Integrated electrochemical dyeing method based on vat dye deep dyeing
By modifying the three-dimensional graphite felt/non-noble metal composite electrode and using surfactants, the problem of small contact area of dye in the electrocatalytic hydrogenation reduction dye system is solved, and the deep dyeing and electrode catalytic activity are improved are achieved, which significantly improves the dyeing effect and performance.
Patent Information
- Application Number
- CN202510065298.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-16
- Publication Date
- 2025-05-06
AI Technical Summary
In the existing electrocatalytic hydrogenation reducing dye system, the contact time between the dye and the catalytic electrode is short and the contact area is small, resulting in poor reduction effect.
The three-dimensional graphite felt/non-noble metal composite electrode was used as the cathode, and the electrode surface was modified through plasma treatment and electrodeposition technology, and combined with the surfactant in the cathode electrolyte, an H-type electrolytic cell device was constructed for constant current reduction.
The deep dye performance of the dye is achieved, the catalytic activity and dyeing depth of the electrode are improved, and the general performance of the dyed cloth sample is enhanced, such as dry friction fastness, wet friction fastness and wash-stain/discoloration fastness.
Smart Images
Figure CN119932933A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of reducing dye dyeing, and in particular to an integrated electrochemical dyeing method based on reducing dye deep dyeing. Specifically, it includes a three-dimensional graphite felt / non-precious metal composite electrode as a cathode, a platinum electrode as an anode, and an H-type electrolytic cell. The optimal experimental system is determined by studying the components of the cathode electrolyte, the related reducing dyeing indicators in the electrochemical reduction, the qualitative and quantitative relationship between the reducing efficiency, the dyeing depth and the parameters such as the applied voltage, the reducing time, and the electrode area. Background Art
[0002] Reduction dyes are insoluble in water. Traditional processes use hydrosulfite as a reducing agent, but it releases toxic gases when it encounters acid. At the same time, high-concentration sulfates, sulfites and other products will be produced during the reduction process, increasing the burden of sewage treatment. For this reason, there are a variety of new electrochemical reduction methods for reduction dye dyeing, such as direct electrochemical reduction, indirect electrochemical reduction and electrocatalytic hydrogenation reduction. Among them, electrocatalytic hydrogenation reduction has the characteristics of mild reaction conditions and easy control, and is a green and environmentally friendly process. At present, different cathode materials such as porous graphite electrodes and nickel-sulfur alloys have been studied, but their operation time is long and the catalytic activity is not high. Precious metal catalysts are still the most efficient electrocatalysts due to their small overpotential and high selectivity. However, their application is limited by their small reserves, easy poisoning and high cost. Therefore, non-precious metal catalysts have been developed one after another, among which Mo-based catalysts can inhibit the competitive hydrogen evolution reaction (HER), so they can be used as ideal electroreduction reaction materials. However, the electrocatalytic reaction needs to be carried out under alkaline conditions, and the single metal catalyst has low conductivity, poor corrosion resistance and activity, and is easy to agglomerate. Studies have found that selecting multiple transition metals for composite and multi-element doping can effectively reduce the proton adsorption free energy and improve the electrocatalytic activity.
[0003] In the current electrocatalytic hydrogenation reduction dye system, the reduction dye is mostly water-insoluble solid particles, which are two-phase with water. Therefore, the contact time between the reduction dye and the catalytic electrode is short, the contact area is small, and the reduction effect is poor. Based on this, the introduction of multi-element doped Mo-based catalysts will further interact with oxygen atoms with a larger electron cloud density, increasing the polarity of C=O and the positive charge of carbonyl carbon. Therefore, a composite electrode with high specific surface area, high conductivity and high catalytic activity is urgently needed.
[0004] Graphite felt can be used as a base material because of its intrinsic three-dimensional characteristics, good electronic conductivity, high specific surface area and strong mechanical properties. However, the functional groups on the surface of graphite felt are inert, and the interaction between them and solvents and other media is weak. Therefore, this patent proposes to use plasma treatment and electrodeposition technology to achieve material surface modification, which can integrate nitrogen doping regulation elements and surface structure changes, and combine with the assistance of surfactants in the cathode electrolyte to achieve deep dyeing performance of reduced dyes. The electrocatalytic hydrogenation reduction process is simple, the equipment cost is low, and the process is easy to control. Summary of the invention
[0005] In view of this, the present invention aims to address the deficiencies in the prior art, and its main purpose is to provide an integrated electrochemical dyeing method based on vat dye deep dyeing, which can integrate nitrogen doping regulation elements and surface structure changes, combined with the assistance of surfactants in the cathode electrolyte, to achieve vat dye deep dyeing performance.
[0006] To achieve the above purpose, the present invention adopts the following technical solutions:
[0007] An integrated electrochemical dyeing method based on deep dyeing with vat dyes comprises the following steps:
[0008] (1) Preparation of three-dimensional electrode: The graphite felt CF is ultrasonically treated with dilute hydrochloric acid and acetone, then washed with deionized water for several times and dried; then the graphite felt CF is placed in a radio frequency plasma reaction chamber, and nitrogen is introduced in a vacuum atmosphere for a treatment time of 130 to 150 seconds and a treatment height of 2 to 3 mm as surface activation before deposition to improve the bonding effect between the graphite felt CF and the catalyst; then, the treated graphite felt CF is used as a working electrode, a counter electrode is a platinum electrode, and a reference electrode is a saturated calomel electrode, and a constant current electrodeposition is performed in a three-electrode system to prepare an electrode. After the deposition is completed, it is transferred to a tubular furnace for sintering to obtain a three-dimensional electrode;
[0009] (2) Constructing an electrocatalytic reduction dyeing system for reducing dye dyeing: using an H-type electrolytic cell device, wherein the cathode is the three-dimensional electrode prepared in step (1), the anode is a platinum electrode, the cathode electrolyte is 1M NaOH, 0.5-1g / L reducing dye and surfactant, the diaphragm is a Nafion membrane, the anode electrolyte is 1M NaOH, the cotton cloth is placed in the cathode electrolyte, N2 is first introduced for deoxygenation for 10-15 minutes, and then power is applied for constant current reduction, the current density is 40A / m 2 ~50A / m 2 , the temperature is 40-60℃, the reduction time is 40-60min; then take out the cotton cloth and air oxidize it for 5-10min, then wash it with hot water at 50-60℃, and then perform soap boiling, water washing and drying in sequence.
[0010] Preferably, the three-dimensional electrode is a three-dimensional P@MoS2 / CF electrode, and the electrolyte used in its preparation is 0.3-0.5 mol Na2MoO4·2H2O, 0.4-0.6 mol thiourea and 0.1-0.2 mol NaH2PO4·H2O solution.
[0011] Preferably, the three-dimensional electrode is a three-dimensional MoS2 / CF electrode, and the electrolyte used in its preparation is 0.3-0.5 mol Na2MoO4·2H2O and 0.4-0.6 mol thiourea.
[0012] Preferably, the current of the electrolyte is 150-200 mA, the deposition time is 40 min-60 min, and the deposition temperature is 60°C.
[0013] Preferably, the ultrasonic treatment time in step (1) is 30 minutes.
[0014] Preferably, the power of the radio frequency plasma reaction chamber in step (1) is 500-600W.
[0015] Preferably, the flow rate of nitrogen introduced in step (1) is 500-600 mL / min.
[0016] Preferably, the surfactant in step (2) is a quaternary ammonium salt, a sulphur salt or a phosphate salt.
[0017] Preferably, the quaternary ammonium salt is C 17 H 35 CONHCH2CH2N(CH3)3Cl、C 17 H 35 CONHCH2CH2NH3Cl and C 17 H 35 CONHCH2CH2N(C2H5) 33 One or more of Cl, the sulfide salt is H 25 C 12 S(CH3)3Cl, the phosphine salt is H 25 C 12 P(CH3)3Cl.
[0018] Preferably, the soap boiling treatment in step (2) uses 4 g / L soap powder and 3 g / L sodium carbonate at 95° C. for 20 min.
[0019] Compared with the prior art, the present invention has obvious advantages and beneficial effects. Specifically, it can be seen from the above technical solution that:
[0020] (1) Industrial graphite felt is used as the electrode substrate. Simple plasma etching has the advantages of time saving and cleaning, and can greatly increase the specific surface area. The etching points can be used as attachment points for activated particles, which is conducive to the combination and loading of multi-element doped Mo-based catalysts.
[0021] (2) A large number of carbon defect structures and oxygen vacancies can be produced by one-step electrodeposition of multi-element doped Mo-based catalysts, which integrate hydrogen production and hydrogenation catalysis. The active hydrogen generated in situ by water electrolysis can be used to reduce the dye, and hydrogen intermediates can be adsorbed at the same time to reduce the occurrence of hydrogen evolution side reactions and improve the catalytic activity of the electrode.
[0022] (3) Adding surfactants such as quaternary ammonium salts, sulfonates or phosphates to the cathode electrolyte can greatly increase the current transfer efficiency and the dyeing depth and fastness of cotton cloth through electrolysis.
[0023] (4) Optimize the electrochemical reduction system of reduced dyes to achieve the following performance indicators of electrocatalytic hydrogenation reduced dyes: K / S value of dyed fabric ≥ K / S value of traditional hydrosulfite dyed fabric (dye with the same concentration); dyeing dry friction fastness ≥ 4-5 levels; wet friction fastness ≥ 3 levels; washing staining / discoloration fastness ≥ 4-5 levels; when the reduced dye solution is recycled for ≥ 10 times, the change rate of K / S value of the dyed fabric is ≤ 5%. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 The surface SEM images of the three-dimensional graphite felt / P@MoS2 electrode prepared by the present invention when the deposition time is 40min and 60min;
[0025] Figure 2 : is the cyclic voltammetry curve of the three-dimensional P@MoS2 / CF electrode of the present invention at different indigo concentrations;
[0026] Figure 3 This is the electrochemical reduction dyeing cloth sample of the present invention (a is reduction red R, b is reduction brilliant green FFB, c is reduction yellow G, d is indigo, and the dye concentration is 1.0 g / L). DETAILED DESCRIPTION
[0027] The present invention discloses an integrated electrochemical dyeing method based on deep dyeing with vat dyes, comprising the following steps:
[0028] (1) Preparation of three-dimensional electrode: The graphite felt CF is ultrasonically treated with dilute hydrochloric acid and acetone, then washed with deionized water for several times and dried; then the graphite felt CF is placed in a radio frequency plasma reaction chamber, and nitrogen is introduced in a vacuum atmosphere. The treatment time is 130 to 150 seconds, and the treatment height is 2 to 3 mm as surface activation before deposition to improve the bonding effect between the graphite felt CF and the catalyst; then, the treated graphite felt CF is used as the working electrode, the counter electrode is a platinum electrode, and the reference electrode is a saturated calomel electrode. The electrode is prepared by constant current electrodeposition in a three-electrode system. After the deposition is completed, it is transferred to a tube furnace for sintering to obtain a three-dimensional electrode. The three-dimensional electrode is a three-dimensional P@MoS2 / CF electrode or a three-dimensional MoS2 / CF electrode. When the three-dimensional electrode is a three-dimensional P@MoS2 / CF electrode, the electrolyte used in its preparation is 0.3 to 0.5 mol Na2MoO4·2H2O, 0.4 to 0.6 mol thiourea and 0.1 to 0.2 mol NaH2PO4·H2O solution. When the three-dimensional electrode is a three-dimensional MoS2 / CF electrode, the electrolyte used in its preparation is 0.3-0.5 mol Na2MoO4·2H2O and 0.4-0.6 mol thiourea. The current of the electrolyte is 150-200 mA, the deposition time is 40 min-60 min, and the deposition temperature is 60°C. The time of the ultrasonic treatment is 30 min. The power of the radio frequency plasma reaction chamber is 500-600 W. The flow rate of the nitrogen gas is 500-600 mL / min. The graphite felt CF is industrial graphite felt CF.
[0029] (2) Constructing an electrocatalytic reduction dyeing system for reducing dye dyeing: using an H-type electrolytic cell device, wherein the cathode is the three-dimensional electrode prepared in step (1), the anode is a platinum electrode, the cathode electrolyte is 1M NaOH, 0.5-1g / L reducing dye and surfactant, the diaphragm is a Nafion membrane, the anode electrolyte is 1M NaOH, the cotton cloth is placed in the cathode electrolyte, N2 is first introduced for deoxygenation for 10-15 minutes, and then power is applied for constant current reduction, the current density is 40A / m 2 ~50A / m 2 , the temperature is 40-60°C, the reduction time is 40-60 minutes; then the cotton cloth is taken out and air oxidized for 5-10 minutes, then washed with hot water at 50-60°C, and then soaped, washed and dried in sequence. The surfactant is a quaternary ammonium salt, a sulfur salt or a phosphate salt. The quaternary ammonium salt is C 17 H 35 CONHCH2CH2N(CH3)3Cl、C 17 H 35 CONHCH2CH2NH3Cl and C 17 H 35 CONHCH2CH2N(C2H5)33 One or more of Cl, the sulfide salt is H 25 C 12 S(CH3)3Cl, the phosphine salt is H 25 C 12 The soap boiling treatment uses 4g / L soap powder and 3g / L sodium carbonate at 95°C for 20min.
[0030] The electrocatalytic activity and electrochemical active area of different electrodes (cathodes) are different, as shown in Tables 1 and 2 below:
[0031] Table 1 Electrocatalytic activity of different electrodes (cathodes)
[0032]
[0033] Table 2 Electrochemical active areas of different electrodes (cathodes)
[0034]
[0035] Test performance and methods
[0036] (1) K / S value test
[0037] Dyeing depth is one of the important evaluation indicators of dyeing performance. K represents the absorption coefficient of the object being tested, and S represents the scattering coefficient. According to the Kubelka-Munk reflection function, both coefficients have a certain functional relationship with the concentration C of the colored substance, that is, the higher the solid concentration, the darker the color, and the larger the K / S value. Before the test, the sample needs to be controlled at standard humidity and temperature under constant temperature and humidity conditions, and then the K / S value is measured on the Datacolor 650 computer colorimeter for 4 times and the average value is taken.
[0038] (3) Dry / wet abrasion fastness test
[0039] The experiment was carried out on a cotton fabric of 5cm×14cm size for dry and wet rubbing fastness test according to the standard test method of GB / T3920-2008 "Textiles - Tests for Colour Fastness - Colour Fastness to Rubbing". At the same time, the standard test of GB / T 251-2008 "Textiles - Tests for Colour Fastness - Grey Scale for Assessing Staining" was used to assess the colour fastness grade.
[0040] (4) Soap fastness test
[0041] The experiment was carried out on a cotton fabric of size 10cm×4cm for soap fastness test according to the standard method of GB / T3921-2008D "Textiles - Colour Fastness Tests - Colour Fastness to Washing". At the same time, the standard test of GB / T250-2008 "Textiles - Colour Fastness Tests - Grey Scale for Assessing Discoloration" was used to assess the colour fastness to soap washing.
[0042] The present invention is further described in detail with multiple embodiments below:
[0043] Embodiment 1:
[0044] (1) Preparation of three-dimensional electrodes: The industrial graphite felt CF was ultrasonically treated with dilute hydrochloric acid and acetone for 30 minutes, then washed several times with deionized water and dried. Then the industrial graphite felt CF was placed in a radio frequency plasma reaction chamber with a power of 600W, and nitrogen was introduced in a vacuum atmosphere with a flow rate of 500mL / min, a treatment time of 130s, and a treatment height of 2mm as surface activation before deposition to improve the bonding effect between the industrial graphite felt CF and the catalyst. The treated industrial graphite felt CF was used as the working electrode, the counter electrode was a platinum electrode, and the reference electrode was a saturated calomel electrode. The electrode was prepared by constant current electrodeposition in a three-electrode system. The electrolyte was 0.5mol Na2MoO4·2H2O, 0.6mol thiourea and 0.1mol NaH2PO4·H2O solution. The electrolyte current was 200A / m 2 The deposition time was 40 min, the deposition temperature was 60 °C, and then it was transferred into a tube furnace and sintered at 400 °C in N2 atmosphere for 2 h, and cooled to room temperature to prepare a three-dimensional P@MoS2 / CF electrode.
[0045] (2) Construction of an electrocatalytic reduction dyeing system for reducing dyes (adding surfactants): An H-type electrolytic cell device was used, in which the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1 cm*2 cm), the anode was a platinum electrode (1 cm*2 cm), and the cathode electrolyte was 1 M NaOH, 1.0 g / L reducing yellow G (100 mL) and surfactant C 17 H 35 CONHCH2CH2NH3Cl, the diaphragm is Nafion membrane, the anolyte is 1M NaOH (100mL), the cotton cloth is placed in the catholyte, N2 is first introduced for deoxygenation for 10-15min, and then the power is turned on for constant current reduction, the current density is 40A / m 2 , the temperature is 50℃, and the reduction time is 60min. Then take out the cotton cloth and oxidize it in air for 10min, wash it in hot water at 60℃, boil it in soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0046] Alternatively, an electrocatalytic reduction dyeing system for reducing dye dyeing (without surfactant) was constructed: an H-type electrolytic cell device was used, wherein the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1cm*2cm), the anode was a platinum electrode (1cm*2cm), the cathode electrolyte was 1M NaOH and 1.0g / L reducing yellow G (100mL), the diaphragm was a Nafion membrane, the anode electrolyte was 1M NaOH (100mL), the cotton cloth was placed in the cathode electrolyte, N2 was first introduced for deoxygenation for 10 to 15 minutes, and then power was turned on for constant current reduction, and the current density was 40A / m 2 , the temperature is 50℃, and the reduction time is 60min. Then take out the cotton cloth and oxidize it in air for 10min, wash it in hot water at 60℃, boil it in soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0047] Traditional hydrosulfite reduction dyeing process:
[0048] Use deionized water to dissolve caustic soda and insurance powder respectively, pour in the dye, and when the solution turns dark blue and is completely reduced to a leuco form, add pure cotton fabric at a bath ratio of 1:100, dye for 45 minutes, and then place in the air to oxidize until it no longer changes color. Then rinse with warm water first, then with cold water, and soap wash at a bath ratio of 1:50, boil at 97℃ for 10 minutes, wash with water, and dry.
[0049] Table 3 Electrocatalytic hydrogenation reduction dyeing results
[0050]
[0051] Embodiment 2:
[0052] (1) Preparation of three-dimensional electrode: The industrial graphite felt CF was ultrasonically treated with dilute hydrochloric acid and acetone for 30 minutes, then washed several times with deionized water and dried. Then the industrial graphite felt CF was placed in a radio frequency plasma reaction chamber with a power of 600W, and nitrogen was introduced in a vacuum atmosphere with a flow rate of 500mL / min, a treatment time of 130s, and a treatment height of 2mm as surface activation before deposition to improve the binding effect between the industrial graphite felt CF and the catalyst. The treated industrial graphite felt CF was used as the working electrode, the counter electrode was a platinum electrode, and the reference electrode was a saturated calomel electrode. The electrode was prepared by constant current electrodeposition in a three-electrode system. The electrolyte was 0.5mol Na2MoO4·2H2O, 0.6mol thiourea and 0.1mol NaH2PO4·H2O solution. The electrolyte current was 200 mA, the deposition time was 40 min, the deposition temperature was 60 ° C, and then it was transferred into a tubular furnace, sintered at 400 ° C, N2 atmosphere for 2 h, and cooled to room temperature to prepare a three-dimensional P@MoS2 / CF electrode.
[0053] (2) Construction of an electrocatalytic hydrogenation reduction system for reducing dyes: An H-type electrolytic cell device was used, in which the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1 cm*2 cm), the anode was a platinum electrode (1 cm*2 cm), and the cathode electrolyte was 1 M NaOH, 1.0 g / L reduced emerald green FFB (100 mL) and a surfactant H 25 C 12 S(CH3)3Cl, the diaphragm is Nafion membrane, the anolyte is 1M NaOH (100mL), the cotton cloth is placed in the catholyte, N2 is first introduced for deoxygenation for 15min, and then the power is turned on for constant current reduction, the current density is 40A / m 2 , the temperature is 60℃, and the reduction time is 45min. Then take out the cotton cloth and air oxidize it for 10min, wash it with hot water at 60℃, boil it with soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0054] Alternatively, an electrocatalytic reduction dyeing system for reducing dye dyeing (without surfactant) was constructed: the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1cm*2cm), the anode was a platinum electrode (1cm*2cm), the cathode electrolyte was 1M NaOH and 1.0g / L reducing emerald green FFB (100mL), the diaphragm was a Nafion membrane, the anode electrolyte was 1M NaOH (100mL), the cotton cloth was placed in the cathode electrolyte, N2 was first introduced for deoxygenation for 15min, and then power was turned on for constant current reduction, and the current density was 40A / m 2 , the temperature is 60℃, and the reduction time is 45min. Then take out the cotton cloth and air oxidize it for 10min, wash it with hot water at 60℃, boil it with soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0055] Traditional hydrosulfite reduction dyeing process:
[0056] Use deionized water to dissolve caustic soda and insurance powder respectively, pour in the dye, and when the solution turns dark blue and is completely reduced to a leuco form, add pure cotton fabric at a bath ratio of 1:100, dye for 45 minutes, and then place in the air to oxidize until it no longer changes color. Then rinse with warm water first, then with cold water, and soap wash at a bath ratio of 1:50, boil at 97℃ for 10 minutes, wash with water, and dry.
[0057] Table 4 Electrocatalytic hydrogenation reduction dyeing results
[0058]
[0059] Embodiment 3:
[0060] (1) Preparation of three-dimensional electrode: The industrial graphite felt CF was ultrasonically treated with dilute hydrochloric acid and acetone for 30 minutes, then washed several times with deionized water and dried. Then the industrial graphite felt CF was placed in a radio frequency plasma reaction chamber with a power of 500W, and nitrogen was introduced in a vacuum atmosphere with a flow rate of 600mL / min, a treatment time of 150s, and a treatment height of 2mm as surface activation before deposition to improve the binding effect between the industrial graphite felt CF and the catalyst. The treated industrial graphite felt CF was used as the working electrode, the counter electrode was a platinum electrode, and the reference electrode was a saturated calomel electrode. The electrode was prepared by constant current electrodeposition in a three-electrode system. The electrolyte was 0.5mol Na2MoO4·2H2O, 0.6mol thiourea and 0.2mol NaH2PO4·H2O solution. The electrolyte current was 150 mA, the deposition time was 60 min, the deposition temperature was 60 ° C, and then it was transferred into a tube furnace, sintered at 400 ° C, N2 atmosphere for 2 h, and cooled to room temperature to prepare a three-dimensional P@MoS2 / CF electrode.
[0061] (2) Construction of an electrocatalytic hydrogenation reduction system for reducing dyes: An H-type electrolytic cell device was used, in which the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1 cm*2 cm), the anode was a platinum electrode (1 cm*2 cm), and the cathode electrolyte was 1 M NaOH, 1.0 g / L indigo (100 mL) and a surfactant H 25 C 12 P(CH3)3Cl, the diaphragm is Nafion membrane, the anolyte is 1MNaOH (100mL), the cotton cloth is placed in the catholyte, N2 is first introduced for deoxygenation for 15min, and then the power is turned on for constant current reduction, the current density is 40A / m 2 , the temperature is 40℃, and the reduction time is 60min. Then take out the cotton cloth and oxidize it in air for 10min, wash it in hot water at 60℃, boil it with soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0062] Alternatively, an electrocatalytic reduction dyeing system for reducing dye dyeing (without surfactant) was constructed: the cathode was the prepared three-dimensional P@MoS2 / CF electrode (1cm*2cm), the anode was a platinum electrode (1cm*2cm), the cathode electrolyte was 1M NaOH and 1.0g / L indigo (100mL), the diaphragm was a Nafion membrane, the anode electrolyte was 1M NaOH (100mL), the cotton cloth was placed in the cathode electrolyte, N2 was first introduced for deoxygenation for 15min, and then power was turned on for constant current reduction at a current density of 40A / m 2, the temperature is 40℃, and the reduction time is 60min. Then take out the cotton cloth and oxidize it in air for 10min, wash it in hot water at 60℃, boil it with soap (4g / L soap powder, 3g / L sodium carbonate, and treat it at 95℃ for 20min), wash it with water, and dry it.
[0063] Traditional hydrosulfite reduction dyeing process:
[0064] Use deionized water to dissolve caustic soda and insurance powder respectively, pour in the dye, and when the solution turns dark blue and is completely reduced to a leuco form, add pure cotton fabric at a bath ratio of 1:100, dye for 45 minutes, and then place in the air to oxidize until it no longer changes color. Then rinse with warm water first, then with cold water, and soap wash at a bath ratio of 1:50, boil at 97℃ for 10 minutes, wash with water, and dry.
[0065] Table 5 Electrocatalytic hydrogenation reduction dyeing results
[0066]
[0067] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.
Claims
1. An integrated electrochemical dyeing method based on deep dyeing with vat dyes, characterized in that: The following steps are included: (1) Preparation of three-dimensional electrode: The graphite felt CF is ultrasonically treated with dilute hydrochloric acid and acetone, then washed with deionized water for several times and dried; then the graphite felt CF is placed in a radio frequency plasma reaction chamber, and nitrogen is introduced in a vacuum atmosphere for a treatment time of 130 to 150 seconds and a treatment height of 2 to 3 mm as surface activation before deposition to improve the bonding effect between the graphite felt CF and the catalyst; then, the treated graphite felt CF is used as a working electrode, a counter electrode is a platinum electrode, and a reference electrode is a saturated calomel electrode, and a constant current electrodeposition is performed in a three-electrode system to prepare an electrode. After the deposition is completed, it is transferred to a tubular furnace for sintering to obtain a three-dimensional electrode; (2) Constructing an electrocatalytic reduction dyeing system for reducing dye dyeing: using an H-type electrolytic cell device, wherein the cathode is the three-dimensional electrode prepared in step (1), the anode is a platinum electrode, the cathode electrolyte is 1M NaOH, 0.5-1g / L reducing dye and surfactant, the diaphragm is a Nafion membrane, the anode electrolyte is 1M NaOH, the cotton cloth is placed in the cathode electrolyte, N2 is first introduced for deoxygenation for 10-15 minutes, and then power is applied for constant current reduction, the current density is 40A / m 2 ~50A / m 2 , the temperature is 40-60℃, the reduction time is 40-60min; then take out the cotton cloth and air oxidize it for 5-10min, then wash it with hot water at 50-60℃, and then perform soap boiling, water washing and drying in sequence.
2. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 1, characterized in that: The three-dimensional electrode is a three-dimensional P@MoS2 / CF electrode, and the electrolyte used in its preparation is 0.3-0.5 mol Na2MoO4·2H2O, 0.4-0.6 mol thiourea and 0.1-0.2 mol NaH2PO4·H2O solution.
3. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 1, characterized in that: The three-dimensional electrode is a three-dimensional MoS2 / CF electrode, and the electrolyte used in its preparation is 0.3-0.5 mol Na2MoO4·2H2O and 0.4-0.6 mol thiourea.
4. An integrated electrochemical dyeing method based on deep dyeing with vat dyes as claimed in claim 2 or 3, characterized in that: The current of the electrolyte is 150-200 mA, the deposition time is 40-60 minutes, and the deposition temperature is 60°C.
5. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 1, characterized in that: The ultrasonic treatment time in step (1) is 30 minutes.
6. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 1, characterized in that: The power of the radio frequency plasma reaction chamber in the step (1) is 500-600W.
7. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 1, characterized in that: The flow rate of nitrogen introduced in step (1) is 500-600 mL / min.
8. The integrated electrochemical dyeing method based on deep dyeing with vat dyes according to claim 1, characterized in that: In the step (2), the surfactant is a quaternary ammonium salt, a sulphur salt or a phosphate salt.
9. The integrated electrochemical dyeing method based on vat dye deep dyeing according to claim 8, characterized in that: The quaternary ammonium salt is C 17 H 35 CONHCH2CH2N(CH3)3Cl、C 17 H 35 CONHCH2CH2NH3Cl and C 17 H 35 CONHCH2CH2N(C2H5) 33 One or more of Cl, the sulfide salt is H 25 C 12 S(CH3)3Cl, the phosphine salt is H 25 C 12 P(CH3)3Cl.
10. The integrated electrochemical dyeing method based on deep dyeing with vat dyes according to claim 1, characterized in that: In the step (2), the soap boiling treatment uses 4 g / L soap powder and 3 g / L sodium carbonate and is processed at 95° C. for 20 minutes.