CN1320202C - Electrochemical reduction of dyes - Google Patents
Electrochemical reduction of dyes Download PDFInfo
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- CN1320202C CN1320202C CNB2004100563474A CN200410056347A CN1320202C CN 1320202 C CN1320202 C CN 1320202C CN B2004100563474 A CNB2004100563474 A CN B2004100563474A CN 200410056347 A CN200410056347 A CN 200410056347A CN 1320202 C CN1320202 C CN 1320202C
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- 239000000975 dye Substances 0.000 title abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000004020 conductor Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 230000002441 reversible effect Effects 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 abstract description 36
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 238000011282 treatment Methods 0.000 abstract description 2
- 239000003014 ion exchange membrane Substances 0.000 abstract 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000004744 fabric Substances 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000002211 ultraviolet spectrum Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SUOFREPYJDSUTJ-UHFFFAOYSA-N iron sulfurous acid Chemical compound [Fe].S(O)(O)=O SUOFREPYJDSUTJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVEIHEAVXXJNFL-UHFFFAOYSA-N C1(=CC=CC=2C(C=3C(=CC=CC3C(C12)=O)S(=O)(=O)O)=O)S(=O)(=O)O.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O Chemical compound C1(=CC=CC=2C(C=3C(=CC=CC3C(C12)=O)S(=O)(=O)O)=O)S(=O)(=O)O.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O AVEIHEAVXXJNFL-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
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Abstract
The invention discloses an electrochemical dye reduction method, which is to make reducible substances flow through an electrolytic cell designed in a filter screen type or multi-cathode mode and complete electrochemical reduction by means of electron transfer of an intermediate under alkaline conditions. The electrolytic cell comprises a plurality of cathodes and an anode, the cathodes and the anode are separated by an ion exchange membrane, a cathode area and an anode area are respectively formed between the ion exchange membrane and the cathodes and between the ion exchange membrane and the anode, the cathode area is filled with a filtering conductive material for reducing reversible redox water-soluble substances, and the cathode area is provided with an inlet and an outlet for reducing dyes to flow in and out. The electrochemical reduction method can effectively reduce the reduced dye into a soluble dye, and then carry out dyeing and oxidation treatment processes.
Description
Technical field
The present invention relates to a kind of method of reducing of dyestuff, more particularly, relate to a kind of method that adopts a screen pack and many negative electrodes pattern designed electrolytic cell to carry out reducing dye.
Background technology
In bleachinging and dyeing industry, be comparatively general mature technology by dyestuff being gone back the original utilization rate that improves dyestuff, for example: bipseudoindoxyl dye because of it has unique color and luster and light resistance, and is widely used in the dyeing of denim.But water insoluble because of itself again, therefore need reduce in advance, and then carry out dyeing course, promptly indigo reduction is become water soluble state by reductant, and then through repeatedly bleachinging and dyeing and just can finishing by the step of air oxidation fixation.In traditional handicraft, a large amount of chemical reducing agents is used in the reduction of bipseudoindoxyl dye mostly, for example: sodium hydrosulfite (sodium hydrogensulfite) etc.Yet use chemical reducing agent not only to have the production cost height, and to problems such as the expense of wastewater treatment are also high.
The method that has for this reason occurred the electroreduction bipseudoindoxyl dye at present, promptly replace reductant that reducing dyes is become water-soluble attitude by electric energy, dye according to traditional step then, so can significantly reduce the discharging of the consumption and the waste water of reductant, the overall manufacturing cost is reduced.
But at present the electroreduction dye method that utilizes is only applicable to the laboratory mostly, disclosedly among No. 3,953,307, the United States Patent (USP) US directly adds electric protection and reduces the consumption process that reductant is subjected to oxygen comprising having; Disclosed Direct Electrochemistry reduction process among the Electrochimica Acta 47 (2002) 1989; And in No. 5,244,549, United States Patent (USP) US the disclosed process of transmitting as electronics by intermediate.Wherein directly add electric protection method and fail thoroughly to solve and replace the reductant process of adding, and the Direct Electrochemistry reduction process, owing to be subjected to the contacting efficiency influence of insoluble reducing dye to electrode, reduction efficiency is not ideal enough, in can not really being applied to produce.And utilize intermediate, for example: the complex compound of Fe (II)/(III) or some redox organic matters, for example anthraquinone (anthraquinone-1,5-disulfonic acid) can improve reduction efficiency greatly as the medium that electronics transmits.The general requirement of selecting for use of intermediate is a kind of water-soluble substances of the reversible redox at alkaline medium, and reduction potential-more than the 500mV.This process be intermediate when going back ortho states, the intermediate that can become itself reducing dyes oxidation state by the negative electrode regeneration of the electrolytic tank ortho states that returns, carries out next one and circulates again.Though utilize the intermediate can be effectively reducing dyes, although and this process has higher efficient, in can being applied to produce, but in actual production, require to have huge electrolysis area, need be up to 200 to 500 square metres electrolysis area for an about 5000L of production line to the dye vat of 10000L, and general two conventional electrode electrolytic pools need go to install with huge space.Large-area like this electrolytic tank also brings the dead volume problem easily, can acquire a certain degree of difficulty in manufacture process.
For this reason, The present invention be directed to the needs of production and design a kind of have the occupation of land space is little, electrode area is big, dead volume is little filtering type and multiple filtration cathode flow electrolytic tank, utilize the method for reducing of this electrolytic tank not only can reach the consumption that reduces chemicals, and can make the eluate reuse, reach free of contamination substantially reducing dye dyeing course.
Summary of the invention
Main purpose of the present invention is to provide a kind of consumption that reduces chemicals that not only can reach; And can make the electrochemical reduction method of eluate reuse.
Secondary objective of the present invention is to provide a kind of reducing dye colouring method of basic non-wastewater discharge.
To achieve these goals, the electrochemical reduction dye method among the present invention is to make reducible material flow through screen pack formula or many negative electrodes pattern designed electrolytic cell, and electrochemical reduction is finished in the electronics transmission by means of intermediate under alkali condition.
Described electrolytic tank includes a plurality of negative electrodes and an anode, between described negative electrode and anode, isolate by an amberplex, between described amberplex and negative electrode, anode, form cathodic region and anode region respectively, and being filled with the filtration conductive material that can make as the water-soluble substances reduction of reversible redox in the cathodic region, the cathodic region is provided with for reducing dye and flows into and the inlet and the outlet of flowing out simultaneously.
Described negative electrode and anode are the parallel upright setting, and described negative electrode is positioned at the outside of described anode.
Described negative electrode and anode are presented down placement, are provided with to separate the porous offset plate that negative electrode is used between per two adjacent negative electrodes.
Described filtration conductive material is wire, wire netting, Metal Ball or conductive carbon fiber.
Be filled with the catalytic conductive material between described anode and the amberplex, can handle, COD (chemical oxygen consumption (COC)) content in the waste water is reduced waste water.
Electrochemical reduction method among the present invention is to utilize electrolysis and reduce reducing dye under alkali condition, for example: indigo, SULPHUR DYES etc., and in reduction process, adopt a screen pack and many negative electrodes pattern designed electrolytic cell, make under limited space factory building a high efficiency electrolytic tank can be installed, utilize the help of the intermediate (water-soluble substances of reversible redox) that the conductive material of negative electrode produces simultaneously, promptly on electrode, carry out reduction reaction, thereby can be reduced into water-soluble attitude to reducing dye effectively, and intermediate can reduce on electrode, be returned to the original ortho states of going back, carry out reduction process next time again, so repetitive cycling can be carried out free of contamination substantially dyeing and oxidation processes.
Brief Description Of Drawings
Below in conjunction with accompanying drawing the specific embodiment among the present invention is described in further detail.
Fig. 1 is the structural representation of a vertical type filtration flow electrolytic tank among the present invention;
Fig. 2 is the structural representation of a mobile electrolytic tank of cylindrical multiple filtration electrode among the present invention;
Fig. 3 is vertical type filtration flow electrolyser construction schematic diagram that has wastewater treatment among the present invention;
Fig. 4 is the reducing dye dyeing course schematic diagram of a whole production non-wastewater discharge among the present invention.
The specific embodiment
Electrochemical reduction dye method among the present invention is to make reducible dyes (as bipseudoindoxyl dye) flow through screen pack formula and many negative electrodes pattern designed electrolytic cell, and utilizes intermediate to finish electrochemical reduction under alkali condition.A plurality of embodiment that will utilize screen pack and many negative electrodes pattern designed electrolytic cell to come reducing dye and utilize this dyestuff to dye below describe.
Embodiment one
In a dye vat, connect an electrolytic tank, as shown in Figure 1, this electrolytic tank is erectility, comprise screen pack formula negative electrode, be arranged on the both sides of electrolytic tank, form two distinct area 1 in parallel and an anode that fixedly installs 2, this two negative electrode 1 is connected with anodal with the negative pole of power supply respectively with anode 2, and between negative electrode 1 and anode 2, be provided with an amberplex 3, utilize 3 pairs of two negative electrodes 1 of this amberplex and anode 2 to separate, and form two cathodic regions 4 and an anode region 5 respectively, in two cathodic regions 4, be filled with the filtration conductive material 6 that can produce as the water-soluble substances of reversible redox, for example: wire, wire netting, Metal Ball or conductive carbonizable substance, on two cathodic regions 4, following two ends are respectively arranged with inlet 8 and outlet 7, promote by the cathodic region 4 of solution by the pump (not shown) that is located in the dye vat by inlet 8 inflow electrolytic tanks, and by outlet 7 outflows, make and be reduced solution when flowing through enclosed cathodic region 4, utilize the intermediate that conductive material 6 produces in the cathodic region 4, and dyestuff is reduced, promptly be reduced into the soluble state dyestuff, and in the inflow dye vat, the basic composition of liquid is in this dye vat: bipseudoindoxyl dye 2-5 grams per liter, NaOH 2-10 grams per liter, TEA (triethanolamine) 2-4 milliliter/liter, sulfurous acid iron 0.2-2 grams per liter, temperature is 20 ℃-50 ℃, wherein the current density of electrolysis is 0.02-0.5 ampere/square decimeter in the electrolytic process, and the dye strength that is reduced can be measured by a ultraviolet spectrum instrument.
After this moment cotton being put into dye vat and is bleachinged and dyeing 15 seconds to 1 minute, oxidation 30 seconds to 1.5 minutes in air again, and press dry by press drier, this cotton can carry out 3-7 time repeatedly by the process of bleachinging and dyeing oxidation, dries by washing at last.The colourity of this cloth after bleachinging and dyeing can be passed through a colourity analysis-e/or determining.The intermediate that negative electrode produces is a kind of reversible redox material; Promptly reducible one-tenth is gone back ortho states between reduction potential 500mV-800mV, repeats reducing dyes process next time.
In this embodiment, can in anode region 5, electrolyte be set, and electrolyte can be designed to fixed or flow-type, owing to fixed or being provided with of flow-type electrolyte can be realized those skilled in the art, so no longer describe in detail at this.
Embodiment two
Among this embodiment with embodiment in identical parts illustrate by identical figure number, and structure, the principle of work and power with the parts shown in the same reference numbers described in detail no longer separately.
In a dye vat, connect an electrolytic tank; As shown in Figure 2, this electrolytic tank is round barrel shape, the upper strata is provided with a fixed anode 2, lower floor is the negative electrode 1 that multilayer be arranged in parallel, is separated by an amberplex 3 between the negative electrode 1 of upper strata anode 2 and lower floor, and upper strata anode 2 is connected with the positive pole of each power supply, each negative electrode 1 is connected with the negative pole of each power supply respectively, be each negative electrode to a power supply should be arranged, realize independently-poweredly, prevent that lower floor's negative electrode is because of being subjected to the influence of resistance difference away from power supply.Between per two adjacent negative electrodes, be provided with the offset plate 9 of porous, to be separated into a plurality of stacked on top of one another and parallel cathodic region 4, in each cathodic region 4, be filled with the filtration conductive material 6 that can produce, for example: wire, wire netting, Metal Ball or conductive carbonizable substance etc. as the water-soluble substances of reversible redox.
On cathodic region 4, under be respectively arranged with the inlet 8 with the outlet 7, the pump that utilization is provided with in the dye vat promotes to be reduced the inlet 8 inflow cathodic regions 4 of solution from electrolytic tank, and by outlet 7 outflows, make and be reduced flow of solution when enclosed cathodic region 4, the intermediate that utilizes the conductive material 6 in the cathodic region 4 to produce, and reduce to being reduced solution, promptly be reduced into the aqueous solution that can dye once more, and in the inflow dye vat, the basic composition that is back to the solution in the dye vat is: bipseudoindoxyl dye 2-5 grams per liter, NaOH 2-10 grams per liter, anthraquinone 0.2-2 grams per liter, temperature is 20 ℃-50 ℃, electrolytic current density 0.02-0.5 ampere/square decimeter, the dye strength that is reduced is measured by a ultraviolet spectrum instrument.
After this moment cotton being put into dye vat and is bleachinged and dyeing 15 seconds to 1 minute, oxidation 30 seconds to 1.5 minutes in air again, and press dry by press drier, this cotton can carry out 3-7 time repeatedly by the process of bleachinging and dyeing oxidation, dries by washing at last.The colourity of this cloth after bleachinging and dyeing can be passed through a colourity analysis-e/or determining.
After this moment cotton being put into dye vat and is bleachinged and dyeing 15 seconds to 1 minute, oxidation 30 seconds to 1.5 minutes in air again, and press dry by press drier, this cotton can carry out 3-7 time repeatedly by the process of bleachinging and dyeing oxidation, dries by washing at last.The colourity of this cloth after bleachinging and dyeing can be passed through a colourity analysis-e/or determining.
In this embodiment, also can in anode region 5, electrolyte be set, and electrolyte can be designed to fixed or flow-type, can realize those skilled in the art as for being provided with of fixed or flow-type electrolyte, so no longer describe in detail at this.
Embodiment three
Among this embodiment with embodiment in identical parts illustrate by identical figure number, and structure, the principle of work and power with the parts shown in the same reference numbers described in detail no longer separately.
In a dye vat, connect an electrolytic tank, as shown in Figure 3, this electrolytic tank is erectility, wherein electrolytic tank is divided into a mobile anode region 5 and a mobile cathodic region 4, in the cathodic region 4 and 5 of anode regions have an amberplex 3 to separate, being located at anode region 5 is connected with the both positive and negative polarity of power supply respectively with negative electrode 1 with the anode 2 of 4 inside, cathodic region, in cathodic region 4, be filled with the filtration conductive material that can produce as the water-soluble substances of reversible redox, for example: wire, in the metal, Metal Ball or conductive carbonizable substance etc., in the anode region, be filled with the oxidation catalyst filter conductive material, for example: NiCO
2O
4-Ni wire netting.4 upper and lower side is provided with an outlet 7 and one inlet 8 in the cathodic region, what be reduced dye solution in the dye vat flows into cathodic region 4 by inlet 8 under the promotion of a pump, and by outlet 7 outflows, make and be reduced flow of solution when enclosed cathodic region 4, the intermediate that utilizes the conductive material in the cathodic region 4 to produce, and reduce to being reduced solution, promptly be reduced into the aqueous solution that can dye once more.The waste water that flows out in the dye vat is flowed into by inlet 9, flows out through exporting 10, and waste water is handled, and the COD content in the waste water is reduced.8 basic compositions that flow into the dye vat solution that outlet 7 flows out are from entering the mouth: bipseudoindoxyl dye 50-450 grams per liter, NaOH 10-50 grams per liter, TEA5-50 milliliter/liter, sulfurous acid iron 2-20 grams per liter, temperature is 20 ℃-50 ℃, electrolytic current density is 0.05-1.5 ampere/square decimeter, and the dye strength that is reduced is measured by the ultraviolet spectrum instrument.
When solution under the nitrogen protection after diluting 100 times, bleaching and dyeing, be about to cotton and put into dye vat and bleachinged and dyeing 15 seconds-1 minute; And oxidation pressed dry by press drier by 1.5 minutes in 30 seconds again in air, and each dyeing can be by bleachinging and dyeing oxidizing process 3-7 time repeatedly, and by the washing oven dry, the colourity of the cloth after this is bleachinged and dyeing can be measured by the colorimetric analysis instrument at last.
Embodiment four
In a dye vat, connect an electrolytic tank, as shown in Figure 1, this electrolytic tank adopts the electrolytic tank of embodiment one, the basic composition of solution is in the dye vat by being back to after this electrolytic tank electrolysis: bipseudoindoxyl dye 50-450 grams per liter, NaOH 10-50 grams per liter, anthraquinone 5-15 grams per liter, temperature is 20 ℃-50 ℃, electrolytic current density is 0.05-1.5 ampere/square decimeter, and the dye strength that is reduced is measured by a visible spectrometry.
This solution is bleachinged and dyeing after diluting 100 times under nitrogen protection; be about to cotton by in dye vat, bleachinging and dyeing 15 seconds-1 minute; and oxidation 30 seconds to 1.5 minutes in air; press dry by press drier again; dye cloth by bleachinging and dyeing oxidizing process 3-7 time repeatedly at every turn; by the washing oven dry, the chrominance passband of the cloth after this is bleachinged and dyeing is crossed a colourity analysis-e/or determining at last.
Embodiment five
In a dye vat, connect an electrolytic tank, as shown in Figure 2, this electrolytic tank adopts the electrolytic tank of embodiment two, the basic composition of solution is in the dye vat by being back to after this electrolytic tank electrolysis: black sulfide dye 5-100 grams per liter, NaOH 10-50 grams per liter, TEA5-50 milliliter/liter, sulfurous acid iron 2-15 grams per liter, temperature is 20 ℃-90 ℃, electrolytic current density is 0.02-0.5 ampere/square decimeter, and this is reduced the back dye strength and measures by a visible spectrometry.
Then cotton is inserted and bleaching and dyeing 15 seconds-1 minute in the dye vat, and oxidation pressed dry by press drier by 1.5 minutes in 30 seconds again in air, dyed cloth by bleachinging and dyeing oxidizing process 3-7 time repeatedly at every turn, by the washing oven dry, the chrominance passband of the cloth that this is bleachinged and dyeing is crossed a colourity analysis-e/or determining at last.
Embodiment six
In a dye vat, connect an electrolytic tank, as shown in Figure 3, this electrolytic tank adopts the electrolytic tank among the embodiment three, the basic composition of solution is in the dye vat by being back to after this electrolytic tank electrolysis: black sulfide dye 5-100 grams per liter, NaOH 10-50 grams per liter, anthraquinone 0.5-5 grams per liter, temperature is 20 ℃-90 ℃, electrolytic current density is 0.02-0.5 ampere/square decimeter, and this dye strength that is reduced is measured by a ultraviolet spectrum instrument.
Insert cotton and bleaching and dyeing 15 seconds-1 minute in the dye vat this moment, and oxidation pressed dry by press drier by 1.5 minutes in 30 seconds again in air, dye cloth at every turn by bleaching and dyeing, oxidizing process 3-7 time repeatedly, at last by washing, dry.The chrominance passband of the cloth that this is bleachinged and dyeing is crossed a colourity analysis-e/or determining.
Embodiment seven
In a dye vat, connect an electrolytic tank, as shown in Figure 2, this electrolytic tank adopts the electrolytic tank among the embodiment two, the basic composition of solution is in the dye vat by being back to after this electrolytic tank electrolysis: bipseudoindoxyl dye 2-5 grams per liter, NaOH 2-10 grams per liter, TEA2-4 milliliter/liter, sulfurous acid iron 0.2-2 grams per liter, temperature is 20 ℃-50 ℃, electrolytic current density is 0.02-0.5 ampere/square decimeter, and this dye strength that is reduced is measured by a ultraviolet spectrum instrument.
This moment with cotton insert bleachinged and dyeing in the dye vat 15 seconds-1 minute and in air oxidation pressed dry by press drier again by 1.5 minutes in 30 seconds, dye cloth at every turn by bleaching and dyeing, oxidizing process 3-7 time repeatedly, at last by washing, dry.The cloth colourity of bleachinging and dyeing can be passed through a colourity analysis-e/or determining.
Electrolytic tank in the present embodiment also can adopt the electrolytic tank shown in Fig. 3, makes waste water flow into the anode region, carries out electrolytic treatments simultaneously, makes the COD content in the waste water reduce by 10 to 100 times.
As shown in Figure 4, it is the reducing dye dyeing course of a basic non-wastewater discharge of whole production, liquid, the liquid after 12 washings of washing cylinder after dying cloth in a plurality of dye vats that are set up in parallel 11 are back in the electrolytic tank 14 after filtering through filter 13 more in the lump, again liquid is failed back in the dye vat by the electrolytic tank processing, realize recycling and the purpose that reduces production costs, after electrolysis, have only simultaneously seldom part waste water discharge, thereby reach the purpose of basic non-pollution discharge.
Claims (8)
1. an electrochemical reduction dye method it is characterized in that making reducible material to flow through screen pack formula or many negative electrodes pattern designed electrolytic cell, and the electronics transfer function by means of intermediate is finished electrochemical reduction under alkali condition.
2. according to the electrochemical reduction dye method described in the claim 1, it is characterized in that: described electrolytic tank includes a plurality of negative electrodes and an anode, between described negative electrode and anode, isolate by an amberplex, between described amberplex and negative electrode, anode, form cathodic region and anode region respectively, and being filled with the filtration conductive material that makes as the water-soluble substances reduction of reversible redox in the cathodic region, the cathodic region is provided with for reducing dye and flows into and the inlet and the outlet of flowing out simultaneously.
3. according to the electrochemical reduction dye method described in the claim 2, it is characterized in that: described negative electrode and anode are the parallel upright setting, and described negative electrode is positioned at the outside of described anode.
4. according to the electrochemical reduction dye method described in the claim 2, it is characterized in that: described negative electrode is parallel placement up and down with anode, is provided with between per two adjacent negative electrodes and separates the porous offset plate that negative electrode is used.
5. according to the electrochemical reduction dye method described in the claim 4, it is characterized in that: described negative electrode is independent respectively to be connected with the negative pole that is connected.
6. according to the electrochemical reduction dye method described in the claim 2, it is characterized in that: described filtration conductive material is wire, wire netting, Metal Ball or conductive carbonizable substance.
7. according to the electrochemical reduction dye method described in the claim 2, it is characterized in that: be filled with the conductive material of catalytic between described anode and the amberplex, can handle, the COD content in the waste water is reduced waste water.
8. according to the electrochemical reduction dye method described in the claim 7, it is characterized in that: described catalytic conductive material is NiCO
2O
4-Ni wire netting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK04100435A HK1067926A2 (en) | 2004-01-20 | 2004-01-20 | An electrochemical dye reducing method. |
| HK04100435.9 | 2004-01-20 |
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| Publication Number | Publication Date |
|---|---|
| CN1644790A CN1644790A (en) | 2005-07-27 |
| CN1320202C true CN1320202C (en) | 2007-06-06 |
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| CNB2004100563474A Expired - Fee Related CN1320202C (en) | 2004-01-20 | 2004-08-06 | Electrochemical reduction of dyes |
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| CN (1) | CN1320202C (en) |
| HK (1) | HK1067926A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174731B (en) * | 2011-03-04 | 2012-11-07 | 东华大学 | Dyeing device for electrochemical reduction |
| CN102154793A (en) * | 2011-03-23 | 2011-08-17 | 东华大学 | Dyeing apparatus for electrochemical reduction of cotton yarns |
| CN102433770A (en) * | 2011-08-31 | 2012-05-02 | 常州耀春格瑞纺织品有限公司 | Dyeing process for rapid electrochemical cleaning of vat dye |
| CN103835164B (en) * | 2014-03-10 | 2016-01-13 | 江南大学 | A kind of continuous method of cathode electrode in electrochemistry indirect reduction dyeing |
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| CN113227458A (en) * | 2018-12-14 | 2021-08-06 | 拉德伊莱克技术公司 | Electrochemical reactor |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068372A (en) * | 1991-07-10 | 1993-01-27 | 訾风兰 | Diphenyl amine dyestuff intermediate electrosynthesis and device |
| US5244549A (en) * | 1989-06-01 | 1993-09-14 | Verein Zur Forderung Der Forschung Und Entwicklung In Der Textilwirtschaft | Process for the reduction of dyes |
| CN1408037A (en) * | 1999-12-22 | 2003-04-02 | 德意志戴斯达纺织品及染料两合公司 | Electrochemical reduction for reducible dyes |
-
2004
- 2004-01-20 HK HK04100435A patent/HK1067926A2/en not_active IP Right Cessation
- 2004-08-06 CN CNB2004100563474A patent/CN1320202C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244549A (en) * | 1989-06-01 | 1993-09-14 | Verein Zur Forderung Der Forschung Und Entwicklung In Der Textilwirtschaft | Process for the reduction of dyes |
| CN1068372A (en) * | 1991-07-10 | 1993-01-27 | 訾风兰 | Diphenyl amine dyestuff intermediate electrosynthesis and device |
| CN1408037A (en) * | 1999-12-22 | 2003-04-02 | 德意志戴斯达纺织品及染料两合公司 | Electrochemical reduction for reducible dyes |
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| Publication number | Publication date |
|---|---|
| HK1067926A2 (en) | 2005-03-24 |
| CN1644790A (en) | 2005-07-27 |
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