the mixed solution is completely dissolved in formamide (DMF), transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24 hours at 150 ℃; cooling, naturally cooling to room temperature, filtering by a vacuum pump, and repeatedly washing with absolute ethyl alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the precursor based on the metal-organic framework material.
(2) Filling the precursor prepared in the step (1) with N at the temperature of 700 DEG C2Roasting for 2.0 hours in a tubular furnace with the flow rate of 20 mL/min; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material.
Example 3
A method for deriving a hollow magnetic composite carbon material based on a metal-organic framework material comprises the following steps:
(1) preparing a precursor: 0.873g (3mM) of Co (NO)3)2·6H2O、0.596g(3mM)FeCl2·4H2Dissolving O and 0.498g (3mM) of 2, 5-dihydroxyterephthalic acid in 60mL of N, N-Dimethylformamide (DMF), stirring the mixed solution until the mixed solution is completely dissolved, transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a program-controlled oven, and carrying out solvothermal reaction for 24 hours at 150 ℃; cooling, naturally cooling to room temperature, filtering by a vacuum pump, and repeatedly washing with absolute ethyl alcohol, N-Dimethylformamide (DMF) and deionized water to obtain a coffee precipitate; and (3) drying the precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain black solid powder, namely the precursor based on the metal-organic framework material.
(2) Filling the precursor prepared in the step (1) with N at the temperature of 800 DEG C2Roasting for 2.0 hours in a tubular furnace with the flow rate of 20 mL/min; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material.
Example 4
And (3) adding the OG removal rate based on the metal-organic framework material derived hollow magnetic composite carbon material and potassium monoperoxysulfate, or based on the metal-organic framework material derived hollow magnetic composite carbon material or potassium monoperoxysulfate.
A conical flask is adopted as a reactor, the reaction volume of the wastewater is 100mL, the initial concentration of OG contained in the wastewater is 0.2mM, and the pH value is 2.86; three processing groups were set: wherein, the treatment group 1 simultaneously added the metal-organic framework material-based derived hollow magnetic composite carbon material (prepared by the method of example 1) and potassium monoperoxysulfate (final concentrations of 0.05g/L and 2mM, respectively) to the reaction flask, and the treatment group 2 separately added the metal-organic framework material-based derived hollow magnetic composite carbon material (final concentration of 0.05g/L) without adding potassium monoperoxysulfate; the treatment group 3 added potassium monoperoxysulfate (final concentration of 2mM) alone without adding a metal-organic framework material-based derivative hollow magnetic composite carbon material; placing the three treatment group reaction bottles in a shaking bed, reacting at the rotation speed of 100rpm and the temperature of 25 ℃, detecting the content of OG in a reaction system at regular time, and calculating the OG removal rate; the results of the comparison of the OG removal rates of the different treatment groups are shown in table 1.
TABLE 1
The results in table 1 show that the OG cannot be effectively degraded and removed by a metal-organic framework material derived hollow magnetic composite carbon material and a potassium monoperoxysulfate system, the OG treatment effect is very obvious in a metal-organic framework material derived hollow magnetic composite carbon material activated potassium monoperoxysulfate system, and after the reaction is carried out for 30min, the OG removal rate reaches 98.2%, so that the method can quickly and effectively treat the wastewater difficult to be biochemically treated.
Example 5
The OG removal rate of potassium peroxymonosulfate activated by a hollow magnetic composite carbon material derived based on a metal-organic framework material under acidic, neutral and alkaline conditions is improved.
A conical flask is adopted as a reactor, the reaction volume of the wastewater is 100mL, and the initial concentration of OG contained in the wastewater is 0.2 mM; four processing groups are set: adding potassium monoperoxysulfate into a reaction bottle before the reaction starts to enable the concentration of the potassium monoperoxysulfate to be 2mM, respectively adjusting the pH value of wastewater to be 2.86 (treatment group 1), 5.0 (treatment group 2), 7.0 (treatment group 3), 9.0 (treatment group 4) and 11.0 (treatment group 5), then adding a metal-organic framework material-derived hollow magnetic composite carbon material (prepared by the method of example 1) into the reaction bottle to enable the reaction concentration to be 0.05g/L, placing the reaction bottle into a shaking bed, carrying out reaction under the conditions that the rotating speed is 100rpm and the temperature is 25 ℃, regularly detecting the content of OG in the reaction system, and calculating the removal rate of OG; the results of the effect of pH on OG degradation based on activation of potassium monoperoxysulfate based on the metal-organic framework material derived hollow magnetic composite carbon material are shown in Table 2.
TABLE 2
The results in table 2 show that the oxidation method of the iron-cobalt bimetallic-organic framework material activated potassium monoperoxysulfate has very good degradation effect on OG under acidic and near-neutral conditions, saves the acid feeding cost and ensures the high efficiency of the advanced oxidation technology. The treatment effect is best under the condition that the pH value is 7.0, the consumption of the hollow magnetic composite carbon material derived based on the metal-organic framework material is less, and the activation efficiency is high.
Example 6
Based on the influence of different adding amounts of the metal-organic framework material derived hollow magnetic composite carbon material on the OG removal rate.
A conical flask is used as a reactor, the reaction volume of wastewater is 100mL, the initial concentration of OG contained in the wastewater is 0.2mM, the pH is 6.1, potassium monoperoxysulfate is added into the reaction flask to enable the concentration to be 2mM before the reaction starts, and four treatment groups are set: adding a metal-organic framework material-derived hollow magnetic composite carbon material (prepared by the method of example 3) into a reaction bottle to enable the reaction concentration to be 0.025g/L (treatment group 1), 0.05g/L (treatment group 2), 0.075g/L (treatment group 3) and 0.1g/L (treatment group 4), finally placing the reaction bottle into a shaking bed, carrying out reaction under the conditions of the rotating speed of 100rpm and the temperature of 25 ℃, detecting the content of OG in a reaction system at fixed time, and calculating the removal rate of OG; the results of the effect of the concentration of the hollow magnetic composite carbon material derived based on the metal-organic framework material on degradation of OG by activated potassium monoperoxysulfate are shown in table 3.
TABLE 3
The results in Table 3 show that the concentration of the hollow magnetic composite carbon material derived based on the metal-organic framework material has a certain influence on the degradation of OG by activated potassium peroxymonosulfate, the degradation rate of OG is increased along with the increase of the concentration of the hollow magnetic composite carbon material derived based on the metal-organic framework material, the degradation rate of OG is the highest when the concentration of the hollow magnetic composite carbon material derived based on the metal-organic framework material is 0.1g/L, and OG is degraded within 20min by 100%. The hollow magnetic composite carbon material derived based on the metal-organic framework material has high activity and small dosage. Therefore, the method has wide application prospect in organic wastewater difficult to biochemically treat.
In conclusion, the highly dispersed cobalt-iron alloy in the hollow magnetic composite carbon material can react with the monopersulfate to generate active substances such as sulfate radicals, hydroxyl radicals, singlet oxygen and the like with strong oxidizing property, so that the refractory organic pollutants in the wastewater are removed. The hollow magnetic composite carbon material derived based on the metal-organic framework material is suitable for treating various organic wastewater, has high efficiency, good durability, convenient operation and environmental protection, and provides wide prospect for treating toxic, harmful and nonbiodegradable organic wastewater.
Compared with the technical scheme of application number 2019109886078, the invention has the following substantial differences: the invention creatively adds a step of roasting link, the crystal structure of the catalyst material obtained after roasting is essentially changed, and iron and cobalt ions in the MOF framework are converted into simple substances, which directly causes different effect application and mechanism of the catalyst material in wastewater treatment, for example, for methylene blue simulated wastewater with the same concentration of 0.2 millimole, the MOF takes 30-45 minutes for complete decolorization, while the catalyst obtained after modification roasting only takes 10-30 minutes. The technical scheme of application No. 2019109886078 is mainly to oxidize and degrade organic pollutants by catalyzing monoperoxybisulfate to generate sulfate radicals and hydroxyl radicals, while the technical scheme of the hollow magnetic composite carbon material derived from the metal-organic framework material degrades organic matters only in a small part through the mechanism, and the removal of the organic matters is more to convert monoperoxybisulfate into singlet oxygen and other active substances by depending on the composite material of metal simple substances and carbon. The metal-organic framework material derived hollow magnetic composite carbon material has strong magnetism, and can directly adsorb and separate the catalyst by a magnet after reaction. The technical scheme of the invention is obviously superior to the technical scheme of application number 201910988131.8.
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 method for deriving a hollow magnetic composite carbon material based on a metal-organic framework material is characterized by comprising the following steps:
(1) dissolving cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid in N, N-dimethyl amide, uniformly mixing, and carrying out solvothermal reaction at the temperature of 150 ℃; cooling, washing and drying to obtain a precursor;
(2) roasting the precursor prepared in the step (1) in a tubular furnace filled with inert gas at a certain flow rate at the temperature of 600-900 ℃; and cooling to obtain the metal-organic framework material-based derived hollow magnetic composite carbon material.
2. The method for derivatizing a hollow magnetic composite carbon material based on a metal-organic framework material according to claim 1, wherein: in the step (1), cobalt nitrate hexahydrate, ferrous chloride tetrahydrate and 2, 5-dihydroxy terephthalic acid are mixed according to a molar ratio of 4: 1: 2.5-1: 4: 2.5.
3. the method for derivatizing a hollow magnetic composite carbon material based on a metal-organic framework material according to claim 1, wherein: in the step (2), the inert gas is nitrogen or argon, and the flow rate of the inert gas is 20-40mL min-1。
4. The method for derivatizing a hollow magnetic composite carbon material based on a metal-organic framework material according to claim 1 or 3, wherein: and (2) roasting for 1.5-4.0 h.
5. A hollow magnetic composite carbon material characterized by: derived by the method of any one of claims 1 to 4.
6. The hollow magnetic composite carbon material according to claim 5, wherein: the shape of the hollow magnetic composite carbon material is a regular hollow polyhedral structure.
7. A method for treating wastewater, characterized by comprising the steps of: the method of treating wastewater comprising adding hydrogen monoperoxysulfate as an oxidizing agent and the hollow magnetic composite carbon material derived from the metal-organic framework material according to claim 5 or 6 as a catalyst to wastewater to carry out a wastewater treatment reaction.
8. The wastewater treatment method according to claim 7, characterized in that: the monoperoxybisulfate is sodium monoperoxysulfate or potassium monoperoxysulfate.
9. The wastewater treatment method according to claim 8, characterized in that: the mole ratio of the monoperoxybisulfate to the organic pollutants in the wastewater is 1-300: 1, the addition amount of the metal-organic framework material-based derived hollow magnetic composite carbon material is 20-1000 mg/L.
10. A method for treating wastewater according to any of claims 7 to 9, characterized in that: the temperature of the wastewater treatment reaction is 20-60 ℃, and the time is 2-180 min; the wastewater treatment reaction is carried out under the condition of stirring or oscillation, and the rotating speed of the stirring or oscillation is 50-200 rpm; the wastewater is organic wastewater, and the pH value of the organic wastewater is 3.0-11.0.
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| CN112076752A (en) * | 2020-10-13 | 2020-12-15 | 南京林业大学 | MOF-74 derived magnetic composite catalyst and preparation method and application thereof |
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| CN110841714A (en) * | 2019-10-17 | 2020-02-28 | 杭州电子科技大学 | Iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof |
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