CN111450855B - Preparation method of modified electrolytic manganese slag and application of modified electrolytic manganese slag in efficient degradation of X-3B - Google Patents
Preparation method of modified electrolytic manganese slag and application of modified electrolytic manganese slag in efficient degradation of X-3B Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011572 manganese Substances 0.000 title claims abstract description 81
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 80
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- 239000003403 water pollutant Substances 0.000 description 5
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
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- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B01J35/56—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of decolorization and degradation treatment of printing and dyeing wastewater containing X-3B, in particular to a preparation method of modified electrolytic manganese slag and application thereof in efficient degradation of X-3B. Firstly, carrying out hydrothermal reaction on electrolytic manganese slag, naOH solution and EDTA-2Na for 3-6 hours at 100-150 ℃ to obtain modified electrolytic manganese slag, then adding the modified electrolytic manganese slag prepared by the method and hydrogen peroxide into wastewater containing X-3B, regulating the pH value of a system to 1-5, and standing for a certain time to achieve the purpose of degrading X-3B. Experiments on simulated wastewater show that the technical scheme of the invention can effectively degrade X-3B, the removal rate is over 99 percent, and the COD removal rate in wastewater is over 80 percent.
Description
Technical Field
The invention relates to the technical field of innocent treatment of wastewater containing X-3B, in particular to a preparation method of modified electrolytic manganese slag and application thereof in efficient degradation of X-3B.
Background
The textile printing and dyeing industry is an important industry in China and is one of the industrial departments with the largest wastewater discharge. About 9 hundred million tons of wastewater are discharged each year, and the sixth place of the discharge amount of industrial wastewater in China is occupied. The printing and dyeing wastewater in a large amount accounts for 80 percent, and the printing and dyeing wastewater containing X-3B (reactive brilliant red) is typical azo reactive printing and dyeing wastewater. Therefore, a large amount of untreated or unqualified printing and dyeing wastewater is directly discharged, which not only endangers human health, but also damages water, soil and ecological structures. The printing and dyeing wastewater has the characteristics of large water quantity, deep chromaticity, unstable water quality, complex components, degradation of X-3B into more than 20 carcinogenic organic intermediates in nature and the like, so that the printing and dyeing wastewater is one of the typical industrial wastewater which is generally accepted in the industry and is difficult to treat.
The unstable water quality (high pH value, partial anions and cations, unstable temperature) of the printing and dyeing wastewater and the biotoxicity of X-3B lead to poor biodegradability of the wastewater containing X-3B and low biological treatment efficiency. The traditional flocculation precipitation, filtration and adsorption method only carry out phase transfer on X-3B, and does not really realize harmless treatment. Currently, advanced oxidation processes are being developed for treating X-3B wastewater, which are of great interest due to their high efficiency. However, the catalyst is expensive, the catalyst regeneration is difficult to be corroded, and the treatment method has the defects of complex process and the like. Meanwhile, the conventional advanced oxidation method (comprising Fenton, photocatalysis and electrocatalysis) is difficult to thoroughly and synchronously realize the degradation and mineralization of X-3B, and the COD/TOC in the wastewater is still higher and still needs further treatment.
Therefore, the development of a method for efficiently degrading and mineralizing X-3B by using an inexpensive catalyst and a related method is of great significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention utilizes the modified electrolytic manganese slag and develops and utilizes the modified electrolytic manganese slag and H 2 O 2 The method is used for efficiently treating the wastewater containing the X-3B, so as to provide reference for the treatment of the industrial wastewater containing the X-3B.
The invention also aims to provide a novel method for removing the X-3B in the wastewater, which has the advantages of low treatment cost, simple operation condition and high treatment efficiency, and the water quality after treatment reaches the national relevant standard.
The invention provides a preparation method of modified electrolytic manganese slag, which comprises the following specific operation steps:
mixing the dried electrolytic manganese slag with NaOH solution and EDTA-2Na, and reacting completely under ultrasound (the time is preferably 20-40 min); standing to remove supernatant, transferring the remaining pasty substances into a hydrothermal reaction kettle, sealing, reacting for 3-6 hours at 100-150 ℃, performing suction filtration and washing, and finally drying the obtained solid at 60-80 ℃ to obtain modified electrolytic manganese slag;
the dosage ratio of the dried electrolytic manganese slag to NaOH and EDTA-2Na in the NaOH solution is 1g: (2-4) mmol: (0.01-0.1 g), preferably 1g:2mmol:0.03g.
Further, the volume ratio of the dried electrolytic manganese slag to the hydrothermal reaction kettle is 1g:4mL.
Further, the preparation method comprises the following specific operation steps:
mixing the dried electrolytic manganese slag with NaOH solution and EDTA-2Na, and reacting for 30min under ultrasound; and standing to remove supernatant, transferring the remaining pasty substances into a hydrothermal reaction kettle, reacting for 5 hours at 130 ℃, carrying out suction filtration and washing, and finally drying the obtained solid at 75 ℃ to obtain the modified electrolytic manganese slag.
Further, the concentration of the NaOH solution is 1-3M.
Further, the dried electrolytic manganese slag is: drying the electrolytic manganese slag at 55-75 ℃ for 48-72h, grinding, sieving with a 100-200 mesh sieve, and putting into use.
The invention also provides application of the modified electrolytic manganese slag prepared by the method in high-efficiency degradation of X-3B.
Further, the steps of the application are as follows:
adding the modified electrolytic manganese slag and hydrogen peroxide prepared by the method into the wastewater containing X-3B, then adjusting the pH value of the system to 1-5 (preferably 1.0-2.5), and standing for a certain time to achieve the purpose of degrading X-3B;
the dosage ratio of the modified electrolytic manganese slag to the content of X-3B in the X-3B wastewater is (2-5) mg: (3-20) mg: (0.01-0.1) mL, preferably 2mg: (3-20) mg: (0.01-0.03) mL;
further, the hydrogen peroxide is H 2 O 2 Hydrogen peroxide with the content of 30 weight percent.
Further, 0.1M NaOH and/or 0.1M M H are used in the application 2 SO 4 The pH of the system is regulated.
Further, the concentration of X-3B in the wastewater containing X-3B is 30-200mg/L.
The technical scheme of the invention can effectively degrade X-3B, the removal rate of the X-3B is more than 99%, and the COD removal rate of the wastewater is more than 80%. The final effluent quality chromaticity after being treated by the method is 2-10, which is far lower than the standard which is not more than 70 and is specified in the national emission standard of water pollutants in textile dyeing and finishing industry (GB/T4287-2012) and meets the primary standard of the highest allowable emission concentration of the basic control project (GB 3838-2002) of the surface water environment quality standard (GB 3838-2002).
Compared with the prior art, the innocent treatment method for the water body containing X-3B has the following advantages and beneficial effects:
1. the wastewater after the treatment by the method can reach the corresponding recycling standard: the final effluent quality chromaticity after being treated by the method is 2-10, which is far lower than the standard of not more than 70 specified in the national emission standard of water pollutants in textile dyeing and finishing industry (GB/T4287-2012), and accords with the first-level standard of not more than 30 of the highest allowable emission concentration of the basic control project of the quality standard of surface water environment (GB 3838-2002), thus achieving the aim of harmlessness.
2. The degradation rate of the invention to the wastewater with the concentration of X-3B of 30-200mg/L is more than 99%, and the wastewater can be completed within 16min, which shows that the invention has high efficiency.
3. Catalyst (modified electrolytic manganese slag) and H 2 O 2 The dosage of the catalyst is low, and the catalyst can be recycled.
4. High value-added utilization of industrial waste resource: the method adopts the waste electrolytic manganese slag as the raw material, does not need high-temperature calcination and the like, effectively solves the problem of processing the materials, and has a green preparation process.
Drawings
FIG. 1 is a process flow diagram of the method for degrading X-3B in wastewater by utilizing modified electrolytic manganese slag.
FIG. 2 is an XRD pattern of the modified electrolytic manganese slag prepared in example 1, wherein EMR in FIG. 2 is the original electrolytic manganese slag, EMR-1 is a material prepared without EDTA-2Na, and N-EMR is the modified electrolytic manganese slag prepared in example 1. Can be sent from the figureThe crystalline phase substance of the original electrolytic manganese slag is mainly CaSO 4 ·2H 2 O and SiO 2 After modification, caSO is mainly used 4 ·0.5H 2 O and a small part of SiO 2 However, without modification with EDTA-2Na, caSO could not be produced 4 ·0.5H 2 O。
FIG. 3 is an SEM-EDS spectrum of modified electrolytic manganese slag (N-EMR) prepared in example 1, and it is clear from the graph that the modified electrolytic manganese slag (N-EMR) has a honeycomb nano-lamellar structure (100-200 nm) as a whole, greatly increasing the specific surface area thereof, and meanwhile, the surface thereof is distributed with iron-manganese elements (having the catalysis of H 2 O 2 Is a function of (2).
FIG. 4 is a graph of XPS (X-Ray Photoelectron Spectroscopy) elemental analysis of N-EMR prepared in example 1 as compared with C.D.Wagner, W.M.Riggs, L.E Davis, J.F.Moulder, G.E.Muilenberg (1979), handbook of X-Ray Photoelectron spectra. Perkin-Elmer Corporation Physical Electronics Division 6509Flying Cloud Drive Eden Prairie,Minnesota 55344. And Distributed by the Measurement Services Division of the National Institute of Standards and Technology (NIST) Material Measurement Laboratory (MML) NIST is an agency of the U.S. device of Commerce Last updated: september 15,2012 (Created: june 06,2000): the iron and manganese elements in the modified electrolytic manganese slag (N-EMR) prepared in the embodiment 1 of the invention are mainly Fe 2 O 3 、Fe 3 O 4 、MnO 2 And Mn of 2 O 3 。
FIG. 5 is a Raman spectrum of modified electrolytic manganese slag (N-EMR) prepared in example 1, which further verifies the analysis result of XPS, and N-EMR+X-3B in the figure represents the Raman spectrum of the material N-EMR recovered after use of the modified electrolytic manganese slag in example 2, and the structure is substantially unchanged compared with the spectrum before use, indicating that the modified electrolytic manganese slag has stability.
FIG. 6 is an ESR analysis chart of modified electrolytic manganese slag (N-EMR) prepared in example 1, in which N-EMR and H can be seen 2 O 2 The system of (2) can generate hydroxyl free radical (left graph) and superoxide free radical (right graph) (the free radical is detected by replacing the same volume of X-3B wastewater with water, which isIn the middle panel, N-EMR represents a system of N-EMR+water, N-EMR+H 2 O 2 Represents modified electrolytic manganese slag, water and H 2 O 2 A system of (2) a system of (3).
FIG. 7 shows the degradation effect of the reuse of the modified electrolytic manganese slag N-EMR on X-3B in example 5.
Detailed Description
The following detailed description of the preparation and application of the product of the present invention will be provided by the applicant in connection with specific examples to facilitate a clear understanding of the present invention to those skilled in the art. It should be understood that the following examples should not be construed in any way as limiting the scope of the application.
The electrolytic manganese slags (EMR) used in the following examples were all from slags discharged by an electrolytic manganese producer in the left-hand region of Guangxi province.
Example 1 a method for preparing modified electrolytic manganese slag, comprising the steps of:
placing the electrolytic manganese slag EMR in a 75 ℃ oven for drying for 48 hours, and grinding and sieving the electrolytic manganese slag EMR with a 100-mesh sieve; weighing 50g of sieved electrolytic manganese slag, and mixing with 100mL of 1M NaOH solution and 1.5g of EDTA-2 Na; placing the reactants into a polytetrafluoroethylene conical flask, and reacting for 30min under ultrasonic; then, standing to remove most of supernatant, transferring the remaining pasty substances into a hydrothermal reaction kettle with the liner volume of 200mL, sealing and manually spirally solidifying, and reacting for 5 hours at 130 ℃; then taking out the substances in the reaction kettle, carrying out suction filtration and washing with deionized water for 8 times; finally, the obtained solid was dried at 75℃to obtain modified electrolytic manganese slag (N-EMR) for use in the following examples.
Preparation of EMR-1 material: the preparation method is the same as the experimental steps of the preparation of the N-EMR, except that EDTA-2Na is not added, and other steps and experimental conditions are the same.
XRD (X-ray diffraction analysis) (FIG. 2), XPS (X-ray photoelectron spectroscopy) (FIG. 4), raman (Raman spectroscopy) (FIG. 5), SEM-EDS (scanning electron microscopy) and ESR (electron paramagnetic resonance spectroscopy) (FIG. 6) were performed on the modified electrolytic manganese slag (N-EMR).
The main components of the EMR of the electrolytic manganese slag (XRF analysis) are shown in Table 1.
TABLE 1
In the following examples:
the content and chromaticity (GB 3838-2002) of the simulated wastewater are measured by adopting an ultraviolet spectrophotometry, and the content of COD in the simulated wastewater is measured by adopting a (GB 11914-89) dichromate method;
with 0.1M NaOH and 0.1. 0.1M H 2 SO 4 The pH of the system is regulated.
H in the hydrogen peroxide 2 O 2 The concentration was 30wt%.
Example 2 application of modified electrolytic manganese slag in degrading X-3B in wastewater comprises the following specific steps:
the first experiment and the operation process are shown in the operation flow chart of fig. 1:
preparing X-3B-containing simulated wastewater with the concentration of X-3B of 30.0mg/L by using active brilliant red X-3B solid and deionized water, taking 100mL of the prepared X-3B-containing simulated wastewater, and adding 2mg of modified electrolytic manganese slag N-EMR prepared in example 1 and 0.01mL of hydrogen peroxide into the mixed wastewater; then regulating the pH value of the system to 1.0, shaking up by hand to obtain a mixed system, standing for 16min, measuring the content of X-3B and COD in the solution, further calculating the removal rate of X-3B and COD, and filtering to recover the modified electrolytic manganese slag at the bottom.
Calculating the removal rate of X-3B in the simulated wastewater containing X-3B:
wherein D is the removal rate, and C is calculated when the X-3B removal rate is calculated 0 X-3B concentration for the original system (i.e., simulated wastewater containing X-3B); c is the concentration of X-3B in the system after 16min of reaction;
meanwhile, the removal rate of COD in the simulated wastewater containing X-3B is calculated and obtained:
wherein D is the removal rate, and C 'is calculated when the COD removal rate is calculated' 0 COD concentration is the original system (simulated wastewater containing X-3B); c' is the concentration of COD in the system after 16min of reaction.
After detection calculation, after 16 minutes of reaction, the COD removal rate is 83.52%, the X-3B removal rate is 99.89%, the content of X-3B in the treated wastewater is 0.033mg/L, the chromaticity is 2, the standard which is far lower than 70 and is specified in the national emission standard of water pollutants in textile dyeing and finishing industry (GB/T4287-2012) is met, and the requirement that the primary standard of the highest allowable emission concentration of the basic control project of the quality standard of surface water environment (GB 3838-2002) is not more than 30 can be directly emitted or further recycled.
And examining the removal effect of modified electrolytic manganese slag N-EMR on X-3B and COD in wastewater under different system pH conditions in a second experiment and a third experiment, wherein the experimental process is the same as the step of the first application experiment, the difference is that the pH of the system is respectively regulated to 2.0 and 2.5, after 16 minutes, the removal rate of X-3B is respectively 99.77% and 99.96%, and the removal rate of COD is respectively calculated to be: 86.01% and 87.33%.
And examining the effect of EMR and EMR-1 on removing X-3B in wastewater in the fourth experiment and the fifth experiment, wherein the experiment process is the same as the first experiment, and the difference is that N-EMR is respectively changed into EMR and EMR-1 with equal mass, after 16 minutes, the removal rates of the EMR and the EMR-1 on X-3B are respectively 38.56% and 59.87%, and the removal rates on COD are respectively: 13.31% and 22.26%.
In the present invention, the principle of N-EMR degradation should be:
N-EMR catalyzed H 2 O 2 Generates hydroxyl free radical and superoxide free radical to attack X-3B, thus achieving the purpose of degradation. The reaction process is as follows:
≡Fe(II)+H 2 O 2 →≡Fe(III)+OH - +·OH (1)
≡Fe(III)+H 2 O 2 →≡Fe(II)+HO 2 +H + (2)
≡Fe(III)+HO 2 ·→≡Fe(II)+O 2 +H + (3)
≡Mn(III)+H 2 O 2 →≡Mn(IV)+OH - +·OH (4)
≡Mn(IV)+H 2 O 2 →≡Mn(III)+HO 2 +H + (5)
≡Mn(IV)+HO 2 ·→≡Mn(III)+O 2 +H + (6)
example 3 application of modified electrolytic manganese slag in degrading X-3B in wastewater, the specific steps are as follows:
experiment one, as shown in the operational flow chart of fig. 1: preparing X-3B-containing simulated wastewater with the concentration of X-3B of 100.0mg/L by utilizing X-3B solid and deionized water, taking 100mL of the X-3B-containing simulated wastewater, and adding 2mg of the modified electrolytic manganese slag prepared in the example 1 and 0.02mL of hydrogen peroxide into the 100mL of the X-3B-containing simulated wastewater; regulating the pH value of the system to 2.0, shaking up by hand to obtain a mixed system, standing for 16min, measuring the content of X-3B and COD in the solution, calculating the removal rate, and filtering to recover the modified electrolytic manganese slag at the bottom.
After 16 minutes, the COD removal rate is calculated to be 85.24%, the X-3B removal rate is calculated to be 99.97%, the content of X-3B in the treated wastewater is 0.03mg/L, the chromaticity is 5, the standard which is far lower than 70 and is specified in the national emission standard of water pollutants in textile dyeing and finishing industry (GB/T4287-2012) is met, and the standard meets the requirement that the primary standard of the highest allowable emission concentration of the basic control project of the surface water environment (GB 3838-2002) is not more than 30, so that the wastewater can be directly discharged or further recycled.
And examining the removal effect of modified electrolytic manganese slag N-EMR on X-3B in wastewater under different system pH conditions in a second experiment and a third experiment, wherein the experimental process is the same as the first experiment, and the difference is that when the pH of the system is adjusted to be 1.0 and 2.5, the removal rate of X-3B is 99.87% and 99.81%, and the removal rate of COD is respectively: 84.78% and 85.04%.
Example 4 application of modified electrolytic manganese slag in degrading X-3B in wastewater, the specific steps are as follows:
experiment one, as shown in the operational flow chart of fig. 1: preparing X-3B-containing simulated wastewater with the concentration of X-3B of 200.0mg/L by utilizing X-3B solid and deionized water, taking 100mL of the X-3B-containing simulated wastewater, and adding 2mg of the modified electrolytic manganese slag prepared in the example 1 and 0.03mL of hydrogen peroxide into the 100mL of the X-3B-containing simulated wastewater; regulating the pH value of the system to 2.5, shaking up by hand to obtain a mixed system, standing for 16min, measuring the content of X-3B and COD in the solution, calculating the removal rate of the X-3B and COD, and filtering to recover the modified electrolytic manganese slag at the bottom.
After 16 minutes, the COD removal rate is 84.89%, the X-3B removal rate is 99.52%, the content of X-3B in the treated wastewater is 0.96mg/L, the chromaticity is 10, the wastewater is far lower than the standard which is not more than 70 and is specified in the national emission standards of water pollutants for textile dyeing and finishing industry (GB/T4287-2012), and the wastewater meets the requirement that the primary standard of the maximum allowable emission concentration of the basic control project of the surface water environment standard (GB 3838-2002) is not more than 30, and can be directly discharged or further recycled.
And examining the removal effect of modified electrolytic manganese slag N-EMR on X-3B in wastewater under different system pH conditions in a second experiment and a third experiment, wherein the experimental process is the same as the first experiment, and the difference is that when the pH of the system is adjusted to be 1.0 and 2.0, the removal rate of X-3B is 99.53% and 99.50%, and the removal rate of COD is respectively: 83.59% and 84.22%.
Example 5 application of recycling modified electrolytic manganese slag in degrading X-3B in wastewater, the specific steps are as follows:
and (3) recycling the modified electrolytic manganese slag after the reaction in the examples 2-4 by using a suction filtration method, drying the modified electrolytic manganese slag obtained after the solid-liquid separation by suction filtration in an oven at 75 ℃ for 48 hours to realize the regeneration of the modified electrolytic manganese slag, and then repeating the experiment I in the examples 2-4 respectively as shown in the operation flow chart of fig. 1. The removal of X-3B and COD was calculated as shown in Table 2:
TABLE 2
As can be seen from Table 2, the recovered modified electrolytic manganese slag still has good X-3B removal performance.
The reusability of the material is an important index for judging the stability and economy of the catalyst. The N-EMR recovered used in example 2 was ultrasonically washed with deionized water, dried at 75℃for 48 hours in an oven to effect regeneration of the modified electrolytic manganese slag, and then reused five times in accordance with the procedure of experiment one of example 2, and the results are shown in FIG. 7.
From the above graph, it can be seen that the degradation efficiency of the N-EMR on X-3B is still good (basically unchanged) after repeating for five times, and only slightly decreases in the fifth time, and the removal rate is 98.89%.
Claims (7)
1. The preparation method of the modified electrolytic manganese slag comprises the following specific operation steps:
drying the electrolytic manganese slag at 55-75 ℃ for 48-72 hours, and grinding the electrolytic manganese slag and sieving the electrolytic manganese slag with a 100-200 mesh sieve to obtain dried electrolytic manganese slag;
mixing the dried electrolytic manganese slag with NaOH solution and EDTA-2Na, and completely reacting under ultrasound; then standing, removing supernatant, transferring the remaining pasty substances into a hydrothermal reaction kettle, sealing, reacting for 3-6 hours at 100-150 ℃, performing suction filtration and washing, and finally drying the obtained solid at 60-80 ℃ to obtain modified electrolytic manganese slag;
the dosage ratio of the dried electrolytic manganese slag to NaOH and EDTA-2Na in the NaOH solution is 1g (2-4) mmol: (0.01-0.1) g.
2. The preparation method according to claim 1, characterized in that the specific operating steps of the preparation method are as follows:
mixing the dried electrolytic manganese slag with NaOH solution and EDTA-2Na, and reacting for 30min under ultrasound; and standing to remove supernatant, transferring the remaining pasty substances into a hydrothermal reaction kettle, sealing, reacting for 5 hours at 130 ℃, carrying out suction filtration and washing, and finally drying the obtained solid at 75 ℃ to obtain the modified electrolytic manganese slag.
3. The method of claim 1, wherein the NaOH solution has a concentration of 1-3M.
4. Use of the modified electrolytic manganese slag degradation wastewater obtained by the preparation method of any one of claims 1 to 3 for X-3B.
5. The use according to claim 4, characterized in that the step of the use is as follows:
adding the modified electrolytic manganese slag and hydrogen peroxide into the wastewater containing X-3B, then adjusting the pH value of the system to 1-5, and standing;
the dosage ratio of the modified electrolytic manganese slag to the content of X-3B in the X-3B wastewater is (2-5) mg: (3-20) mg: (0.01-0.1) mL; the hydrogen peroxide is H 2 O 2 Hydrogen peroxide with the content of 30 weight percent.
6. The use according to claim 5, wherein 0.1M NaOH and/or 0.1. 0.1M H is used in the use 2 SO 4 The pH of the system is regulated.
7. The use according to claim 5, wherein the concentration of X-3B in the X-3B containing wastewater is 30-200mg/L.
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