EP0426832A1 - Verfahren zur reduktion von farbstoffen. - Google Patents
Verfahren zur reduktion von farbstoffen.Info
- Publication number
- EP0426832A1 EP0426832A1 EP90908918A EP90908918A EP0426832A1 EP 0426832 A1 EP0426832 A1 EP 0426832A1 EP 90908918 A EP90908918 A EP 90908918A EP 90908918 A EP90908918 A EP 90908918A EP 0426832 A1 EP0426832 A1 EP 0426832A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- potential
- dye
- cathode
- reducing agent
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000975 dye Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 230000002829 reductive effect Effects 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000012546 transfer Methods 0.000 claims abstract description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000004043 dyeing Methods 0.000 description 17
- 239000010949 copper Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000000988 sulfur dye Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000984 vat dye Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000987 azo dye Substances 0.000 description 4
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 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
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003452 sulfinic acid derivatives Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- OZTBHAGJSKTDGM-UHFFFAOYSA-N 9,10-dioxoanthracene-1,5-disulfonic acid Chemical compound O=C1C=2C(S(=O)(=O)O)=CC=CC=2C(=O)C2=C1C=CC=C2S(O)(=O)=O OZTBHAGJSKTDGM-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000004338 hydroxy anthraquinones Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000010447 natron Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007585 pull-off test Methods 0.000 description 1
- 238000009895 reductive bleaching Methods 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000004048 vat dyeing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- D06P1/221—Reducing systems; Reducing catalysts
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2016—Application of electric energy
Definitions
- the invention relates to a process for reducing dyes in aqueous solution with pH> 9, using a reducing agent with a redox potential of over 400 mV, which is present in a reduced and oxidized form, wherein a pair of electrodes is introduced into the solution. whose cathode potential is kept below the value at which hydrogen development occurs.
- vat dyes are used for textile finishing.
- Dyeing of cellulose fibers represents a considerable share of the market (approx. 12.5%, world consumption approx. 25,000 t / year).
- this dye class is one of the high-quality dyes.
- the primarily non-fiber-insoluble dye particles are converted into their alkaline, soluble leuco form by reduction.
- the reduced dye has a high affinity for the substrate and is now quickly absorbed by the material to be dyed.
- the pull-up phase has ended, the leuco form is oxidized to fix the dye, and the water-insoluble pigment forms.
- the basic chemical structure of the dyes is often anthrachi noide or indigoide.
- sulfur dyes are inferior to vat dyes, but they are very cheap in price, so that they have a relatively large market share in cellulose dyeing (25%, 50,000 t / year).
- the sulfur dyes are used analogously to the vat dyes, the reduction of the sulfur dyes being possible even at lower redox potentials.
- Reducing agents are also used to destroy excess bleaching agents, for reductive bleaching (wool) and reductive wastewater treatment (decolorization).
- the main reducing agent for vat dyeing and for the reductive cleavage of azo dyes is Na ? S-, 0, Nat ri umdi thi oni t ("Hydro"), which has a reduction potential of approximately -1000 mV in an alkaline environment.
- Sulfinic acid derivatives are used for reductions at higher temperatures (steaming processes, HT processes) (reduction potential at 50 C approx. -1000 mV ) .
- Sulfinic acid derivatives can by the use of heavy metal compounds, such as Ni-Cyan ⁇ komplexjsn, Co-Ko p lexen et c. to be activated. It has been proposed to use anth rach i non compounds as accelerators for the reducing agents used, but is practically not carried out.
- Other reducing agents are Th i oharnstoffdi ox id
- indigo lies between the vat dyes and sulfur dyes.
- hydroxyacetone / sodium hydroxide solution can also be used here as the reducing agent.
- iron vitriol (FeSO,) -Ka Ik vats, zinc-lime vats and fermentation vats have been enacted. Because of the lower required reduction potential, others can also be used for sulfur staining
- Reducing agents are used.
- the main reductions are Na_S and NaHS (reduction potential approx. -500 mV).
- Mixtures of glucose / sodium hydroxide solution were also used.
- a method of the type described in the introduction has already been proposed, in which the consumption of Nat ri umdi thi oni by applying a DC voltage t is reduced.
- This reduction is due to the fact that the reducing agent is converted at the cathode into a form which has an increased reducing capacity.
- this substance breaks down into the same products as the sodium di-thi oni t itself. These products cannot be regenerated with the voltage applied to the cathode.
- This voltage is in any case at a level which can only be used with the mercury electrode used, but which would already lead to harmful hydrogen evolution in the case of practically applicable electrode materials.
- aS- j O is a relatively expensive chemical that has to be imported by many countries.
- a large excess of Na-SO based on the amount theoretically required for the reduction, must be used in the dyeing processes.
- the oxygen present in the liquor must first be removed, only then can the dye begin to be reduced.
- atmospheric oxygen from the environment continuously consumes a ⁇ S ⁇ O.
- the quantities used are approx. 1.25 to 2.5 kg of reducing agent per kg of dye.
- the reducing agent bath leads to a considerable generation of oxygen in the wastewater, which leads to learning about wastewater.
- the procurement costs are relatively low, but the wastewater problem is becoming increasingly important here, since in addition to oxygen generation there are also considerable toxicity and odor problems.
- the invention is based on the object of avoiding the illustrated disadvantages of the previous reducing agents. This is achieved by using a reducing agent whose redox potential (half-stage potential i a L), increased by the charge transfer overvoltage for the return of the oxidized form of the reducing agent into the reduced one, which is below the cathode potential, at the cathode.
- the dye is therefore not reduced directly at the electrode, which has already been proposed, but has not proven successful. Rather, a reducing agent is used which reduces the dye in the usual way, is oxidized in the process and reaches the cathode in this oxidized form, where it is neither returned to its original state.
- Redox systems of this type are known in electrochemistry as
- the cathode thus reduces the reversible redox system which, in turn, is able to reduce the dye after the reduction potential of the dye has been reached.
- the upstream reversible redox system has the task of generating a continuously regenerable reduction potential in the dyeing liquor, so that no further reducing agent has to be added to the dyeing liquor.
- the proportion of reducing agent consumed by air toxicity is continuously renewed at the cathode. No secondary products result from the addition of reducing agents in the dye liquor. Enrichment by the usually necessary addition of reducing agent also does not occur.
- the dye bath After removing the unfixed dye (centrifugation, filtration, ..), the dye bath can be reused, only the liquor volume lost with the goods having to be replaced. Chemical consumption in the usual sense does not occur. Even the dye re-oxidation can be carried out in the dye bath, which, according to the literature, should lead to an improvement in the fastness to rubbing of the dye (doubtful. This procedure is not economically justifiable with the reducing agents currently used, since at the end of the dyeing process, large reduction medium L quantities remain in the dye liquor and draining the dye liquor is more cost-effective. A closed recycling of the entire dyeing liquor without time-consuming reprocessing is also out of the question here due to the ongoing enrichment with reducing agent secondary products.
- Inorganic compounds for the invention Use usable r, one has to look above all under the Meta L Ikomp lexsa Izen.
- the Fe (II / III) triethanolamine natron lye system is suitable as a reduction mediator.
- the attainable potentials of up to -980 mV enable the reduction of all common vat dyes, indigoid dyes, sulfur dyes, azo dyes without the use of other reducing substances.
- the invention is then explained in more detail using a device for carrying out the method and by means of some application examples.
- the device for carrying out the method is shown schematically in the single drawing.
- the device shown comprises a container 11, on the bottom of which there is a working cathode 1 made of copper. To accelerate the removal of the
- Reduction products are located above the working cathode 1, a magnetic stirrer 8.
- a reference electrode 4 (Ag / AgCl) is provided for measuring the cathode potential i a Is by means of the voltmeter 5. The potential in solution is measured using a dedicated measuring electrode 3
- a container 10 filled with textiles to be colored is introduced into the cathode side of the electrolytic chamber with respect to the diaphragm 7, through which the solution is sucked by means of the liquor circulation pump 9, whereupon it gets back into the container 11.
- the working cathode consists of Cu (area 36 cm 2 ), the working anode consists of Pt (area 10 cm 2 ).
- the working potential of the Cu cathode is -1150 mV against an AgCl Re ⁇ nzeie electrode.
- the goods are wetted with the alkali at 40 C C.
- the potential in the solution rises to -94 mV within 20 min and is held there for 1 hour.
- the reduced dye on the goods is oxidized by rinsing
- the dyeing is completed by boiling soap according to the dye manufacturer's instructions.
- the color depth achieved during coloring corresponds to the guidelines of the dye manufacturers.
- the working cathode consists of Cu (area 36 cm 2 , the working anode consists of Pt (area 10 cm 2 ).
- the working potential of the Cu cathode is -1150 mV against an AgCl reference electrode.
- the goods are wetted with the alkali at room temperature After the addition of the redox system and the switching on of the working current (approx.
- the potential in the solution rises to over -800 m within 20 min and is held there for 40 min "" C increases, the working current rises to 60 mA, the potential in the solution reaches -870 mV.
- the reduced dye on the goods is oxidized by rinsing.
- the dyeing is completed by boiling soap The color depth achieved during the dyeing corresponds to the guide values of the dye manufacturers.
- Color depth starting color 10 g color / kg fabric ( KV-colored ) dye bath: 8.8 g / 1 aOH, 4 g / 1 triethanolamine, 0.5 g / 1 Fe2 ( SO, ) 3
- the working cathode consists of Cu (area 36 cm 2), the working anode is ⁇ (Pt surface 10 cm 2).
- the working potential of the Cu cathode is -1150 mV against an AgCl reference electrode.
- the goods are wetted with the lye.
- the potential in the solution rises to -450 mV within 20 min.
- Dye bath 1.4 g / 1 NaOH, 30 g / 1 Na2 S04, 4 g / 1 triethanola in, 0.5 g / 1 FeS ⁇ 4.7H20
- the working cathode consists of Cu (area 36 cm 2 ), which consists of the working anode made of Pt (area 10 cm 2 ).
- the working potential of the Cu cathode is -1150 mV against an AgCl reference electrode.
- the goods are wetted with the lye.
- the potential in the solution rises to over -870 mV within 50 min, especially after adding the Xa2 SO4.
- the dyeing temperature is increased to approx. 45'C.
- the reduced dye on the goods is oxidized by rinsing.
- the dyeing is completed by boiling soap according to the dye manufacturer's instructions.
- the color depth achieved in the coloring corresponds to the guide values of the dye manufacturers.
- Dyebath 4 g / 1 NaOH, 0.5 g / 1 anthraquinone-1, 5-disulfonic acid, 10 mg / 1 hydron blue 3R
- the working cathode consists of Cu (area 88 cm 2 ), the working anode consists of Pt (area 6 cm 2 ).
- the working potential of the Cu cathode is -850 mV against an AgCl reference element!
- the reduction of the dye is monitored colorimetrically. Even at room temperature, the upstream anthraquinone system is reduced by up to approx. 34% within 20 minutes (reaching the half-step potential), the sulfur dye now added is immediately quantitatively reduced. After the working current has been switched off, the reoxidation of the sulfur dye can be observed.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT9090908918T ATE105345T1 (de) | 1989-06-01 | 1990-05-31 | Verfahren zur reduktion von farbstoffen. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT1329/89 | 1989-06-01 | ||
AT0132989A AT398316B (de) | 1989-06-01 | 1989-06-01 | Verfahren zur reduktion von farbstoffen |
PCT/AT1990/000052 WO1990015182A1 (de) | 1989-06-01 | 1990-05-31 | Verfahren zur reduktion von farbstoffen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0426832A1 true EP0426832A1 (de) | 1991-05-15 |
EP0426832B1 EP0426832B1 (de) | 1994-05-04 |
Family
ID=3511548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90908918A Expired - Lifetime EP0426832B1 (de) | 1989-06-01 | 1990-05-31 | Verfahren zur reduktion von farbstoffen |
Country Status (6)
Country | Link |
---|---|
US (1) | US5244549A (de) |
EP (1) | EP0426832B1 (de) |
AT (1) | AT398316B (de) |
DE (1) | DE59005612D1 (de) |
ES (1) | ES2054358T3 (de) |
WO (1) | WO1990015182A1 (de) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992009740A1 (de) * | 1990-12-03 | 1992-06-11 | Verein Zur Förderung Der Forschung Und Entwicklung In Der Textilwirtschaft | Verfahren zur reduktion von textilfarbstoffen |
TW251325B (de) * | 1993-03-30 | 1995-07-11 | Basf Ag | |
DE19513839A1 (de) * | 1995-04-12 | 1996-10-17 | Basf Ag | Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen |
DE19723889A1 (de) | 1997-06-06 | 1998-12-10 | Consortium Elektrochem Ind | System zur elektrochemischen Delignifizierung ligninhaltiger Materialien sowie Verfahren zu seiner Anwendung |
AT408455B (de) * | 1997-09-04 | 2001-12-27 | Basf Ag | Verfahren zur reduktion von schwefelfarbstoffen |
DE59912528D1 (de) * | 1998-11-24 | 2005-10-13 | Walter Marte | Verfahren und apparatur zur reduktion von küpen- und schwefelfarbstoffen |
DE19919746A1 (de) * | 1999-04-29 | 2000-11-02 | Basf Ag | Verfahren zur Herstellung von wäßrig-alkalischen Lösungen reduzierter indigoider Farbstoffe |
DE19962155A1 (de) * | 1999-12-22 | 2001-06-28 | Basf Ag | Verfahren zur elektrochemischen Reduktion von Küpenfarbstoffen |
DE10010060A1 (de) * | 2000-03-02 | 2001-09-06 | Dystar Textilfarben Gmbh & Co | Mediatorsysteme auf Basis gemischter Metallkomplexe zur Reduktion von Farbstoffen |
DE10010059A1 (de) | 2000-03-02 | 2001-09-06 | Dystar Textilfarben Gmbh & Co | Mediatorsysteme auf Basis gemischter Metallkomplexe zur Reduktion von Farbstoffen |
DE10161265A1 (de) * | 2001-12-13 | 2003-06-26 | Dystar Textilfarben Gmbh & Co | Verfahren zur Farbveränderung von gefärbten textilen Substraten |
DE10234825A1 (de) * | 2002-07-31 | 2004-02-19 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Verfahren zum Färben mit Schwefel- und Schwefelküpenfarbstoffen |
EP1563137A1 (de) * | 2002-11-06 | 2005-08-17 | Tex-A-Tec Ag | Verfahren zur elektrochemischen reduktion von küpen- und schwefelfarbstoffen |
ES2222077B1 (es) * | 2002-12-23 | 2006-03-16 | Argelich, Termes Y Cia S.A. | Proceso de tintura con colorantes de tina y similares mediante reduccion electrolitica. |
HK1067926A2 (en) * | 2004-01-20 | 2005-03-24 | Hong Kong Productivity Council | An electrochemical dye reducing method. |
DE102004040601A1 (de) * | 2004-08-21 | 2006-03-02 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Neuartige flüssige Chinonimin-Schwefelfarbstoff-Zusammensetzungen sowie Verfahren zu ihrer Herstellung und ihre Verwendung zum Färben von cellulosehaltigem Material |
DE102005040469A1 (de) * | 2005-08-26 | 2007-03-01 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Farbstoffzubereitungen von indigoiden Farbstoffen, von Küpen- und Schwefelfarbstoffen enthaltend anorganische und/oder organische elektrochemisch aktive Mediatorsysteme sowie deren Verwendung |
EP1870494A1 (de) | 2006-06-23 | 2007-12-26 | ETH Zürich, ETH Transfer | Elektrochemischer Reaktor |
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CN102174731B (zh) * | 2011-03-04 | 2012-11-07 | 东华大学 | 一种电化学还原的染色装置 |
CN102154793A (zh) * | 2011-03-23 | 2011-08-17 | 东华大学 | 一种用于棉纱线电化学还原的染色装置 |
CN102433770A (zh) * | 2011-08-31 | 2012-05-02 | 常州耀春格瑞纺织品有限公司 | 还原染料电化学快速清洁染色工艺 |
BR112015004395A2 (pt) | 2012-08-30 | 2016-02-16 | Cargill Inc | agente redutor para corantes de enxofre, processo para fabricar o agente redutor, uso do agente, método para reduzir os corantes de enxofre e método para tingir tecidos |
CN108691116A (zh) * | 2018-05-24 | 2018-10-23 | 武汉纺织大学 | 一种导电纱线电化学还原染色装置及方法 |
EP3887575A1 (de) | 2018-11-30 | 2021-10-06 | Sedo Engineering SA | Leukofarbstoff (wie z. b. leukoindigo) als dispergierhilfsmittel |
CN113166954A (zh) | 2018-11-30 | 2021-07-23 | 赛杜工程股份有限公司 | 电化学反应器和它的清洁或再生 |
EP3887577B1 (de) | 2018-11-30 | 2022-12-07 | Sedo Engineering SA | Entfernung von nebenprodukten (verunreinigungen) |
CN113549938B (zh) * | 2021-06-17 | 2022-06-21 | 武汉纺织大学 | 一种回收废旧牛仔激光废灰中靛蓝的方法 |
CN113416967B (zh) * | 2021-06-17 | 2022-09-06 | 武汉纺织大学 | 一种回收废旧牛仔中靛蓝染料的方法和织物染色方法 |
WO2023161441A2 (en) | 2022-02-25 | 2023-08-31 | Laboratoire Biosthetique Kosmetik Gmbh & Co. Kg | Colorant composition comprising leucoindigo for coloring fibers and fabrics |
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DE534464C (de) * | 1928-06-21 | 1931-09-28 | Walter Haendel | Verfahren zum Faerben und Bemustern von Geweben, Wirkwaren, Geflechten, Leder und anderen Stoffen aus pflanzlichen und tierischen Fasern durch elektrolytische Zersetzung einer im Gut befindlichen Loesung |
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DE3065361D1 (en) * | 1979-07-02 | 1983-11-24 | Hoechst Ag | Two-phase printing process for the manufacture of conversion style and discharge resist articles |
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DK153412C (da) * | 1984-11-22 | 1988-12-19 | Ferring A S | Fremgangsmaade til fremstilling af p-aminophenoler ved elektrolyse |
-
1989
- 1989-06-01 AT AT0132989A patent/AT398316B/de not_active IP Right Cessation
-
1990
- 1990-05-31 EP EP90908918A patent/EP0426832B1/de not_active Expired - Lifetime
- 1990-05-31 DE DE59005612T patent/DE59005612D1/de not_active Expired - Lifetime
- 1990-05-31 WO PCT/AT1990/000052 patent/WO1990015182A1/de active IP Right Grant
- 1990-05-31 US US07/613,670 patent/US5244549A/en not_active Expired - Lifetime
- 1990-05-31 ES ES90908918T patent/ES2054358T3/es not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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See references of WO9015182A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE59005612D1 (de) | 1994-06-09 |
EP0426832B1 (de) | 1994-05-04 |
ATA132989A (de) | 1994-03-15 |
ES2054358T3 (es) | 1994-08-01 |
WO1990015182A1 (de) | 1990-12-13 |
AT398316B (de) | 1994-11-25 |
US5244549A (en) | 1993-09-14 |
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