CN114560548A - Method for removing dye in water by activating persulfate through loofah sponge charcoal catalyst - Google Patents

Method for removing dye in water by activating persulfate through loofah sponge charcoal catalyst Download PDF

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CN114560548A
CN114560548A CN202210118471.7A CN202210118471A CN114560548A CN 114560548 A CN114560548 A CN 114560548A CN 202210118471 A CN202210118471 A CN 202210118471A CN 114560548 A CN114560548 A CN 114560548A
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loofah sponge
dye
catalyst
persulfate
biochar
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CN114560548B (en
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袁兴中
戴欢
赵燕兰
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Hunan University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • B01J35/56
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/084Decomposition of carbon-containing compounds into carbon
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a method for removing dye in water by activating persulfate through a loofah sponge biochar catalyst, which is to degrade dye wastewater by activating persulfate through the loofah sponge biochar catalyst, wherein the loofah sponge biochar catalyst is prepared by calcining loofah sponge and performing acid modification, and the calcining temperature is 750-850 ℃. The loofah sponge charcoal catalyst has the advantages of high graphitization degree, ordered overall structure, thin tube wall, rich microporous structure, large specific surface area, excellent catalytic activity and the like, and when the loofah sponge charcoal catalyst is used for activating persulfate to degrade dyes in water, the loofah sponge charcoal catalyst has the advantages of simplicity in operation, no need of large-scale equipment, low cost, wide application range, small usage amount, high treatment efficiency, good treatment effect, strong reusability, environmental friendliness and the like, can efficiently degrade the dyes in water, and has good application value.

Description

Method for removing dye in water by activating persulfate through loofah sponge charcoal catalyst
Technical Field
The invention belongs to the field of loofah sponge recycling and advanced oxidation treatment of environmental pollutants, and particularly relates to a method for removing dye in water by activating persulfate through a loofah sponge charcoal catalyst.
Background
With the development of the printing and dyeing industry and the intermediate industrial and chemical industry, a large amount of dye wastewater is discharged into a water body, particularly, the azo dye wastewater can account for more than two thirds of the printing and dyeing wastewater, so that serious harm is caused to the water body and water body organisms, and the azo dye becomes a research focus and a difficult point due to the characteristics of high chromaticity, poor biodegradability, complex components, high toxicity and the like. In order to decolorize and mineralize the dye in the wastewater, more and more researchers are dedicated to searching for a dye treatment method with high efficiency, energy conservation, environmental protection and lower cost.
At present, the main treatment technical methods of dye wastewater can be divided into destructive methods and non-destructive methods. Non-destructive methods include adsorption, precipitation filtration, membrane separation, etc., which can directly remove dye molecules but cannot degrade or mineralize them; destructive methods are mainly advanced oxidation methods and biological methods, and such treatments can directly destroy the structure of the dye molecule or mineralize it. Biological methods are widely used because of their economy and good effect; but the operation is complex, the requirement on the quality of inlet water is high, and the method is not suitable for dye wastewater with high toxicity and poor biodegradability. Therefore, the search for a green and environment-friendly treatment method capable of efficiently degrading dyes is a big problem in the current society.
The advanced oxidation method is most widely applied in the field of water treatment, and the method adopts the reaction of an oxidant and organic pollutants in a water body to destroy the molecular structure of the pollutants, so that the pollutants are converted into other small molecular substances and even completely mineralized, and the aim of removing the pollutants is fulfilled. The use of persulfate (e.g., sodium persulfate, PS) based advanced oxidation technology is believed to be an efficient method for dye elimination, and persulfate-generated sulfate radicals (SO 4. cndot. -) have a higher redox potential, a wider range of pH applications, greater selectivity for target pollutants, and a longer half-life than hydroxyl radical (. OH-) based advanced oxidation technology, thereby enabling higher levels of mineralization of dyes in water. From the viewpoint of radical-based degradation mechanisms, the extremely active radicals can react with dye molecules by addition or other reactions, thereby breaking chemical bonds of the dye molecules, or mineralizing them directly into carbon dioxide and water.
Since persulfates are very stable at room temperature, activators become critical for persulfate systems, and much research has focused on the activation of persulfates. In the existing persulfate activation method, methods such as heat, ultraviolet light, ultrasonic wave and the like need high energy and strict reaction conditions; transition metal ion activation requires complex post-treatment to keep clean; alkaline activation requires adjustment of the pH of the system, which may increase the risk of corrosion of the equipment. Therefore, the carbon-rich biochar becomes a popular high-efficiency green catalyst with the advantages of good pore structure, large specific surface area, low cost, wide source and the like. Waste biomass such as wood, sludge, manure, pesticide residues and the like can be used for producing biochar through a thermochemical process, and the obtained biochar can be used for activating persulfate so as to generate Reactive Oxygen Species (ROS) to degrade organic pollutants. However, the present inventors found in previous studies that: the existing biochar prepared from waste biomass such as wood, sludge, manure, pesticide residue and the like is usually used as an adsorbent for adsorbing organic pollutants in a water body, the organic pollutants are not completely removed, and the problems of complex subsequent recovery treatment, complex steps and the like exist; in addition, even if the catalyst is used for activating persulfate, the problems of poor activation effect, large catalyst consumption, long treatment time, low dye removal rate in water and the like exist, and the aim of efficiently degrading the dye in the water is difficult to achieve.
Therefore, the loofah sponge charcoal catalyst which is high in graphitization degree, ordered in integral structure, thin in tube wall, rich in microporous structure, large in specific surface area and excellent in catalytic activity is obtained, and has important significance for effectively activating persulfate and realizing effective degradation of dye.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for removing the dye in the water body by activating the persulfate through the loofah sponge biochar catalyst, which has the advantages of simple operation, no need of large-scale equipment, low cost, wide application range, small using amount, high treatment efficiency, good treatment effect, strong reusability and environmental friendliness.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for removing dye in water by utilizing loofah sponge charcoal catalyst to activate persulfate, which is to degrade dye wastewater by utilizing loofah sponge charcoal catalyst to activate persulfate; the loofah sponge charcoal catalyst is prepared by calcining loofah sponge and performing acid modification; the calcining temperature is 750-850 ℃.
In the above method, further improvement, the preparation method of the loofah sponge biochar catalyst comprises the following steps:
S1, calcining the loofah sponge under the protection of inert gas to obtain a calcined product;
s2, mixing the calcined product obtained in the step S1 with an acid solution, standing, washing and drying to obtain the loofah sponge biochar catalyst.
In a further improvement of the above method, in step S1, the temperature increase rate during the calcination process is 5 ℃/min, and the calcination time is 2 h.
In the above method, further improvement is provided, in step S2, the concentration of the acid solution is 6mol/L, the acid solution is nitric acid, and the standing time is 12 h.
In a further improvement of the above method, in step S1, the inert gas is nitrogen, and the loofah sponge further includes the following pretreatment before calcination: washing and drying the loofah sponge; the temperature of the drying was 60 ℃.
In a further improvement of the above method, in step S2, the drying temperature is 110 ℃, and the drying time is 12 hours; the drying process further comprises the following steps: and grinding the dried product, and sieving the ground product by a 100-mesh sieve.
In the above method, further improvement, the degradation treatment is: mixing the loofah sponge biochar catalyst with the dye wastewater, stirring, and adding persulfate to perform degradation reaction to complete degradation of the dye in the wastewater.
In the method, the addition amount of the loofah sponge biochar catalyst is further improved, and 0.05 g-0.2 g of the loofah sponge biochar catalyst is added into each liter of dye wastewater.
In the method, the initial concentration of the dye wastewater is 0.1 mg/L-20 mg/L, the initial pH value of the dye wastewater is 3-10, and the dye in the dye wastewater comprises at least one of rhodamine B, acid orange, methyl orange and malachite green; the addition amount of the persulfate is 5-15 mmol of persulfate added in each liter of dye wastewater, and the persulfate is sodium persulfate.
In the method, the stirring time is 30min, and the degradation reaction time is 30-60 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for removing dye in water by activating persulfate through a loofah sponge biochar catalyst, which is characterized in that dye wastewater is degraded by activating persulfate through the loofah sponge biochar catalyst, wherein the adopted loofah sponge biochar catalyst is prepared by calcining loofah sponge and performing acid modification, and the calcining temperature is 750-800 ℃. Compared with the conventional biochar catalyst, the loofah sponge is selected as the precursor of the biochar, the loofah sponge has an obvious three-dimensional network tube bundle-shaped structure, and meanwhile, the components of the loofah sponge mainly contain cellulose, hemicellulose and lignin, wherein the cellulose and the lignin are beneficial to preparing the porous biochar material with a developed pore structure, and the catalyst has the advantages that the conventional biochar catalyst does not have. Therefore, the loofah sponge charcoal catalyst prepared by the invention has a rich cellular porous structure, can provide more active sites in the degradation reaction process, is easier to generate multi-electron transfer, and improves the catalytic activity; moreover, researches show that the catalytic mechanism and inactivation of the catalyst are closely related to the swelling effect, and the loofah sponge biochar is used for catalyzing The porous structure of the agent is more beneficial to adsorbing reactants on the surface or in pores of the catalyst, and the swelling effect formed by the porous structure can enable the reactants to be better contacted with active groups, so that the catalytic efficiency is further improved, and finally, the efficient removal of the dye in the water body is realized. Taking acid orange as an example, the degradation principle is shown in formulas (1) to (11), and specifically: catalytic sites on the surface of the loofah sponge biochar catalyst activate persulfate to generate SO4 ·-OH and O2 Isoradicals and1O2persulfates may react with water to form SO4 ·-Free radicals and1O2the groups react with pollutants adsorbed on the surface of the catalyst to degrade the dye (acid orange) into small molecular substances until finally degrading into water and carbon dioxide, thereby realizing high-efficiency degradation of the dye. In the degradation reaction process, besides the action of free radicals, an electrochemical characterization means is used for proving a non-free radical way mainly based on charge transfer, namely the loofah sponge biochar catalyst and Persulfate (PS) form an LSB-PS complex, and electrons are transferred to the LSB-PS complex from pollutants, so that the decomposition of the persulfate and the degradation of acid orange are accelerated. The method can be carried out at normal temperature and normal pressure, can mineralize various dyes (such as acid orange, methyl orange, rhodamine B, malachite green and the like) into water and carbon dioxide, can effectively carry out solid-liquid separation, has no secondary pollution, has the advantages of simple operation, no need of large-scale equipment, low cost, wide application range, small usage amount, high treatment efficiency, good treatment effect, strong reusability, environmental friendliness and the like, can efficiently degrade the dyes in the water body, and has good application value.
S2O8 2-+2H2O→HO2 -+2SO4 2-+3H+ (1)
S2O8 2-+HO2 -→SO4 ·-+SO4 2-+·O2 -+H+ (2)
SO4 ·-+OH→SO4 2-+HO· (3)
SO4 ·-+H2O→HSO4 -+HO· (4)
2·O2 -+2H2O→H2O2+2OH+1O2 (5)
LSBsurface-OOH+S2O8 2-→LSBsurface-OO·-+SO4 ·-+HSO4 - (6)
LSBsurface-OH+S2O8 2-→LSBsurface-O·-+SO4 ·-+HSO4 - (7)
AO7+SO4 ·-/HO·/·O2 /1O2→intermediates+CO2+H2O (8)
LSB+S2O8 2-→[LSB-PS*] (9)
[LSB-PS*]+AO7→2SO4 2-+LSB+AO7OX (10)
S2O8 2-+2e-→2SO4 2- (11)
(2) Compared with other biochar catalysts prepared from waste biomass such as wood, sludge, manure, pesticide residue and the like, the loofah sponge biochar catalyst disclosed by the invention is added in an amount of 0.05-0.2 g per liter of dye wastewater, has the advantages of small catalyst usage amount, high degradation efficiency, short degradation time and the like from the viewpoints of catalyst usage amount, degradation reaction time and removal rate, and can effectively activate persulfate so as to realize the purpose of efficiently degrading dye in water.
(3) The loofah sponge biochar catalyst is prepared by taking loofah sponge as a raw material through simple pretreatment, calcination and acid modification, is a green, environment-friendly and economic heterogeneous catalytic material, and has the advantages of high graphitization degree, ordered overall structure, thin tube wall, rich microporous structure, large specific surface area, excellent catalytic activity and the like; the raw materials for preparation are wide in source and low in price, and the standard of modern science and technology which is green, environment-friendly, high in quality and low in price is better met; the preparation method has the advantages of simple process, mild reaction conditions, convenient operation, cleanness, no pollution and the like, is suitable for large-scale preparation, and is convenient for industrial utilization.
(4) In the invention, the crystallinity of the used loofah sponge biochar catalyst is not obviously changed after the loofah sponge biochar catalyst is repeatedly utilized for four times, the used catalyst recovery method is simpler, most of the catalyst can be obtained only by suction filtration, and the loss rate of the catalyst is lower. Therefore, the loofah sponge biochar catalyst disclosed by the invention is stable in structure and has the advantages of simplicity in recovery, high recovery rate and the like.
(5) In the invention, the loofah sponge biochar catalyst can also show higher catalytic activity when degrading dyes in the presence of various anions; meanwhile, the catalyst can degrade dye wastewater within the pH value of 3-10, can show higher catalytic activity, and has the advantage of wide application range. In addition, the loofah sponge biochar catalyst disclosed by the invention can be used for realizing the efficient degradation of conventional dye wastewater (such as rhodamine B, malachite green and the like) and also realizing the efficient degradation of azo dye wastewater (such as acid orange, methyl orange and the like), which shows that a degradation system constructed by the loofah sponge biochar catalyst and persulfate can be used for effectively degrading dyes in wastewater, and the removal rate can reach more than 95%.
(6) The loofah sponge biochar catalyst used in the invention can still show higher catalytic activity in actual water (tap water, river water and lake water) and can well operate in high-concentration and low-concentration dye wastewater (0.1-20 mg/L).
Drawings
Fig. 1 is an SEM picture of the loofah sponge charcoal catalyst (LSB-800) prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the loofah sponge charcoal catalyst (LSB-400, LSB-600, LSB-800) prepared in example 1 of the present invention.
Fig. 3 is a graph showing the degradation effect of the loofah sponge charcoal catalyst prepared under different calcination temperature conditions on acid orange in example 1 of the present invention.
FIG. 4 is a graph showing the degradation effect of Siberian solomonseal rhizome charcoal catalyst (LSB-800) on acid orange under different pH conditions in example 3 of the present invention.
Fig. 5 is a graph showing the degradation effect of the cucurbitacin carbon catalyst (LSB-800) on rhodamine B, acid orange, methyl orange, tetracycline hydrochloride, and levofloxacin in example 4 of the present invention.
Fig. 6 is a graph showing the degradation effect of the cucurbituril bio-carbon catalyst (LSB-800) on acid orange under different water body conditions in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
a method for removing dye in water by utilizing loofah sponge biochar catalyst to activate persulfate, in particular to a method for degrading acid orange wastewater by utilizing loofah sponge biochar catalyst to activate persulfate, which comprises the following steps:
Weighing 20mg of loofah sponge biochar catalysts (LSB-400, LSB-600 and LSB-800) prepared under different calcination temperature conditions, respectively adding the loofah sponge biochar catalysts into 100mL of 20mg/L acid orange (AO7) solution (the initial pH value of the solution is 3.42), magnetically stirring for 30min to ensure that adsorption balance is achieved, then adding 10mM of sodium Persulfate (PS), and carrying out degradation reaction for 60 min to complete removal of the acid orange in the water body.
PS group: no catalyst was added, and the other conditions were the same.
LSB-800 group: no persulfate was added, and the other conditions were the same.
In this embodiment, the loofah sponge charcoal catalyst (LSB-800) is prepared by calcining loofah sponge and modifying with acid, and includes the following steps:
(1) removing seeds from the collected retinervus Luffae fructus, washing with deionized water to remove dust, drying at 60 deg.C in a forced air drier, completely drying, and storing in a sealed container. And (3) putting the dried loofah sponge into a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen atmosphere, calcining, and carbonizing for 2h to obtain a calcined product.
(2) The calcined product was washed with 100mL of 6M HNO3Soaking for 12 hours, washing with deionized water to neutrality after soaking is completed, and drying at 110 deg.C for 12 hours. Grinding the dried solid sample into powder, and sieving with 100 mesh sieve (particle size) <0.15mm) to obtain the loofah sponge biochar catalyst which is marked as LSB-800.
In this embodiment, the preparation method of the loofah sponge charcoal catalyst (LSB-400) is substantially the same as the preparation method of the loofah sponge charcoal catalyst (LSB-800), and the differences are only that: the calcination temperature for preparing LSB-400 is 400 ℃.
In this embodiment, the preparation method of the loofah sponge biochar catalyst (LSB-600) is basically the same as the preparation method of the loofah sponge biochar catalyst (LSB-800), and the differences are only that: the calcination temperature for preparing LSB-600 is 600 ℃.
The loofah sponge charcoal catalysts (LSB-400, LSB-600 and LSB-800) prepared in example 1 of the invention under different calcination temperature conditions were characterized: phase composition XRD, microscopic morphology SEM.
Fig. 1 is an SEM image of the loofah sponge charcoal catalyst (LSB-800) prepared in example 1 of the present invention. As can be seen from fig. 1, the loofah sponge charcoal catalyst (LSB-800) has an obvious honeycomb structure, which provides more catalytic active sites during the subsequent degradation reaction and provides a channel for electron transfer, which is beneficial to improving the catalytic activity of the loofah sponge charcoal catalyst. Meanwhile, the network framework structure widely connected with LSB-800 provides conditions for the attachment of dye, thereby providing a good channel for electron mass transfer. In addition, compared with LSB-400 and LSB-600, the LSB-800 of the invention has higher graphitization degree, more ordered integral structure, thinnest tube wall and more favorable electron transfer, and meanwhile, the LSB-800 has larger specific area and abundant micropores, thereby providing more active sites in the degradation catalytic reaction process and finally realizing the high-efficiency removal of the dye in the water body.
Fig. 2 is an XRD pattern of the loofah sponge charcoal catalyst (LSB-400, LSB-600, LSB-800) prepared in example 1 of the present invention. As can be seen from fig. 2, the characteristic peak of the loofah sponge charcoal catalyst corresponds to the characteristic peak C, and the main phase composition thereof is graphitic carbon.
In the degradation reaction process, 2mL of sample is taken by an injector and placed in a 5mL centrifuge tube (0.5 mL of methanol quencher is added in advance to stop the reaction) for 5min, 10min, 20min, 30min and 60min respectively, and then the concentration of the sample is measured by ultraviolet at the wavelength of 485nm, so that the removal rate of different loofah sponge biochar catalysts on acid orange is obtained.
Fig. 3 is a graph showing the degradation effect of the loofah sponge charcoal catalyst on acid orange, which is prepared under different calcination temperature conditions in example 1 of the present invention. As can be seen from FIG. 3, when PS is used alone (PS group), the removal rate of acid orange is only 10%; when LSB-800 was used alone (LSB-800 group), the acid orange removal rate was less than 25% within one hour due to the adsorption of LSB-800 itself. When the loofah sponge biochar catalyst and the PS are used in combination, the removal rates of the LSB-400, the LSB-600 and the LSB-800 to acid orange are respectively 11%, 12% and 100%, and the reason that the removal rates of the LSB-400 and the LSB-600 are low is that: on one hand, the graphitization degree of the loofah sponge charcoal catalyst is too low due to too low calcination temperature, so that an ordered integral structure cannot be obtained; on the other hand, the calcination temperature is too low, the specific surface area of the loofah sponge charcoal catalyst prepared by the method is too small, the adsorption to the dye is poor, more catalytic active sites cannot be provided in the degradation reaction process, and the removal effect of the loofah sponge charcoal catalyst to the dye is finally influenced. Therefore, the loofah sponge biochar catalyst (LSB-800) prepared by the method greatly improves the degradation efficiency of acid orange, has the removal rate of the acid orange up to 100%, can completely degrade and remove the acid orange, and shows that the loofah sponge biochar catalyst can efficiently activate PS and has excellent catalytic performance. Therefore, LSB-800 shows the best catalytic performance under the conditions that the initial pH is 3.42, the PS concentration is 10mM and the catalyst dosage is 0.2g/L, and the removal rate of acid orange can reach 100% within one hour.
Example 2:
a method for removing dye in water by using catalyst activated persulfate, in particular to a method for degrading acid orange wastewater by using different catalysts activated persulfate, which comprises the following steps:
adding sludge biochar, magnetic sludge biochar, iron-doped sludge biochar, rice bran biochar, rice hull biochar, wood chip biochar and the loofah sponge biochar catalyst (LSB-800) prepared in example 1 into the acid orange solution (AO7) respectively, stirring, adding persulfate, performing degradation reaction, and removing acid orange in the water body.
The catalyst, pollutants, process parameters of the catalyst and the removal rate of acid orange are shown in table 1 (the sludge biochar, magnetic sludge biochar, iron-doped sludge biochar, rice bran biochar, rice hull biochar and wood chip biochar in table 1 are all prepared by the prior art).
TABLE 1 degradation Effect of different catalysts on acid orange
Figure BDA0003497436870000071
As can be seen from table 1, compared with other biochar catalysts, the loofah sponge biochar catalyst disclosed by the invention can realize efficient degradation of dye pollutants under the condition of relatively small usage amount, is a novel fenton catalyst with excellent performance, has the advantages of small usage amount of the catalyst, high degradation efficiency, short degradation time and the like, can be widely used for degrading dyes in water, and has high use value and good application prospect.
Example 3:
a method for removing dye in water by utilizing loofah sponge biochar catalyst to activate persulfate, in particular to a method for degrading acid orange wastewater by utilizing loofah sponge biochar catalyst to activate persulfate, which comprises the following steps:
taking 6 parts of 100mL and 20mg/L acid orange solution, respectively adjusting the pH values to 3, 3.42, 5, 7, 9 and 11, adding 20mg of the loofah sponge biochar catalyst (LSB-800) prepared in example 1, magnetically stirring for 30min to reach adsorption balance, then adding 10mM PS, and carrying out degradation reaction for 30min to complete removal of acid orange in the water body.
In the degradation reaction process, 2mL of sample is taken by an injector and placed in a 5mL centrifuge tube (0.5 mL of methanol quencher is added in advance to stop the reaction) for 5min, 10min, 20min and 30min respectively, and then the concentration of the sample is measured at the wavelength of 485nm by ultraviolet to obtain the removal rate of different loofah sponge biochar catalysts to acid orange.
FIG. 4 is a graph showing the degradation effect of Siberian solomonseal rhizome charcoal catalyst (LSB-800) on acid orange under different pH conditions in example 3 of the present invention. As can be seen from fig. 4, the removal rates of LSB-800 of the present invention to acid orange at pH values of 3, 3.42, 5, 7, and 9 were 87.6%, 96%, 83.9%, 91.1%, and 82.2% in sequence; and the removal rate of LSB-800 to acid orange is less than 70 percent under the condition that the pH value is 11. Therefore, the loofah sponge charcoal catalyst can achieve high removal rate to acid orange within the pH value range of 3-10, which shows that the pH value application range of a degradation system constructed by the loofah sponge charcoal catalyst and PS is wide. In the degradation process of acid orange, when the initial pH of the acid orange solution is 3.0-9.0, the pH in the reaction system gradually changes to be acidic or neutral; however, when the initial pH of the acid orange solution is 11.0, the reaction system still keeps strong alkalinity. Therefore, when the initial pH of the acid orange solution is 11.0, the pH is adjusted to the pH range of the solution >In the heterogeneous system of pHpzc, the electrostatic repulsion of acid orange is increased, so that the removal efficiency of acid orange is obviously reduced; at the same time, at higher pH, PS will decompose itself to SO via a non-radical pathway4 2-,O2And H and2o, thereby inhibiting the active group SO4 ·-Generating; in addition, under alkaline conditions, the active group SO4 ·-Will react with OH-The reaction generates OH (hydroxyl radical), but the hydroxyl radical is quenched by the by-products generated by the self-decomposition of PS, thereby reducing the rate of the degradation reaction.
Example 4:
a method for removing dyes in a water body by activating persulfate through a loofah sponge biochar catalyst specifically comprises the following steps of performing degradation treatment on rhodamine B wastewater, acid orange wastewater, methyl orange wastewater, tetracycline hydrochloride and levofloxacin by activating persulfate through the loofah sponge biochar catalyst:
weighing 5 parts of the loofah sponge charcoal catalyst (LSB-800) prepared in example 1, adding 20mg of the loofah sponge charcoal catalyst into 100mL of rhodamine B solution, 20mg/L of the loofah sponge charcoal catalyst into 20mg/L of the loofah sponge charcoal catalyst (wherein the initial pH value of the loofah sponge charcoal catalyst solution is 3.42), magnetically stirring for 30min to ensure that adsorption balance is achieved, adding 10mM of PS (polystyrene), and performing degradation reaction for 60 min to complete removal of the loofah sponge charcoal catalyst (LSB-800) in water.
In the degradation reaction process, 2mL of samples are taken by an injector and placed in a 5mL centrifuge tube (0.5 mL of methanol quencher is added in advance to stop the reaction) for 5min, 10min, 20min, 30min and 60min respectively, and then the concentration of the samples is measured under the wavelength of 485nm by ultraviolet to obtain the removal rate of the loofah sponge biochar catalyst on different dye wastewater.
Fig. 5 is a graph of the degradation effect of the cucurbitacin carbon biocatalyst (LSB-800) on rhodamine B, acid orange, methyl orange, tetracycline hydrochloride, and levofloxacin in example 4 of the present invention. As can be seen from FIG. 5, the LSB-800 of the present invention has 100%, 70% and 58% of removal rate for rhodamine B, acid orange, methyl orange, tetracycline hydrochloride and levofloxacin. Therefore, the loofah sponge charcoal catalyst has a general degradation effect on antibiotic wastewater, and has an excellent degradation effect on different dye wastewater, which shows that a degradation system constructed by the loofah sponge charcoal catalyst and PS can actually degrade the dye in the wastewater, and can achieve a removal rate of 100%.
Example 5:
a method for removing dye in water by utilizing loofah sponge biochar catalyst to activate persulfate, in particular to a method for degrading acid orange wastewater by utilizing loofah sponge biochar catalyst to activate persulfate, which comprises the following steps:
Weighing 4 parts of the loofah sponge charcoal catalyst (LSB-800) prepared in the example 1, adding 20mg of each loofah sponge charcoal catalyst into deionized water containing acid orange, tap water, river water and lake water (the parameters of the wastewater are all 100mL and 20mg/L, and the initial pH value is 3.42), magnetically stirring for 30min to ensure that the adsorption balance is achieved, then adding 10mM PS, and performing degradation reaction for 30min to complete removal of the acid orange in the water body.
In the degradation reaction process, 2mL of samples are taken by an injector and placed in a 5mL centrifuge tube (0.5 mL of methanol quencher is added in advance to stop the reaction) for 5min, 10min, 20min and 30min respectively, and then the concentration of the samples is measured by ultraviolet at the wavelength of 485nm, so that the removal rate of the loofah sponge biochar catalyst on acid orange under different water body conditions is obtained.
Fig. 6 is a graph of the degradation effect of the cucurbituril bio-carbon catalyst (LSB-800) on acid orange in example 5 of the present invention under different water conditions. As can be seen from fig. 6, the removal rates of LSB-800 of the present invention to acid orange in deionized water, tap water, river water and lake water are 96%, 98.4%, 91.6% and 95.4% in this order. Therefore, the loofah sponge biochar catalyst disclosed by the invention runs well in actual water, and acid oranges in different water are effectively degraded.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the invention in any way. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (10)

1. A method for removing dye in water by activating persulfate through a loofah sponge charcoal catalyst is characterized in that the method is to degrade dye wastewater by activating persulfate through the loofah sponge charcoal catalyst; the loofah sponge charcoal catalyst is prepared by calcining loofah sponge and performing acid modification; the calcining temperature is 750-850 ℃.
2. The method for removing the dye in the water body by using the loofah sponge biochar catalyst activated persulfate according to claim 1, wherein the preparation method of the loofah sponge biochar catalyst comprises the following steps:
S1, calcining the loofah sponge under the protection of inert gas to obtain a calcined product;
and S2, mixing the calcined product obtained in the step S1 with an acid solution, standing, washing and drying to obtain the loofah sponge charcoal catalyst.
3. The method for removing dye in water by using loofah sponge biochar catalyst to activate persulfate, which is disclosed by claim 2, is characterized in that in the step S1, the temperature rise rate in the calcination process is 5 ℃/min, and the calcination time is 2 h.
4. The method for removing dye in water by using loofah sponge biochar catalyst activated persulfate according to claim 3, wherein in the step S2, the concentration of the acid solution is 6mol/L, the acid solution is nitric acid, and the standing time is 12 h.
5. The method for removing dye in water by using the loofah sponge biochar catalyst activated persulfate, which is characterized in that in the step S1, the inert gas is nitrogen, and the loofah sponge further comprises the following pretreatment before calcination: washing and drying the loofah sponge; the temperature of the drying was 60 ℃.
6. The method for removing the dye in the water body by using the loofah sponge biochar catalyst activated persulfate as recited in any one of claims 2 to 4, wherein in the step S2, the drying temperature is 110 ℃, and the drying time is 12 h; the drying process further comprises the following steps: and grinding the dried product, and sieving the ground product by a 100-mesh sieve.
7. The method for removing the dye in the water body by using the loofah sponge biochar catalyst activated persulfate according to any one of claims 1-4, wherein the degradation treatment is as follows: mixing the loofah sponge biochar catalyst with the dye wastewater, stirring, and adding persulfate to perform degradation reaction to complete degradation of the dye in the wastewater.
8. The method for removing dye from water by using the loofah sponge biochar catalyst activated persulfate according to claim 7, wherein the addition amount of the loofah sponge biochar catalyst is 0.05 g-0.2 g per liter of dye wastewater.
9. The method for removing the dye in the water body by using the loofah sponge biochar catalyst to activate the persulfate, according to claim 8, is characterized in that the initial concentration of the dye wastewater is 0.1-20 mg/L, the initial pH value of the dye wastewater is 3-10, and the dye in the dye wastewater comprises at least one of rhodamine B, acid orange, methyl orange and malachite green; the addition amount of the persulfate is 5-15 mmol of persulfate added in each liter of dye wastewater, and the persulfate is sodium persulfate.
10. The method for removing the dye in the water body by using the loofah sponge biochar catalyst to activate the persulfate, according to claim 9, is characterized in that the stirring time is 30min, and the degradation reaction time is 30 min-60 min.
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