CN112279344A - Method for fully recycling dye waste liquid - Google Patents
Method for fully recycling dye waste liquid Download PDFInfo
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- CN112279344A CN112279344A CN202010948978.6A CN202010948978A CN112279344A CN 112279344 A CN112279344 A CN 112279344A CN 202010948978 A CN202010948978 A CN 202010948978A CN 112279344 A CN112279344 A CN 112279344A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for fully recycling dye waste liquid, which belongs to the field of electrochemistry and mainly comprises the steps of electrolyzing the dye waste liquid by using a high-efficiency electrolytic catalyst to obtain hydrogen and oxygen, obtaining dye precipitate by centrifugal separation and drying after the waste liquid in the dye is completely electrolyzed, and obtaining a cathode of a lithium ion battery with high specific capacity by a calcining method. The method has simple operation, needs cost, can realize industrial production, and has important significance for environmental protection and obtaining clean energy.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a method for obtaining clean energy by treating dye waste liquid in an electrolysis mode.
Background
In the current society pursuing individuation, the textile industry develops vigorously, various clothes with colorful colors enter the market, not only meet the living needs of people, but also bring a lot of environmental problems, and a large amount of dye waste liquid is discharged, thereby seriously affecting the human health and the ecological environment. Although there are many treatment methods for these waste liquids, including physical adsorption, membrane separation, chemical oxidation, and biodegradation, most dye waste liquid treatment technologies cannot meet the requirement of complete and effective degradation of waste liquid due to the inherent disadvantages of the technologies; therefore, it is important to find a simple and effective method for treating the dye waste liquid.
Electrocatalysis and catalytic materials thereof play important roles in the development and the use of new energy resources. And the electrolyzed water is also an important technology for efficiently preparing clean energy hydrogen and high-purity oxygen. The electrolysis of water involves two half-reactions, the anodic Oxygen Evolution Reaction (OER) and the cathodic Hydrogen Evolution Reaction (HER). Four electrons need to be transferred when the anode completes the oxygen evolution reaction, the reaction kinetics is relatively slow, and the OER process is difficult, so that the promotion of the OER reaction process is the key for improving the water electrolysis efficiency. The invention mainly utilizes a high-efficiency oxygen evolution catalyst to electrolyze the waste liquid in the dye to completely take clean energy hydrogen, then to isolate air to calcine the dye precipitate to obtain a heteroatom-doped porous carbon material, and to use the heteroatom-doped porous carbon material as an electrode material for a lithium ion battery cathode.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for fully recycling dye waste liquid, which is simple to operate, low in cost and applicable to industrial application.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for fully recycling dye waste liquid comprises the following steps:
s1, processing the sheet-shaped substrate material by a hydrothermal method or an electrodeposition method, and preparing a self-supporting electrode material containing metal ion active sites or a precursor of the self-supporting electrode material as a catalyst;
s2, adding a buffering agent into the dye waste liquid, and adjusting the pH value of the waste liquid;
s3, searching a proper potential for electrolysis through the catalyst prepared in the step S1, regulating and controlling the decomposition voltage according to the amount of residual electrolytic dye waste liquid, and stopping electrifying when the dye waste liquid cannot completely coat the substrate material;
and S4, processing the dye residue to prepare the heteroatom-doped porous carbon-based material after the electrolysis is finished.
The technical scheme of the invention is further improved as follows: the aqueous solution used in the hydrothermal or electrodeposition treatment of the sheet-like base material in step S1 is a solution composed of one or more metal salts and a buffer, wherein the metal salts include any one or more of iron salts, nickel salts, manganese salts, and cobalt salts, the iron salt is ferric nitrate or ferric acetate, the nickel salt is nickel nitrate or nickel acetate, the manganese salt is manganese nitrate or manganese acetate, the cobalt salt is cobalt nitrate or cobalt acetate, and the buffer in step S1 is urea or ammonium fluoride.
The technical scheme of the invention is further improved as follows: the sheet-shaped substrate material is rectangular, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 10 hours; the electrodeposition is carried out by a two-electrode system or a three-electrode system, the electrodeposition voltage is-0.6 to-1.2V, and the electrodeposition time is 2 to 60 min.
The technical scheme of the invention is further improved as follows: the sheet-shaped substrate material used in step S1 is any one of foamed titanium, foamed nickel, foamed iron, foamed copper, stainless steel sheet, carbon steel sheet, iron sheet, and nickel sheet.
The technical scheme of the invention is further improved as follows: the subsequent processing mode of preparing the self-supporting electrode material containing the metal ion active sites as the precursor in the step S1 is phosphorization, vulcanization or nitridation.
The technical scheme of the invention is further improved as follows: the processing modes of phosphorization, vulcanization and nitridation comprise that a CVD tubular furnace is used for gasifying a sulfur source, a phosphorus source and a nitrogen source, and then the sulfur source, the phosphorus source and the nitrogen source are uniformly sublimated to the surface of a sheet-shaped substrate material; or the sulfur source, the phosphorus source and the nitrogen source are beaten into a plasma activated state by high pressure, so that the sulfur source, the phosphorus source and the nitrogen source can be quickly coated on the surface of the self-supporting electrode; the sulfur source used for vulcanization during phosphorization, vulcanization or nitridation is sulfur powder or thiourea, the phosphorus source used for phosphorization is sodium hydrogen phosphate or phosphorus powder, and the nitrogen source used for nitridation is nitrogen, ammonium fluoride or ammonium chloride.
The technical scheme of the invention is further improved as follows: the electrolyzed dye waste liquid used in the step S2 is dye waste liquid containing any one or more of azure A, fluorescein sodium, methylene blue and rhodamine B; the buffer for adjusting the pH value in step S2 is potassium hydroxide, sodium hydroxide, glacial acetic acid, sulfuric acid.
The technical scheme of the invention is further improved as follows: the suitable potential is searched in step S3 by assembling the catalyst prepared in step S1 into a two-electrode system, soaking the two-electrode system in the dye waste liquid, measuring the LSV curve of the self-supporting electrode prepared in step S1 in the dye waste liquid by using CHI660 workstation, and searching the current density of 10mAcm through the LSV curve-2The corresponding voltage is full hydrolysis voltage, and then an it curve is measured to carry out constant potential decomposition on the dye waste liquid.
The technical scheme of the invention is further improved as follows: it voltage is 2.2V.
The technical scheme of the invention is further improved as follows: the method for preparing the heteroatom-doped porous carbon-based material by treating the dye residue in the step S4 comprises the steps of placing the dye residue into a crucible, calcining the dye residue at 600-700 ℃ in an Ar atmosphere in a manner of isolating air, and obtaining the heteroatom-doped porous carbon material.
Due to the adoption of the technical scheme, the invention has the technical progress that:
1. the method for recycling the dye in the waste liquid by the electrolysis method has the advantages of simple process and lower experiment cost.
2. The waste liquid of the electrolytic dye can not only obtain clean energy, but also recover the dye in the waste liquid.
3. The pH value of the waste liquid is regulated by adding the buffering agent, so that the oxygen evolution electrolysis voltage can be reduced, the degradation of the dye waste liquid can be accelerated, and the electrolysis cost is saved.
4. The catalyst used for the electrolytic dye waste liquid is a common non-noble metal compound, and is cheap and easy to obtain.
5. Can be produced in large scale and realize industrialization.
Drawings
FIG. 1 is a schematic view of an electrolytic dye waste liquid in examples 1 to 6 of the present invention;
FIG. 2 is an LSV curve of electrolytic methylene blue of example 1 of the present invention;
FIG. 3 is an XRD pattern of the calcined methylene blue dye precipitate of example 1 of the present invention;
FIG. 4 is a diagram of a sample of an electrocatalyst electrolytic rhodamine B dye waste solution prepared in example 2 of the present invention;
FIG. 5 is a diagram showing a dye precipitate obtained by drying after the waste liquid is electrolyzed in examples 1 to 4 of the present invention;
FIG. 6 is an LSV curve of electrolytic methylene blue of example 4 of the present invention;
FIG. 7 is a scanned image of a nickel-iron compound electrocatalyst grown on stainless steel sheet prepared in example 5 of the present invention;
FIG. 8 is a graph showing rate capability of a lithium ion battery made of a porous carbon material obtained by calcining methylene blue in example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
a method for fully recycling dye waste liquid comprises the following steps:
s1, processing the sheet-shaped substrate material by a hydrothermal method or an electrodeposition method, and preparing a self-supporting electrode material containing metal ion active sites or a precursor of the self-supporting electrode material as a catalyst.
The aqueous solution used in the hydrothermal or electrodeposition treatment of the sheet-shaped substrate material is a solution consisting of one or more metal salts and a buffer, wherein the metal salts comprise one or more of ferric salt, nickel salt, manganese salt and cobalt salt, the ferric salt is ferric nitrate or ferric acetate, the nickel salt is nickel nitrate or nickel acetate, the manganese salt is manganese nitrate or manganese acetate, the cobalt salt is cobalt nitrate or cobalt acetate, and the buffer is urea or ammonium fluoride. The sheet-shaped substrate material is foam metal such as foam titanium, foam nickel, foam iron or foam copper, or metal sheet material such as any one of stainless steel sheet, carbon steel sheet, iron sheet and nickel sheet. The sheet-shaped substrate material is rectangular, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 10 hours; the electrodeposition is carried out by a two-electrode system or a three-electrode system, the electrodeposition voltage is-0.6 to-1.2V, and the electrodeposition time is 2 to 60 min.
The subsequent treatment mode for preparing the self-supporting electrode material containing the metal ion active sites as a precursor is phosphorization, vulcanization or nitridation. The processing modes of phosphorization, vulcanization and nitridation comprise that a CVD tubular furnace is used for gasifying a sulfur source, a phosphorus source and a nitrogen source, and then the sulfur source, the phosphorus source and the nitrogen source are uniformly sublimated to the surface of a sheet-shaped substrate material; or the sulfur source, the phosphorus source and the nitrogen source are beaten into a plasma activated state by high pressure, so that the sulfur source, the phosphorus source and the nitrogen source can be quickly coated on the surface of the self-supporting electrode; in the process of phosphorization, vulcanization or nitridation, a sulfur source used for vulcanization is sulfur powder or thiourea, a phosphorus source used for phosphorization is sodium hydrogen phosphate or phosphorus powder, and a nitrogen source used for nitridation is nitrogen, ammonium fluoride or ammonium chloride.
S2, adding a buffering agent into the dye waste liquid, and adjusting the pH value of the waste liquid; the electrolyzed dye waste liquid is the dye waste liquid containing any one or more of azure A, fluorescein sodium, methylene blue and rhodamine B; the buffer for adjusting pH value is potassium hydroxide, sodium hydroxide, glacial acetic acid, and sulfuric acid.
S3, searching proper potential for electrolysis through the catalyst prepared in the step S1, regulating and controlling the decomposition voltage according to the amount of residual electrolytic dye waste liquid, and stopping electrifying when the dye waste liquid can not completely coat the substrate material. The appropriate potential was found by assembling the catalyst prepared in step S1 into a two-electrode system, soaking in dyeMeasuring LSV curve of the self-supporting electrode prepared in S1 in the waste dye liquor by using CHI660 workstation, and searching current density of 10mAcm by using the LSV curve-2The corresponding voltage is full hydrolysis voltage, and then an it curve is measured to carry out constant potential decomposition on the dye waste liquid. it voltage is preferably 2.2V.
And S4, processing the dye residue to prepare the heteroatom-doped porous carbon-based material after the electrolysis is finished.
The specific process is as follows: the method for preparing the heteroatom-doped porous carbon-based material by treating the dye residue comprises the steps of putting the dye residue into a crucible, calcining the dye residue at the temperature of 600-700 ℃ in an Ar atmosphere in a heat insulating mode, and using the obtained heteroatom-doped porous carbon material as the negative electrode of the lithium ion battery.
The following detailed description is given in terms of specific examples:
wherein, fig. 1 is a schematic diagram of the electrolytic dye waste liquid in examples 1-6 of the present invention, the left diagram is before electrolysis, the middle diagram is during electrolysis, the precipitation volume ratio of oxygen and hydrogen is 1:2, the right diagram is after electrolysis, the waste liquid is continuously reduced, the dye precipitate is precipitated while hydrogen and oxygen are prepared, and the precipitated dye precipitate is used as a precursor for preparing the porous carbon material for standby.
Example 1
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking rectangular titanium foam in dilute hydrochloric acid, distilled water and absolute ethyl alcohol in sequence, and ultrasonically cleaning for 20 min. Adding a proper amount of cobalt acetate, nickel acetate and distilled water into a 100ml reaction kettle to prepare a solution, then putting the treated titanium foam into a hydrothermal reaction kettle without overlapping, and carrying out hydrothermal reaction at 120 ℃ for 10 hours. And taking out the foamed titanium sheet in the hydrothermal kettle, ultrasonically cleaning the foamed titanium sheet in distilled water to remove the drug residues which are not firmly grown on the surface of the foamed titanium, and drying the foamed titanium sheet in a 60-degree oven for 4 hours.
(2) Preparing a saturated solution of methylene blue, adding KOH into the saturated solution, and controlling the pH value of the methylene blue dye waste liquid to be about 14.
(3) Electrolyzing dye waste liquid, recycling dye: welding the foamed titanium sheet with nickel-iron compound on the nickel strip, placing into a test tube containing waste dye solution (as shown in figure 1), and connecting the two ends of the nickel stripOn CHI660 workstation, firstly measuring LSV curve of catalyst in dye waste liquid, searching suitable voltage of electrolytic dye waste liquid, and finding out current density of 100mAcm-2When the required voltage is 1.9V, an it curve is measured, and the dye waste liquid is decomposed at constant potential. And finally, putting the obtained methylene blue dye precipitate into a crucible, and calcining the mixture at 600 ℃ in an Ar atmosphere at the isolation of air. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery. FIG. 3 is an XRD pattern of the resulting porous carbon material with carbon peaks, demonstrating that calcination of the dye precipitates results in a heteroatom-doped porous carbon material.
Example 2
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking foamed iron with length, width and height of 1cm 0.8mm in sequence with diluted hydrochloric acid, distilled water and anhydrous ethanol, and ultrasonically cleaning for 20 min. Adding a proper amount of manganese acetate, nickel nitrate, urea and distilled water into a 100ml reaction kettle to prepare a solution, then putting the treated foam iron into a hydrothermal reaction kettle without overlapping, and carrying out hydrothermal reaction for 10 hours at 120 ℃. And taking out the foam iron sheet in the hydrothermal kettle, ultrasonically cleaning the foam iron sheet in distilled water to remove the drug residues with infirm growth on the surface of the foam iron, and drying the foam iron sheet in a 60-DEG oven for 4 hours. And putting the dried substrate material and 0.5g of sulfur powder into a CVD (chemical vapor deposition) tube furnace together, and calcining for 2 hours at 300 ℃ to obtain the vulcanized electrode material and enhance the corrosion resistance of the material.
(2) Preparing saturated solution of rhodamine B, adding acetic acid into the saturated solution, and controlling the pH value of the dye waste liquid to be 5.5-7.
(3) Electrolyzing dye waste liquid, and recovering dye: welding a foam iron sheet with a nickel-iron compound on a nickel strip, oppositely placing the nickel strip in a test tube (shown in figure 1) containing rhodamine B dye waste liquid, connecting two ends of the nickel strip to a CHI660 workstation, firstly measuring an LSV curve of a catalyst in the dye waste liquid, searching for a proper voltage of electrolytic dye waste liquid, then measuring an it curve, and carrying out constant potential decomposition on the dye waste liquid. And finally, putting the obtained rhodamine B dye precipitate into a crucible, and calcining at 650 ℃ in an Ar atmosphere at the same time. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery. FIG. 4 is a diagram of a substance for electrolyzing rhodamine B dye waste liquid by a nickel-iron catalyst.
Example 3
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking foamed nickel with length, width and height of 1cm 0.8mm in sequence with diluted hydrochloric acid, distilled water and absolute ethyl alcohol, and ultrasonically cleaning for 20 min. Adding a proper amount of ferric nitrate, nickel acetate, ammonium fluoride and distilled water into a 100ml reaction kettle to prepare a solution, then putting the treated nickel foam into a hydrothermal reaction kettle without overlapping, and carrying out hydrothermal reaction for 10 hours at 120 ℃. And taking out the foamed nickel sheet in the hydrothermal kettle, ultrasonically cleaning the foamed nickel sheet in distilled water to remove the medicine residues with infirm growth on the surface of the foamed nickel, and drying the foamed nickel sheet in a 60-DEG oven for 4 hours.
(2) Preparing a saturated solution of azure A, adding Na (OH)2And controlling the pH value of the azure A dye waste liquid to be about 14.
(3) Electrolyzing dye waste liquid, and recovering dye: welding a foam nickel sheet with a nickel-iron compound on a nickel strip, oppositely placing the nickel strip in a test tube (shown in figure 1) containing dye waste liquid, connecting two ends of the nickel strip to a CHI660 workstation, firstly measuring an LSV curve of a catalyst in the dye waste liquid, searching for a proper voltage of the electrolytic dye waste liquid, then measuring an it curve, and carrying out constant potential decomposition on the dye waste liquid. And finally, putting the obtained azure A dye precipitate into a crucible, and calcining the azure A dye precipitate at 700 ℃ in an Ar atmosphere in an isolated air mode. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery.
Example 4
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking foamed copper with length, width and height of 1cm 0.8mm in sequence with diluted hydrochloric acid, distilled water and absolute ethyl alcohol, and ultrasonically cleaning for 20 min. Adding a proper amount of ferric nitrate, nickel nitrate, ammonium fluoride, urea and distilled water into a 100ml reaction kettle to prepare a solution, then putting the treated foamy copper into a hydrothermal reaction kettle without overlapping, and carrying out hydrothermal treatment at 120 ℃ for 10 hours. And taking out the foam copper sheet in the hydrothermal kettle, ultrasonically cleaning the foam copper sheet in distilled water to remove the medicine residues with infirm growth on the surface of the foam copper sheet, and drying the foam copper sheet in a 60-DEG oven for 4 hours. And putting the dried substrate material and 0.6g of sodium hydrogen phosphate into a CVD tubular furnace together, and calcining for 2.5 hours at 380 ℃ to obtain a phosphatized electrode material and enhance the oxygen evolution performance of the material.
(2) Preparing saturated solution of fluorescein sodium, adding sulfuric acid, and controlling the pH value of the dye waste liquid to be about 4.8.
(3) Electrolyzing dye waste liquid, and recovering dye: welding a foam copper sheet with a nickel-iron compound on a nickel strip, oppositely placing the nickel strip in a test tube (shown in figure 1) containing dye waste liquid, connecting two ends of the nickel strip to a CHI660 workstation, firstly measuring an LSV curve of a catalyst in the dye waste liquid, searching for proper voltage of electrolytic dye waste liquid, and finding out that the current density is 100mAcm-2When the required voltage is 2.2V, an it curve is measured, and the dye waste liquid is decomposed at constant potential. And finally, putting the obtained fluorescein sodium dye precipitate into a crucible, and calcining at 680 ℃ in an Ar atmosphere at the interval of air. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery. FIG. 6 is an LSV curve of a nickel-iron catalyst electrolytic sodium fluorescein grown on a copper foam showing a current density of 100mAcm-2The required voltage is 2.2V.
Example 5
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking stainless steel sheet with length, width and height of 1.2cm 1mm in diluted hydrochloric acid, distilled water and anhydrous ethanol, and ultrasonic cleaning for 20 min. And (3) forming a two-electrode system by the well-regulated substrate material, applying a voltage of-0.6V, carrying out electrodeposition for 2min, electrodepositing metal ions on the sheet-shaped substrate, taking out the stainless steel sheet after the electrodeposition is finished, carrying out ultrasonic cleaning in distilled water, removing the drug residues with infirm growth on the surface of the stainless steel sheet, and drying in a 60-degree oven for 4 h. And putting the dried substrate material and 0.6g of ammonium fluoride into a CVD tube furnace together, and calcining for 2.5 hours at 380 ℃ to obtain the nitrided electrode material and enhance the hydrogen evolution performance of the material.
(2) Preparing saturated solution of rhodamine B, adding sulfuric acid into the saturated solution, and controlling the pH value of the dye waste liquid to be about 6.5.
(3) Electrolyzing dye waste liquid, and recovering dye: welding a foam copper sheet with a nickel-iron compound on a nickel strip, oppositely placing the nickel strip in a test tube (shown in figure 1) containing dye waste liquid, connecting two ends of the nickel strip to a CHI660 workstation, firstly measuring an LSV curve of a catalyst in the dye waste liquid, searching for a proper voltage of the electrolytic dye waste liquid, then measuring an it curve, and carrying out constant potential decomposition on the dye waste liquid. And finally, putting the obtained rhodamine B dye precipitate into a crucible, and calcining at 680 ℃ in an Ar atmosphere at the same time. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery. Fig. 7 is a scan of the nickel iron compound electrocatalyst grown on stainless steel sheets prepared in this example, with iron nickel spheres clearly visible.
Example 6
(1) Preparing a catalyst required by the electrolytic dye waste liquid: soaking foamed copper with length, width and height of 1.2cm 1cm 0.8mm in sequence with diluted hydrochloric acid, distilled water and absolute ethyl alcohol, and ultrasonically cleaning for 20 min. And (3) forming a three-electrode system by the well-regulated substrate material, saturated calomel carbon and a carbon rod, applying a voltage of-1.2V for 60min to electrodeposit metal ions on the sheet-shaped substrate, taking out the stainless steel sheet after the electrodeposition is finished, ultrasonically cleaning the stainless steel sheet in distilled water to remove the drug residues with unstable growth on the surface of the stainless steel sheet, and drying the stainless steel sheet in a 60-degree oven for 4 h. And (3) putting the dried substrate material into a plasma tube, and electrifying at high voltage to obtain a nitrided electrode material so as to enhance the full-hydrolytic property of the material.
(2) Preparing saturated solution of fluorescein sodium, adding sulfuric acid, and controlling the pH value of the dye waste liquid to be about 4.8.
(3) Electrolyzing dye waste liquid, and recovering dye: welding a foam copper sheet with a nickel-iron compound on a nickel strip, oppositely placing the nickel strip in a test tube (shown in figure 1) containing dye waste liquid, connecting two ends of the nickel strip to a CHI660 workstation, firstly measuring an LSV curve of a catalyst in the dye waste liquid, searching for a proper voltage of the electrolytic dye waste liquid, then measuring an it curve, and carrying out constant potential decomposition on the dye waste liquid. And finally, putting the obtained fluorescein sodium dye precipitate into a crucible, and calcining at 680 ℃ in an Ar atmosphere at the interval of air. And obtaining the porous carbon material doped with the heteroatom as the negative electrode of the lithium ion battery. Fig. 8 is a rate performance diagram when the carbon material is used as a lithium ion battery cathode, and the capacity of the porous carbon material prepared after electrolysis is higher, which shows that the carbon material obtained after electrolysis has better rate performance and larger battery capacity.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A method for fully recycling dye waste liquid is characterized by comprising the following steps:
s1, processing the sheet-shaped substrate material in a hydrothermal or electro-deposition mode, and preparing a self-supporting electrode material containing metal ion active sites or a precursor of the self-supporting electrode material as a catalyst;
s2, adding a buffering agent into the dye waste liquid, and adjusting the pH value of the waste liquid;
s3, searching a proper potential for electrolysis through the catalyst prepared in the step S1, regulating and controlling the decomposition voltage according to the amount of residual electrolytic dye waste liquid, and stopping electrifying when the dye waste liquid cannot completely coat the substrate material;
and S4, processing the dye residue to prepare the heteroatom-doped porous carbon-based material after the electrolysis is finished.
2. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the aqueous solution used in the hydrothermal or electrodeposition treatment of the sheet-like base material in step S1 is a solution composed of one or more metal salts and a buffer, wherein the metal salts include any one or more of iron salts, nickel salts, manganese salts, and cobalt salts, the iron salt is ferric nitrate or ferric acetate, the nickel salt is nickel nitrate or nickel acetate, the manganese salt is manganese nitrate or manganese acetate, the cobalt salt is cobalt nitrate or cobalt acetate, and the buffer in step S1 is urea or ammonium fluoride.
3. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the sheet-shaped substrate material is rectangular, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 10 hours; the electrodeposition is carried out by a two-electrode system or a three-electrode system, the electrodeposition voltage is-0.6 to-1.2V, and the electrodeposition time is 2 to 60 min.
4. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the sheet-shaped substrate material used in step S1 is any one of foamed titanium, foamed nickel, foamed iron, foamed copper, stainless steel sheet, carbon steel sheet, iron sheet, and nickel sheet.
5. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the subsequent processing mode of preparing the self-supporting electrode material containing the metal ion active sites as the precursor in the step S1 is phosphorization, vulcanization or nitridation.
6. The method for fully recycling the waste dye liquor as claimed in claim 5, wherein the method comprises the following steps: the processing modes of phosphorization, vulcanization and nitridation comprise that a CVD tubular furnace is used for gasifying a sulfur source, a phosphorus source and a nitrogen source, and then the sulfur source, the phosphorus source and the nitrogen source are uniformly sublimated to the surface of a sheet-shaped substrate material; or the sulfur source, the phosphorus source and the nitrogen source are beaten into a plasma activated state by high pressure, so that the sulfur source, the phosphorus source and the nitrogen source can be quickly coated on the surface of the self-supporting electrode; the sulfur source used for vulcanization during phosphorization, vulcanization or nitridation is sulfur powder or thiourea, the phosphorus source used for phosphorization is sodium hydrogen phosphate or phosphorus powder, and the nitrogen source used for nitridation is nitrogen, ammonium fluoride or ammonium chloride.
7. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the electrolyzed dye waste liquid used in the step S2 is dye waste liquid containing any one or more of azure A, fluorescein sodium, methylene blue and rhodamine B; the buffer for adjusting the pH value in step S2 is potassium hydroxide, sodium hydroxide, glacial acetic acid, sulfuric acid.
8. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the search for a suitable potential in step S3 is "ONAssembling the catalyst prepared in the step S1 into a two-electrode system, soaking the two-electrode system in dye waste liquid, measuring an LSV curve of the self-supporting electrode prepared in the step S1 in the dye waste liquid by using a CHI660 workstation, and searching for a current density of 10mAcm through the LSV curve-2The corresponding voltage is full hydrolysis voltage, and then an it curve is measured to carry out constant potential decomposition on the dye waste liquid.
9. The method for fully recycling the waste dye liquor as claimed in claim 8, wherein the method comprises the following steps: it voltage is 2.2V.
10. The method for fully recycling the waste dye liquor as claimed in claim 1, wherein the method comprises the following steps: the method for preparing the heteroatom-doped porous carbon-based material by treating the dye residue in the step S4 comprises the steps of placing the dye residue into a crucible, calcining the dye residue at 600-700 ℃ in an Ar atmosphere in a manner of isolating air, and obtaining the heteroatom-doped porous carbon material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112875678A (en) * | 2021-02-23 | 2021-06-01 | 石河子大学 | Method for preparing carbon material by using dye wastewater as raw material |
| CN113529124A (en) * | 2021-06-09 | 2021-10-22 | 武汉纺织大学 | Electrolytic water cathode material, preparation method thereof and application of cathode material in electrocatalytic hydrogenation reduction of dye |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160152648A1 (en) * | 2013-07-03 | 2016-06-02 | Yale University | Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof |
| CN108083519A (en) * | 2017-12-27 | 2018-05-29 | 黄山学院 | A kind of method of rhodamine B degradation waste water |
| CN110255528A (en) * | 2019-07-25 | 2019-09-20 | 燕山大学 | The method and its application of porous carbon materials are prepared using dyestuff waste liquid |
| CN110492093A (en) * | 2019-08-26 | 2019-11-22 | 燕山大学 | The preparation method of self-supporting material |
| CN111097474A (en) * | 2019-12-11 | 2020-05-05 | 江苏大学 | Preparation method of polyphenol or aromatic carboxylic acid for universal construction of single-atom and atom-dispersed multi-metal catalyst |
| CN111495417A (en) * | 2020-05-26 | 2020-08-07 | 盐城工学院 | Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof |
-
2020
- 2020-09-10 CN CN202010948978.6A patent/CN112279344B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160152648A1 (en) * | 2013-07-03 | 2016-06-02 | Yale University | Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof |
| CN108083519A (en) * | 2017-12-27 | 2018-05-29 | 黄山学院 | A kind of method of rhodamine B degradation waste water |
| CN110255528A (en) * | 2019-07-25 | 2019-09-20 | 燕山大学 | The method and its application of porous carbon materials are prepared using dyestuff waste liquid |
| CN110492093A (en) * | 2019-08-26 | 2019-11-22 | 燕山大学 | The preparation method of self-supporting material |
| CN111097474A (en) * | 2019-12-11 | 2020-05-05 | 江苏大学 | Preparation method of polyphenol or aromatic carboxylic acid for universal construction of single-atom and atom-dispersed multi-metal catalyst |
| CN111495417A (en) * | 2020-05-26 | 2020-08-07 | 盐城工学院 | Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 宋秀丽: "《无机材料制备及技术》", 31 December 2008, 中国建材工业出版社 * |
| 陈群玉: "《水污染控制工程》", 30 June 2018, 中国民族大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112875678A (en) * | 2021-02-23 | 2021-06-01 | 石河子大学 | Method for preparing carbon material by using dye wastewater as raw material |
| CN112875678B (en) * | 2021-02-23 | 2022-08-26 | 石河子大学 | Method for preparing carbon material by using dye wastewater as raw material |
| CN113529124A (en) * | 2021-06-09 | 2021-10-22 | 武汉纺织大学 | Electrolytic water cathode material, preparation method thereof and application of cathode material in electrocatalytic hydrogenation reduction of dye |
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