CN109440491B - Denim electroreduction dyeing method - Google Patents

Denim electroreduction dyeing method Download PDF

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CN109440491B
CN109440491B CN201811472599.3A CN201811472599A CN109440491B CN 109440491 B CN109440491 B CN 109440491B CN 201811472599 A CN201811472599 A CN 201811472599A CN 109440491 B CN109440491 B CN 109440491B
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dye
electroreduction
dyeing
denim
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CN109440491A (en
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杨天乔
李正雄
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TAICANG BAONI INDUSTRIAL Co.,Ltd.
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Taicang Baoni Industrial Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a novel denim electroreduction dyeing method, which comprises the following steps: 1) preparing a cathode electrolyte containing 0.05-1 mol/L of nitrogen heterocyclic substances and 0.01-0.1 mol/L of vanadate; 2) the amount of the compound is 10-30 g/L H2SO4The anolyte of (a); 3) after electrifying for a period of time, adding 0.002-0.02mol/L of reduction type dye into the cathode electrolyte, and electrically reducing the dye; and 4) adding the denim into the catholyte for dyeing. The method overcomes a series of potential hazards in the aspects of safety and environmental protection caused by reducing agents such as sodium hydrosulfite and the like in the traditional dyeing process, simultaneously reduces the electroreduction time by 35% -55%, improves the current efficiency by 20-30%, reduces the medium consumption, solves the problems of low iron medium efficiency, long reduction time and high power consumption in the existing medium electroreduction, and has obvious technical effect.

Description

Denim electroreduction dyeing method
Technical Field
The invention relates to a dyeing method of denim, in particular to an electroreduction dyeing method of denim.
Background
Denim is a heavy twill fabric made of pure cotton, which starts in the western united states and is popular with consumers all over the world. Classic denim is dyed with indigo, but with diversified consumer demands, vat and sulfur dyes have been gradually used in recent years. The dye is insoluble in water, and can be reduced into water-soluble leuco sodium salt at 60-80 ℃ by strong alkali and excessive reducing agent to dye the fiber. The common reducing agents are sodium hydrosulfite and sodium sulfide, particularly the most common sodium hydrosulfite, belong to wet inflammable goods, and are exploded or spontaneously combusted in the transportation and storage processes, such as 2018, explosion accidents of sodium hydrosulfite in Chengdu chemical warehouse, 2016, Guannan high speed, transportation spontaneous combustion events of sodium hydrosulfite. In addition, the reducing agent can damage skin and respiratory tract after being contacted for a long time in the production and use processes, harmful waste water and waste gas can be generated during dyeing, the environment is polluted, and workers in China and abroad continuously seek a novel dyeing method which can not use or use less reducing agent.
At present, the research on a new jean dyeing method mainly comprises the following three aspects: first, environmentally friendly reducing agents were developed, such as: thiourea dioxide, iron salt complex, etc., but there are problems such as insufficient reducing power, high price, difficult process control, etc.; secondly, a unique style of 'blue-lining white-through' of the jean is obtained by adopting a water-soluble dye and special treatment, such as: after controlling the pretreatment intensity, dyeing by using active foam, and washing by using enzyme; or a method of stripping and acid washing after active dyeing. Although the above process has no reducing agent, the process is complicated, difficult to control and poor in reproducibility; finally, the novel reduction mode reduces the dye by a catalytic hydrogenation or electroreduction method without a reducing agent; the patent 'hydrogenated indigo dyeing method of cellulose-containing textile material' (publication number: CN1067130C) discloses a method for reducing indigo dye by noble metal catalytic hydrogenation, the dye is reduced by pressure, hydrogen and catalyst, the method is clean and environment-friendly, but has easy explosion hidden trouble and easy over reduction; the electroreduction is to reduce the dye by using cathode electrons, is environment-friendly and safe, is one of the most attractive research directions in the field of current environment-friendly dyeing, and is also the main direction of future development.
In recent years, the most studied electroreduction method at home and abroad is a medium electroreduction method, electrons of a cathode are transferred to dye through a medium in a cathode tank so as to be reduced, a reducing agent and other special conditions are not needed, and the method is environment-friendly, safe and clean. However, as far as the present inventors know, although there are many documents and patents studied, the mediator efficiency is low, so that the electron transfer efficiency is not high, the rate of reducing the dye is slow, and the reduction time is long; the method has the biggest problems of low current utilization efficiency and large power consumption. The researchers concerned are based on the Fe complex medium, or improve the equipment, or screen the ligand, or optimize the process conditions to improve the efficiency. Such as: the patent dyeing equipment for indirect electrochemical reduction (Yangjie, CN102733208B) adopts a method for increasing the area of a cathode, so that the efficiency is improved, but the electrolysis area is large, the cost is high, huge installation space is required, and the dead angle problem is caused; the research on indirect electrochemical dyeing system of vat dye (Caixin, 2013, Siann engineering university) in the literature improves the effect by optimizing Fe ligand and an electroreduction process (voltage, medium concentration, temperature and the like), but does not fundamentally solve the problem and has small improvement amount. Therefore, a more effective solution is developed, a novel electroreduction dyeing method is provided for denim, and the method has important significance for promoting the development of the industry.
Disclosure of Invention
The invention provides an electroreduction dyeing method for denim, which comprises the following steps:
1) preparing a cathode electrolyte containing 0.05-1 mol/L of nitrogen heterocyclic substances and 0.01-0.1 mol/L of vanadate;
2) the amount of the compound is 10-30 g/L H2SO4The anolyte of (a);
3) after electrifying for a period of time, adding 0.002-0.02mol/L of reduction type dye into the cathode electrolyte, and electrically reducing the dye; and
4) and adding the denim into the catholyte for dyeing.
The invention mainly solves the problems of low electron transfer efficiency, low reduction rate of dye and long reduction time of the existing medium electroreduction method; the current utilization efficiency is low, and the power consumption is increased.
In the process of dielectric reduction, electrons flow from the cathode to the cathode, and electron reaction occurs in the cathode tank (the medium obtains electrons from the cathode, transfers the electrons to the dye, the dye is reduced, and the medium losing electrons continuously obtains electrons from the cathode to form circulation); the anode generates electron losing reaction, and meanwhile, electrons in the anode tank are transferred to the cathode through the diaphragm to form a closed loop. The larger the cathode electron absorption amount of the mediator, the more the number of electrons transferred to the dye in the same time, the shorter the time, and the shorter the time for reduction; the more the number of electrons used on the cathode, the less hydrogen evolution side reactions occur and the higher the current utilization efficiency. In addition, in the closed loop, the higher the transfer rate of electrons by the membrane, the higher the circulation efficiency of electrons in the whole closed loop, and the higher the reduction rate and the current efficiency.
The invention creatively adopts a more efficient vanadium salt complex as a novel medium, compared with a + 3-valent iron complex, the vanadium salt complex can absorb 1 electron at a cathode and is changed into a + 2-valent complex, and a + 5-valent vanadium salt complex can absorb 3 electrons and is reduced into the + 2-valent vanadium salt complex, and after the vanadium salt complex is contacted with a dye, the electrons are transferred to the dye to form a water-soluble leuco salt. 1 part of the vanadium salt complex can transfer 3 parts of electrons for 1 time, so that the efficiency is higher; in addition, the vanadium salt complex is in a valence of +5, the attraction force between the vanadium salt complex and a cathode is larger, the adsorption speed is higher, the adsorption quantity is larger, the electron quantity and speed are higher, and the electron transfer speed is high; therefore, the vanadium salt complex is used as a medium, and the reduction rate and the current efficiency are both obviously improved. In addition, in the aspect of the diaphragm, the invention surprisingly discovers that part of alcohol and alcohol ether neutral surfactants have excellent hydrophilicity, wettability and permeability, have good promotion on the exchange rate of proton exchange membranes and accelerate the circulation efficiency of electrons.
Detailed Description
In a preferred embodiment, the invention provides a novel denim electroreduction dyeing method, which comprises the following steps:
1) preparing a cathode electrolyte:
preparing an aqueous solution containing 0.05-1 mol/L of nitrogen heterocyclic substances, stirring for 20min, adding 10-25 g/L of NaOH, adding 0.01-0.1 mol/L of vanadate, stirring for 30min at 30 ℃, adding 1-5 g/L of neutral surfactant to prepare 500ml of aqueous solution, and uniformly stirring for later use.
2) Preparing an anolyte:
preparing a mixture containing 1-5 g/L of neutral surfactant and 15-25 g/L H2SO4250ml of aqueous solution for use.
3) Electroreduction dye
Respectively pouring the prepared catholyte and the prepared anolyte into a yin-yang electrolytic tank, sealing, electromagnetically stirring, heating the electrolyte to 25-45 ℃, preferably about 35 ℃, electrifying for 5-10 min, adding 0.005-0.02 mol/L reduction type dye when the potential in the catholyte reaches the required potential (generally lower than-500 mV, preferably lower than-600 mV, more preferably-500 mV to-1000 mV) for completely reducing the required dye, reducing for 10-60 min, and reducing the water-insoluble dye into the water-soluble leuco sodium salt.
4) The dyeing process comprises the following steps:
and (3) adding 20g of boiled and bleached pure cotton jean into the dye liquor, stirring and dyeing at 35 ℃ for 30-60 min, taking out, oxidizing in air for 10-15 min, and washing with cold water for 10 min.
4) The soaping process comprises the following steps:
and (3) soaping with a soaping agent of 1-2 g/L at the temperature of 98 ℃ for 20min, fully washing with water, drying and testing the performance.
In a more preferred embodiment, the azaheterocyclyl compounds of the present invention are: one or more of imidazole, pyrazine, pyrazole and triazole.
In a more preferred embodiment, the vanadate according to the invention is: one or more of ammonium metavanadate, sodium metavanadate, potassium metavanadate and sodium orthovanadate.
In a more preferred embodiment, the molar ratio of the nitrogen heterocyclic substance to vanadate is 6:1 to 25: 1.
In a more preferred embodiment, the neutral surfactant of the present invention: polyethylene glycol (molecular weight: 200-600), polyethylene glycol with molecular weight of 100-600, and C with oxyethylene unit of 3-108-20One or two of fatty alcohol-polyoxyethylene ether. Said C8-20The fatty alcohol polyoxyethylene ether lauryl alcohol is preferably polyoxyethylene lauryl ether (EO ═ 7), isomeric polyoxyethylene lauryl ether (EO ═ 3, 5, 7) or a mixture thereof.
In a more preferred embodiment, the proton exchange membrane used in the electroreduction apparatus of the present invention is: perfluorosulfonic proton membranes such as Nafion117 or Nafion 324.
In a more preferred embodiment, the vat type dye of the present invention is: one of an indigoid dye, a vat dye, and a sulfur dye.
The denim is dyed by adopting the electro-reduction method provided by the invention, and the dyed fabric with deep color and excellent color fastness can be obtained without dangerous reducing agents such as sodium hydrosulfite and the like; meanwhile, the reduction efficiency is remarkably improved, the electric reduction time is reduced by 35-55%, the current efficiency is improved by 20-30%, the process time is shortened, the electric energy utilization rate is improved, the problems of low iron medium efficiency, long reduction time and high power consumption in the existing medium dielectric reduction are solved, and the technical effect is remarkable.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The examples do not include the techniques or conditions described in the literature in the art or with reference to the product specifications. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The dye sources in each example are as follows: NaOH, sulfuric acid, triethanolamine and ferric sulfate are purchased from Chinese medicine reagents; vanadate was purchased from Shanghai Merlin Biotechnology, Inc.; pure cotton jean, neutral surfactant, soaping agent SW and penetrant JFC are from Shanghai Yayun New Material Co., Ltd; indigo dye, vat brilliant green 3B dye, sulfur black BRN dye from Zhejiang lea soil GmbH.
The low-temperature neutral bleaching agent provided by the invention can be used for bleaching fabrics, and the performance index is measured by the following method:
1) and (3) measuring current efficiency: the copper coulometer method is adopted for measurement, the larger the numerical value is, the larger the current efficiency is, the higher the electric energy utilization rate is, and the smaller the power consumption is.
2) And (3) measuring the color depth K/S value of the dyed fabric: the Datacolor color measuring system, D65 light source, large aperture, measured as the larger the resin, the darker the color.
3) Color fastness to rubbing: GB/T3920-2008 ' color fastness to rubbing ' test of textile color fastness ' determination, the higher the fastness value is, the better the performance is.
4) Fastness to soaping: GB/T3921-2008 soaping color fastness resistance of textile color fastness test, the larger the fastness value is, the better the performance is.
Example 1
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.2mol/L pyrazole and 0.2mol/L pyrazine, stirring for 20min, adding 18g/L NaOH, adding 0.025mol/L potassium metavanadate, stirring for 30min at 30 ℃, adding 0.5g/L polyoxyethylene lauryl ether (n-7) and 1g/L isomeric polyoxyethylene lauryl ether (n-3), preparing 500ml of aqueous solution, and uniformly stirring for later use as a cathode electrolyte.
Preparing an anolyte:
the preparation contains 0.5g/L laurinol polyoxyethylene ether (n ═ 7) and 1g/L isomeric decyl alcohol polyoxyethylene ether (n ═ 7)3) And 20g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Respectively pouring the prepared catholyte and anolyte into a positive and negative electrolytic cell (a diaphragm electrolytic cell, HZC-206, Hangzhou Seao electrochemical experimental equipment, Ltd.), sealing and then electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out voltage 4.0V, electrolyzing for 10min, wherein the potential in the catholyte reaches-950 mv, adding 0.0038mol/L (1.0g) of vat green 3B dye, carrying out electroreduction on the dye, wherein the current shows 0.15A, when the dye liquor is completely changed from insoluble green dispersion liquid into blue transparent solution, indicating that the vat green 3B dye is completely reduced, the electron consumption is 0.0038mol, and recording the electroreduction time as follows: and (6) taking 28 min.
3) The dyeing process comprises the following steps:
adding 20g of boiled and bleached pure cotton denim into the dye solution, stirring and dyeing at 35 ℃ for 45min, taking out, oxidizing in the air for 10min, and washing with cold water for 10 min.
4) The soaping process comprises the following steps:
soaping agent SW: soaping at 98 ℃ for 20min at 1.5g/L, fully washing with water, drying and testing performance.
Comparative example 1
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing water solution containing 0.30mol/L triethanolamine and 18g/L NaOH, stirring for 20min, and adding 0.025mol/L Fe2(SO4)3500ml of aqueous solution is prepared and stirred for 30min for later use as a catholyte.
Preparing an anolyte:
the formulation contains 20g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Pouring the prepared catholyte and anolyte into a positive and negative electrolytic tank (same as above), sealing, electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out voltage 4.0V, electrolyzing for 10min, wherein the potential in the catholyte reaches-950 mv, adding 0.0038mol/L (1.0g) of vat green 3B dye, carrying out electroreduction on the dye, wherein the current shows 0.22A, when the dye liquor is completely changed from insoluble green dispersion liquid into blue transparent solution, the vat green 3B dye is completely reduced, the electron consumption is 0.0038mol, and the time of electroreduction is recorded as follows: and (4) 62 min.
3) The dyeing process comprises the following steps: the procedure is as in example 1.
4) The soaping process comprises the following steps: the procedure is as in example 1.
Example 2
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.8mol/L imidazole, stirring for 20min, adding 25g/L NaOH, adding 0.03mol/L ammonium metavanadate and 0.05mol/L sodium metavanadate, stirring for 30min at 30 ℃, adding 1.5g/L polyethylene glycol (M is 400) and 1.5g/L isomeric dodecyl alcohol polyoxyethylene ether (n is 5), preparing 500ml of aqueous solution, and uniformly stirring for later use as a cathode electrolyte.
Preparing an anolyte:
the preparation contains 1.5g/L of polyethylene glycol (M is 400), 1.5g/L of isomeric decyl alcohol polyoxyethylene ether (n is 5) and 25g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Pouring the prepared catholyte and anolyte into a yin-yang electrolytic tank (same as above), sealing, electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out electrolysis at 5.0V for 10min under the condition that the potential in the catholyte reaches-620 mv, adding 0.0174mol/L (1.0g) of sulfur black BRN dye, carrying out electro-reduction on the dye, wherein the current shows 0.12A, when the dye solution is completely changed into a dark green transparent solution from insoluble black dispersion liquid, the sulfur black BRN dye is completely reduced, the consumed electron amount is 0.0174mol, and recording the electro-reduction time as follows: and (5) 55 min.
3) The dyeing process comprises the following steps:
adding 20g of boiled and bleached pure cotton denim into the dye solution, stirring and dyeing at 35 ℃ for 55min, taking out, oxidizing in the air for 15min, and washing with cold water for 15 min.
4) The soaping process comprises the following steps:
soaping agent SW: 2.0g/L, soaping at 98 ℃ for 20min, fully washing with water, drying and testing performance.
Comparative example 2
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.96mol/L triethanolamine and 25g/L NaOH, stirring for 20min, and then adding 0.08mol/L Fe2(SO4)3500ml of aqueous solution is prepared and stirred for 30min for later use as a catholyte.
Preparing an anolyte:
the formulation contains 25g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Pouring the prepared catholyte and anolyte into a yin-yang electrolytic tank (same as above), sealing, electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out electrolysis at 5.0V for 10min under the condition that the potential in the catholyte reaches-620 mv, adding 0.0174mol/L (1.0g) of sulfur black BRN dye, carrying out electro-reduction on the dye, wherein the current shows 0.21A, when the dye solution is completely changed into a dark green transparent solution from insoluble black dispersion liquid, the sulfur black BRN dye is completely reduced, the consumed electron amount is 0.0174mol, and recording the electro-reduction time as follows: and (4) 125 min.
3) The dyeing process comprises the following steps: the procedure is as in example 2.
4) The soaping process comprises the following steps: the procedure is as in example 2.
Example 3
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.05mol/L pyrazine and 0.15mol/L triazole, stirring for 20min, adding 12g/L NaOH, adding 0.025mol/L sodium orthovanadate, stirring for 30min at 30 ℃, adding 1g/L polyethylene glycol (M is 200) and 3g/L isomeric dodecyl alcohol polyoxyethylene ether (n is 7), preparing 500ml of cathode electrolyte, and uniformly stirring for later use as the cathode electrolyte.
Preparing an anolyte:
preparing the mixture containing 1g/L of polyethylene glycol (M is 200) and 3g/L of isomeric decyl alcohol polyoxyethyleneEther (n-7) and 15g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Pouring the prepared catholyte and anolyte into a yin-yang electrolytic tank (same as above), sealing, electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out voltage of 4.0V, electrolyzing for 10min, wherein the potential in the catholyte reaches-800 mv, adding 0.0046mol/L (0.6g) of indigo dye, carrying out electro-reduction on the dye, wherein the current shows 0.15A, when the dye solution is completely changed from insoluble bluish purple dispersion liquid to yellow green transparent solution, the indigo dye is completely reduced, the electron consumption is 0.0023mol, and the electro-reduction time is recorded as 14 min.
3) The dyeing process comprises the following steps:
adding 20g of boiled and bleached pure cotton denim into the dye solution, stirring and dyeing at 35 ℃ for 40min, taking out, oxidizing in the air for 10min, and washing with cold water for 10 min.
4) The soaping process comprises the following steps:
soaping agent SW: soaping at 98 ℃ for 20min at 1g/L, fully washing with water, drying and testing performance.
Comparative example 3:
1) preparing an electrolyte:
preparing a cathode electrolyte:
preparing water solution containing 0.30mol/L triethanolamine and 12g/L NaOH, stirring for 20min, and adding 0.025mol/L Fe2(SO4)3500ml of aqueous solution is prepared and stirred for 30min for later use as a catholyte.
Preparing an anolyte: the formulation contains 15g/L H2SO4250ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
Pouring the prepared catholyte and anolyte into a yin-yang electrolytic tank (same as above), sealing, electromagnetically stirring, heating the electrolyte to 35 ℃, electrifying, carrying out voltage of 4.0V, electrolyzing for 10min, wherein the potential in the catholyte reaches-800 mv, adding 0.0046mol/L (0.6g) of indigo dye, carrying out electro-reduction on the dye, wherein the current shows 0.22A, when the dye solution is completely changed into a yellow-green transparent solution from an insoluble bluish-purple dispersion liquid, the indigo dye is completely reduced, the electron consumption is 0.0023mol, and the reduction time is recorded as follows: and (3) 30 min.
3) The dyeing process comprises the following steps: the procedure is as in example 3.
4) The soaping process comprises the following steps: the procedure is as in example 3.
Example 4
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.05mol/L pyrazine and 0.15mol/L triazole, stirring for 20min, adding 12g/L NaOH, and then adding 0.025mol/L sodium orthovanadate to prepare 500ml of cathode electrolyte for later use as the cathode electrolyte.
Preparing an anolyte: the formulation contains 15g/L H2SO4200ml of aqueous solution, ready to be used as anolyte.
2) Electroreduction dye
The procedure is as in example 3, voltage 4.0V, current shown as 0.17A, and electroreduction time of indigo dye is recorded as: and (3) 19 min.
3) The dyeing process comprises the following steps: the procedure is as in example 3.
4) The soaping process comprises the following steps: the procedure is as in example 3.
Example 5
1) Preparing an electrolyte:
preparing a cathode electrolyte:
preparing an aqueous solution containing 0.02mol/L pyrazine and 0.06mol/L triazole, stirring for 20min, adding 12g/L NaOH, adding 0.010mol/L sodium orthovanadate, stirring for 30min at 30 ℃, adding 1g/L polyethylene glycol (M is 200) and 3g/L isomeric dodecyl alcohol polyoxyethylene ether (n is 7), preparing 500ml of solution, and uniformly stirring for later use as a cathode electrolyte.
Preparing an anolyte:
the preparation contains 1g/L of polyethylene glycol (M is 200), 3g/L of isomeric decyl alcohol polyoxyethylene ether (n is 7) and 15g/L H2SO4250ml of aqueous solution are ready for use as anolyte.
2) Electroreduction dye
The procedure is as in comparative example 3, voltage 4.0V, current shown as 0.18A, and electroreduction time of indigo dye is recorded as: and (8) the time is 26 min.
3) The dyeing process comprises the following steps: the procedure is as in example 3.
4) The soaping process comprises the following steps: the procedure is as in example 3.
Figure BDA0001891335250000151

Claims (6)

1. An electric reduction dyeing method for denim, which comprises the following steps:
1) preparing a cathode electrolyte containing 0.05-1 mol/L of nitrogen heterocyclic substances and 0.01-0.1 mol/L of vanadate;
2) the amount of the compound is 10-30 g/L H2SO4The anolyte of (a);
3) after electrifying for a period of time, adding 0.002-0.02mol/L of reduction type dye into the cathode electrolyte, and electrically reducing the dye; and
4) adding the denim into the catholyte for dyeing;
the catholyte and the anolyte respectively and independently contain 1-5 g/L of neutral surfactant, and the neutral surfactant is: polyethylene glycol with molecular weight of 100-600, C with oxyethylene unit of 3-108-20One or two of fatty alcohol-polyoxyethylene ether;
the nitrogen heterocyclic substance is as follows: one or more of imidazole, pyrazine, pyrazole and triazole;
the vanadate is one or more of sodium orthovanadate, potassium orthovanadate, ammonium metavanadate, sodium metavanadate and potassium metavanadate.
2. The method for electroreduction dyeing denim according to claim 1, characterized in that: the reduction type dye is as follows: one of vat dyes and sulfur dyes.
3. The method for electroreduction dyeing denim according to claim 1, characterized in that: the reduction type dye is an indigoid dye.
4. The method for electroreduction dyeing denim according to claim 1, characterized in that: the catholyte contains 5-30 g/L alkali metal hydroxide.
5. The method for electroreduction dyeing denim according to claim 4, characterized in that: the catholyte contains 10-25 g/L of sodium hydroxide.
6. The method for electroreduction dyeing denim according to claim 1, characterized in that: it includes oxidation, water washing and soaping processes after dyeing.
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