CN103708659B - Fur chromium-containing dyeing waste liquor electrochemical treatment and reusing method - Google Patents
Fur chromium-containing dyeing waste liquor electrochemical treatment and reusing method Download PDFInfo
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- CN103708659B CN103708659B CN201310711797.1A CN201310711797A CN103708659B CN 103708659 B CN103708659 B CN 103708659B CN 201310711797 A CN201310711797 A CN 201310711797A CN 103708659 B CN103708659 B CN 103708659B
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Abstract
The invention relates to a fur chromium-containing dyeing waste liquor electrochemical treatment and reusing method for fur dyeing, and belongs to the technical field of waste liquid treatment. The method comprises the following processes: (1) removing impurities of solid matters: filtering and removing the impurities of the solid matters in a chrome tanning waste liquid through a sieve screen; (2) carrying out electrochemical oxidation: introducing chromium-containing filtrate into an electrolysis reactor using graphite or a DSA (Dimension Stable Anode) electrode plated with rare metals as an anode and aluminum or the DSA electrode as a cathode for reaction according to the difference between chromaticity and CODCr (Chemical Oxygen Demand Cr) concentration of a dye in a waste liquid; and (3) reusing oxidation dyeing: supplying bichromate in water after electrolytic oxidation treatment according to the concentration of hexavalent chromium in water; and meanwhile, adding the desired chemicals according to a common chrome method and dyeing. With the adoption of the fur chromium-containing dyeing waste liquor electrochemical treatment and reusing method provided by the invention, chrome, salt and water in the dyeing waste water can be entirely reused without follow-up split-flow treatment; the method is an efficient and green water treatment process; the process is simple; and compared with the ordinary treatment process, the cost is greatly reduced, and the use rate of resources is improved.
Description
Technical field
The present invention relates to a kind of method that fur contains chromium dyeing waste liquid electrochemical treatment and cyclically utilizing, belong to technical field of waste water processing.
Background technology
In fur production process, chrome tanning agent is topmost tanning agent in tanning and retanning process, after chrome tanning, leather enters retanning dyeing process, now along with high temperature, acid dyeing condition, combine unstable chromium in fur and reenter waste water, make the chromium containing 50mg/L ~ 100mg/L in dyeing waste-water, contain each type organic such as a large amount of dyestuffs and auxiliary agent in this strand of waste water simultaneously, form the fur dyeing waste water containing low concentrations of chromium thus.Secondly, in fur oxidising dyeing technique, the red vanadium of usual employing carries out mordant dyeing, the chromic salt of 2 ~ 3g/L and a large amount of dyestuffs and dyeing auxiliary is added with in dye liquor, because product requirement is different, organic chemicals addition in dyeing water is different, can form the dyeing waste-water of higher concentration and colourity thus.In country using leather and leather products industry as before key industry implements Heavy Metal Pollution policy, fur dyeing water not as chromate waste water individual curing, but directly enters comprehensive wastewater and carries out second-stage treatment.
Because chromium belongs to first kind priority pollutants, national environmental standard requires must carry out shunting separately except chromium process, fur dyeing water because chromium content is wherein few and complexing degree is high, current usual method be by alkaline chemical precipitation after direct for this type of waste water alkaline chemical precipitation or reduction except after chromium again through biochemical treatment standard discharge.Chromium containing lower concentration in current fur dyeing waste water, general content is about 50mg/L ~ 100mg/L, and conventional alkaline precipitation is difficult to make the chromium in waste water reach the national standard of below 1.5mg/L, must be adsorbed it just can be made up to standard by dosing.Its chromium content of the chromium-bearing sludge formed thus only has 1%-3%, and the resource utilization rate after recovery is low, and the cost that enterprise disposes by dangerous solid waste place fortune is very high, causes the low difficult problem being treated as enterprise containing chromium dyeing waste-water.
Chrome retanned liquid in current fur manufacturing there has been ripe cyclically utilizing technology, and the dyeing water after retanning is because color is different, water quality is complicated, and its cyclically utilizing is lacked for a long time always can for the technology utilized.
Instant invention overcomes the shortcoming that existing chromate waste water treatment technology exists, achieve fur dyeing waste water circulation in dyeing process, no longer remove chromium, achieve the complete cyclically utilizing of salt in water, chromium and water simultaneously.The present invention adopts electrochemical catalytic oxidation technology can be directly used in the medium dyeing of fur in the liquid phase after direct oxidation chromium, this oxidation technology has efficient oxidative degradation ability to organism such as dyestuffs, and the trivalent chromium in waste water all can be oxidized to sexavalent chrome, " precipitate-dissolve again-be oxidized " technology compared with routine has the advantage of the following aspects: (1), without precipitation-dissolution process, decreases treatment scheme; (2) organism is degraded thoroughly, can not have an impact to the Color of the chromium in reuse liquid; (3) chromium, Yan Heshui can obtain reuse, and back segment need not enter biochemical system and process dyeing water.
Summary of the invention
The object of the present invention is to provide a kind of fur containing chromium dyeing waste liquid electrochemical treatment and the method for reuse, to overcome the shortcoming and defect of prior art, fur medium will be back to dye containing the process of chromium staining fluid.
To achieve these goals, technical scheme of the present invention is as follows.
Process hides contains a method for chromium dyeing waste liquid electrochemical treatment and reuse, specifically comprises following technical process:
(1) except solid substance impurity: cross the solid substance impurity filtered in chroming waste liquor.
(2) Classification of water Qualities: what step (1) obtained measures its COD containing chromium filtrate
crand colourity, what division COD was less than 1000mg/L is the low colourity waste water of lower concentration, COD
crwhat be greater than 1000mg/L is high-concentration and high-chromaticity waste water, enters different electrolyzer process respectively.
(3) electrochemical oxidation I: passing into graphite containing chromium filtrate of step (1) being obtained is anode, and iron or aluminium are in the electrolysis reactor of negative electrode, and arranging volts DS is 9 ~ 15V, and current density is 70 ~ 100A/m
2, polar plate spacing is 5 ~ 10cm, and pH value is 5.0, rapid stirring, reaction 20 ~ 40min.After reaction terminates, waste liquid is converted into bronze-colored completely, and trivalent chromium wherein 98% is converted into sexavalent chrome, and meanwhile, the complex compound be combined with trivalent chromium and organic molecule impurity can be removed, comprising organic acid salt and protein polypeptide, and COD
crclearance reach more than 90%.
(4) electrochemical oxidation II; High-concentration and high-chromaticity waste water is passed into negative electrode and anode all adopts in the electrolysis reactor of the DSA electrode being coated with rare metal, arranging volts DS is 10 ~ 15V, and current density is 80 ~ 200A/m
2, polar plate spacing is 3 ~ 5cm, and pH value is 5.0, rapid stirring, reaction 40 ~ 100min; After reaction terminates, waste liquid is converted into yellow completely, and trivalent chromium more than 98% is wherein converted into sexavalent chrome, meanwhile, and COD in waste water
crclearance reach more than 95%.
(5) dyeing reuse: test and adjust degree Beaume and pH, supplements material when other media dyes, for dyeing.After dyeing, waste liquid can again through said process process.
This beneficial effect of the invention is: the complete skill that the present invention proposes a whole set of fur dyeing water treatment and reuse, achieve the fully recovering to chromium, salt and water, do not produce chromium-bearing sludge simultaneously, back segment biochemical treatment need not be carried out again to fur dyeing water, be a kind of water technology of efficient green, and technique is simple, working cost precipitate than existing chromium mud, be oxidized after to restore the expense preparing chrome liquor low, without the need to strong acid, strong oxidizing property appointed condition, drug out loss is few.
Accompanying drawing explanation
Fig. 1 is process and recovering process flow figure in the embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described, better to understand the present invention.
Fig. 1 is process and recovering process flow figure in the embodiment of the present invention 1 and embodiment 2.
Example one:
(1) get a certain amount of fur dyeing waste liquid, adopt the filter screen of 0.01mm to be filtered by suspended substance, the total chrome content recorded in filtrate is 120mg/L, COD
crfor 680mg/L, colourity is 320 extension rates, pH value is 4.5.Under normal temperature condition, by filtrate 500mL, be placed in cubic capacity be 800mL multi-group electrode to form electrolysis reactor, its Anodic adopt Graphite Electrodes, negative electrode is aluminium electrode, arranges polar plate spacing 7cm, and voltage is 10V, and current density is 100A/m
2.Agitator is established in reactor, guarantee that in reaction process, water can homogenize as early as possible, 20min is reacted in electrolyzer, waste water Central Plains organism colourity is removed, raffinate is all converted into orange, use diphenyl carbazide spectrophotometry determination of hexavalent chromium, guarantee that in stoste, total chromium more than 98% is converted into sexavalent chrome, Simultaneously test COD
crconcentration, guarantees COD
crbe down to below 100mg/L, complete electrolysis.
(2) electrolytic solution is poured into medium dyeing paddle-tumble, degree Beaume after mensuration electrolysis in water, guarantee that salt concn is at 35 ~ 40g/L, measure pH value and remain on 5.0, measure chromium content, and supplementing red vanadium to 2.5g/L according to chromium content, other dyeing auxiliary Adding Way are identical with normal dyeing addition, and then dyeing performs routinely.
Example two:
(1) get a certain amount of fur to tan the dyeing waste liquid that is situated between, adopt the filter screen of 0.01mm to be filtered by suspended substance, the total chrome content recorded in filtrate is 1230mg/L, COD
crfor 3580mg/L, colourity is 560 extension rates, pH value is 5.2.Measure 1000mL chrome mordanting look waste liquid, fall in electrolyzer under corresponding pH, normal temperature condition, the negative electrode of electrolyzer and anode all adopt the DSA electrode being coated with rare metal, arrange polar plate spacing 3cm, and voltage is 15V, and current density is 200A/m
2, rapid stirring, reacts 100min in electrolyzer, and waste water Central Plains organism colourity is removed, and raffinate is all converted into orange, uses diphenyl carbazide spectrophotometry determination of hexavalent chromium, guarantees that in stoste, total chromium more than 98% is converted into sexavalent chrome, Simultaneously test COD
crconcentration, guarantees COD
crbe down to below 300mg/L, complete electrolysis.
(2) electrolytic solution is poured into medium dyeing paddle-tumble, degree Beaume after mensuration electrolysis in water, guarantee that salt concn is at 35 ~ 40g/L, measure pH value and remain on 5.0, measure chromium content, and it is identical with normal dyeing addition to other dyeing auxiliary Adding Way of 2.5g/L to supplement red vanadium according to chromium content, then dyeing performs routinely.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (3)
1. fur contains a method for chromium dyeing waste liquid electrochemical treatment and reuse, it is characterized in that: specifically comprise following technical process:
(1) solid substance impurity is removed: by the solid substance impurity in screen filtration removing chroming waste liquor;
(2) Classification of water Qualities: what step (1) obtained measures its COD containing chromium filtrate
crand colourity, divide COD
crwhat be less than 1000mg/L is the low colourity waste water of lower concentration, COD
crwhat be greater than 1000mg/L is high-concentration and high-chromaticity waste water, enters different electrolyzer process respectively;
(3) electrochemical oxidation I: passing into low for lower concentration colourity waste water with graphite is anode, aluminium is in the electrolysis reactor of negative electrode, sets volts DS, current density, polar plate spacing and pH value, rapid stirring, reaction 20 ~ 40min; After reaction terminates, waste liquid is converted into yellow completely, and trivalent chromium more than 98% is wherein converted into sexavalent chrome, and meanwhile, the complex compound be combined with trivalent chromium and organic molecule impurity can be removed, comprising organic acid salt and protein polypeptide, and COD
crclearance reach more than 90%;
(4) electrochemical oxidation II; High-concentration and high-chromaticity waste water is passed into negative electrode and anode all adopts in the electrolysis reactor of the DSA electrode being coated with rare metal, set volts DS, current density, polar plate spacing and pH value, rapid stirring, reaction 40 ~ 100min; After reaction terminates, waste liquid is converted into yellow completely, and trivalent chromium more than 98% is wherein converted into sexavalent chrome, meanwhile, and COD in waste water
crclearance reach more than 95%;
(5) dyeing reuse: test and adjust degree Beaume and pH, supplementing red vanadium, for dyeing; After dyeing, waste liquid can again through said process process.
2. a kind of fur according to claim 1 contains the method for chromium dyeing waste liquid electrochemical treatment and reuse, it is characterized in that: in described step (3), parameter set by electrolysis reactor is, volts DS is 9 ~ 15V, and current density is 70 ~ 100A/m
2, polar plate spacing is 5 ~ 10cm, and pH value is 5.0.
3. a kind of fur according to claim 1 contains the method for chromium dyeing waste liquid electrochemical treatment and reuse, it is characterized in that: in described step (4), parameter set by electrolysis reactor is, volts DS is 10 ~ 15V, and current density is 80 ~ 200A/m
2, polar plate spacing is 3 ~ 5cm, and pH value is 5.0, rapid stirring, reaction 40 ~ 100min.
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| CN201310711797.1A CN103708659B (en) | 2013-12-17 | 2013-12-17 | Fur chromium-containing dyeing waste liquor electrochemical treatment and reusing method |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104496109B (en) * | 2014-11-28 | 2016-04-06 | 陕西科技大学 | The device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby |
| CN104878547A (en) * | 2015-06-06 | 2015-09-02 | 华斯农业开发股份有限公司 | Device and process for recycling dyeing liquid of acid dye for fur |
| CN108797160A (en) * | 2018-06-20 | 2018-11-13 | 绍兴国周针织科技有限公司 | A kind of dyeing and printing process |
| CN112323304A (en) * | 2020-11-06 | 2021-02-05 | 江苏泰慕士针纺科技股份有限公司 | Zero-emission pretreatment process for cotton knitted fabric |
| CN114656027B (en) * | 2022-04-15 | 2023-06-13 | 嘉兴学院 | Recycling treatment method of chrome tanning waste liquid |
| CN115385483A (en) * | 2022-09-16 | 2022-11-25 | 嘉兴学院 | Environment-friendly treatment method for fur processing wastewater |
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| CN1749177A (en) * | 2005-07-07 | 2006-03-22 | 天津大学 | Electric biological processing device and method for waste water containing heavy metal ion and non-degradable organism |
| CN102010107A (en) * | 2010-12-24 | 2011-04-13 | 波鹰(厦门)科技有限公司 | Treatment and cyclic utilization device and method of tannery wastewater |
| WO2012062353A1 (en) * | 2010-11-09 | 2012-05-18 | Voith Patent Gmbh | Method for using waste water arising during the production of lignocellulosic fibrous materials |
| CN102718349A (en) * | 2012-06-25 | 2012-10-10 | 陕西科技大学 | Device and method for electrolytic treatment of acid organic wastewater with high salinity |
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|---|---|---|---|---|
| CN1749177A (en) * | 2005-07-07 | 2006-03-22 | 天津大学 | Electric biological processing device and method for waste water containing heavy metal ion and non-degradable organism |
| WO2012062353A1 (en) * | 2010-11-09 | 2012-05-18 | Voith Patent Gmbh | Method for using waste water arising during the production of lignocellulosic fibrous materials |
| CN102010107A (en) * | 2010-12-24 | 2011-04-13 | 波鹰(厦门)科技有限公司 | Treatment and cyclic utilization device and method of tannery wastewater |
| CN102718349A (en) * | 2012-06-25 | 2012-10-10 | 陕西科技大学 | Device and method for electrolytic treatment of acid organic wastewater with high salinity |
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