CN105776676A - Water-based printing ink wastewater recycling method - Google Patents
Water-based printing ink wastewater recycling method Download PDFInfo
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- CN105776676A CN105776676A CN201410770232.5A CN201410770232A CN105776676A CN 105776676 A CN105776676 A CN 105776676A CN 201410770232 A CN201410770232 A CN 201410770232A CN 105776676 A CN105776676 A CN 105776676A
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Abstract
The invention discloses a water-based printing ink wastewater recycling method. According to the invention, water-based printing ink wastewater is processed through the following steps: (1) acid precipitation is carried out with oxalic acid, and filtering is carried out; and (2) electro-oxidation is carried out. After the process, wastewater COD is no higher than 500mg/L, chromaticity is no higher than 20, and pH value is 6-8. Therefore, recycling requirements are satisfied.
Description
Technical field
The method that disclosed herein is water color ink waste water recycling.Water color ink waste water through step (1) add oxalic acid Acid precipitation filter after, through step (2) electro-oxidation process, waste water COD not higher than 500mg/L, colourity not higher than 20, pH value 6 ~ 8, reach reuse requirement.The power consumption cost of water color ink waste water per ton is not higher than 60Kw.hr/KgCOD.
Background technology
In recent years, the volatilization of oil-based ink pollutes the environment, and in industries such as flexible printing, milk pack things, gets more and more and is replaced by water color ink.Water color ink is producing and in application process, due to the cleaning of equipment, can produce a number of printing ink wastewater.
Water color ink chroma in waste water is high, and content of organics is high, especially with organic band color substance be high molecular Organic substance, be difficult to biodegradation.
The processing method of water color ink waste water is divided into Physical, biochemical process and chemical method.The invention belongs to chemical method.
Physical generally processes water color ink waste water by the mode of membrane filtration, can add flocculant before filtration.CN2178558Y discloses a kind of high concentration printing ink wastewater membrane treatment appts, is made up of ultrafilter membrane group and other loop ultrafiltration equipment.CN203065281U discloses the device of another kind of embrane method treatment of printing ink wastewater, adds activated carbon, and is filtered with filter press.Physical filters the organic molecule that can not intercept in waste water completely, is not easy so clear water part is up to standard, additionally the dense water of the equal generating section of Physical, is difficult to process further.Pure physical method treatment of printing ink wastewater should be also few.
Biochemical process be in sewage disposal should a kind of method, cost is low, and treating capacity is big, also has application on printing ink wastewater processes.Organic substance difficult for biological degradation in printing ink wastewater, biodegradability is poor, and therefore biochemical process processes and generally to coordinate special pre-treating technology or use special strain in biodegradation process.CN834041A discloses a kind of interior raw electrolysis technique in conjunction with biochemical treatment printing ink wastewater.CN103159382A discloses a kind of two grades of A/O biochemical processing process, and its pre-treatment is very complicated, the technique such as including coagulation, flocculation, filter pressing, air supporting.CN103482822 discloses a kind of biochemical process, it is necessary to after dyeing waste water air-flotation process, carry out biochemical treatment together with sanitary sewage.CN103663882A discloses a kind of technique utilizing microbial augmentation MBR treatment of printing ink wastewater, it is characterised in that the preferred and collocation of strain.Biochemical process needs good operation stability, when water instability in toxicity, biodegradability, antibacterial in biochemistry pool needs the adjustment of a rapid lapse of time (generally no less than 1 month) to can be only achieved new stablizing, and printing ink wastewater is all unstable in COD, colourity and contained band color substance, bring difficulty to biochemical treatment.
Chemical Treatment water color ink waste water, generally refers to advanced oxidation processes, is namely CO with oxidant by the oxidation operation in waste water2And water, thus reduce COD and the colourity of waste water.The kind of advanced oxidation processes has Fenton oxidation, ozone oxidation, hypochlorous acid oxidization, electroxidation, light electrolysis, photochemical catalytic oxidation etc..CN20492403U discloses the device of a kind of ultraviolet catalytic oxidation treatment of printing ink wastewater.CN101863526A discloses similar method.CN1765762A discloses a kind of ultraviolet Fenton process, and ferrous sulfate adds hydrogen peroxide, simultaneously irradiation under ultraviolet ray, to strengthen the effect of Fenton process.CN103787551A discloses a kind of similar method, first Fenton oxidation, then treatment with ultraviolet light.CN1834041A discloses a kind of method of microelectrolysis processing printing ink wastewater, and namely by iron and carbon composition, the Organic substance in waste water is aoxidized by micro-electrolysis device.
No matter advanced oxidation processes is as a kind of independent method, or the pre-treatment as biochemical process, is all the prevailing technology for the treatment of of printing ink wastewater.Traditional Fenton process, adds ferrous sulfate and hydrogen peroxide, and after ferrous (ferrous iron) is converted into ferric ion, water can show faint yellow, it is necessary to adds alkali neutralization precipitation, and overall expenses is not low.Ultraviolet method is it is generally required to metal ion is as catalyst, and ultraviolet method limited efficiency, therefore usually needs to carry out treatment of printing ink wastewater in conjunction with additive method.Another kind of oxidizing process, iron-carbon micro-electrolysis, also there is obvious defect.Ferrum carbon constantly consumes in electrolytic process, and ferrum can be converted into iron ion and enter in water.The method of electroxidation treatment of printing ink wastewater of the present invention falls within the one of advanced oxidation processes.
Electroxidation method, also referred to as electrolysis, utilizes the effect of extra electric field, at anode by oxidation operation, i.e. direct oxidation, or male or female produce oxidant, oxidant by oxidation operation, i.e. indirect oxidation.Electroxidation is eco-friendly technology, has many good qualities: electron transfer is only between electrode and waste water component, it is not necessary to add metal ion as catalyst；Process is likely to produce free radical, without selectively oxidation and the pollutant reaction in waste water, seldom produces secondary pollution；Reaction condition is gentle, generally carries out at normal temperatures and pressures, and energy efficiency is high；Reactor apparatus small scale, takes up an area little, and device starts and closes down conveniently；Have air supporting, flocculation, bactericidal action concurrently.
The application in sewage disposal of the electroxidation method is more and more extensive, particularly the scale manufacture of insoluble anode (DSA) and application so that electroxidation device can long-period stable operation.Li Xiaomings etc. have studied electrolytic oxidation and process the technique (China's water supply and drainage, 2001,17(8) of refuse leachate: 14-17).Thesis for the doctorate " research of electrochemical oxidation process process difficult for biological degradation organic industrial sewage " the inner deep electroxidation of having inquired into of vast stretch of wooded country ripple processes the difficult mechanism of biological organism, efficiency etc..Patent CN10041233C discloses the process for the treatment of carbolic acid waste water by electrochemical oxidation.CN100500585C then discloses the method that electroxidation processes the waste water containing chlorobenzene compound.
201410498983.6 the technique disclosing a kind of electroxidation treatment of printing ink wastewater, making anode with DSA, it is with the obvious advantage, process technique is simple, and environmental friendliness does not increase new pollutant, and high treating effect, after process, COD is not higher than 100mg/L, and colourity is not higher than 100.Acid added by this technique is sulphuric acid or hydrochloric acid, after electroxidation processes, it is necessary to adds alkali and neutralizes, and meeting accumulation salt in water after neutralization cannot reuse.The acid that this method is added is oxalic acid, and oxalic acid is oxidized to CO in electro-oxidation process2And H2O, this oxidizing process speed is very fast, is typically in 20 minutes just completing, and the PH of waste water is become neutrality from acidity, and therefore without adding alkali, waste water is without accumulation salinity.After such method processes, it is possible to reach the requirement of reuse, rinse printing press as washings.
Summary of the invention
This patent relates to the reuse technology of water color ink waste water.
Printing-ink is most important printing material, is by printing graphical representation coloured material on stock.Color in ink derives from pigment.Pigment has a variety of, and after water-fast, fast light, heat-resisting, acidproof, alkaline-resisting, solvent resistant, film forming, the performance such as rub resistance, is therefore difficult to degraded.The present invention adopts in advanced oxidation processes a kind of, i.e. electro-oxidation processes carrys out treatment of printing ink wastewater.In multiple advanced oxidation processes, electroxidation possesses the highest oxidability, enough electric current densities and electroxidation time, it is possible to degraded by the Organic substance in waste water 100%, and various conventional advanced oxidation processes are compared by accompanying drawing 2.
Water color ink waste water through step (1) add oxalic acid Acid precipitation filter after, through step (2) electro-oxidation process, waste water COD not higher than 500mg/L, colourity not higher than 20, pH value 6 ~ 8, reach reuse requirement.The power consumption cost of water color ink waste water per ton is not higher than 60Kw.hr/KgCOD.
This technique is divided into two steps.The first step is pretreatment, namely adds oxalic acid precipitation and filters, amount is waste water the 0.01 ~ 0.5% of added oxalic acid, it is preferred to 0.05 ~ 0.15%.After acid adding, some larger molecular organics in major part printing ink wastewater can settle after meeting acid from water, the particularly printing ink wastewater of some high COD.After acid deposition is filtered, the COD of waste water can be down to below 2000mg/L, and the COD of some printing ink wastewater can be down to below 1000mg/L.Added acid is oxalic acid.Therefore control to be 2 ~ 6 by the pH value of waste water, it is preferred to 4 ~ 5.
Second step is that electroxidation processes.The essence of electroxidation is electrocatalytic oxidation, anode surface electrophilic, and strong oxidizing property produces active oxygen and free hydroxyl, and this oxidisability is even strong crosses ozone, and Organic substance in water is oxidized to little molecule, is further oxidized to CO2And H2O.When Different electrodes and different electroxidation, oxidation operation speed is different, and the oxidized speed of different oxide is different.Colored Organic substance containing conjugated double bond is easily by a type organic of electroxidation.
Added oxalic acid can be oxidized to CO by this step2And H2O.The PH of waste water can become neutrality, PH6 ~ 8. therefore can repeatedly reuse when, oxalic acid will not be accumulated.
Electro-oxidation processes, the potential difference at negative and positive the two poles of the earth controls at 0.2 ~ 10V, it is preferable that 1～3V.Potential difference is too low, electroxidation weak effect, it is necessary to time long；Potential difference is too high, and water is hydrogen and oxygen by electroxidation, and energy consumption increases, and electric current service efficiency is deteriorated.
In electro-oxidation processes, electric current density is relevant to electroxidation speed, controls at 100～10000A/m2, it is preferable that 500～3000A/m2.Electric current density is little, and electroxidation speed is slow；Electric current density is big, and anode life reduces, particularly when electric current density is more than 3000A/m2Time, anode life was lower than 3 years.
Electroxidation equipment is made up of one or more pairs of anodic-cathodics.Negative electrode belongs to protected electrode, general seldom damage.Anode belongs to key equipment, and its life-span determines the maintenance cost of electroxidation device.This patent anode has two kinds of one to be titanium substrate anode (DSA), and one is carbon cloth.Titanium substrate anode cost is expensive, but long service life, base material thickness 0.5～5mm, it is preferred to 1～2mm.Coating has four kinds, a kind of with iridium and tantalum for main material, and adds other a small amount of metals, such as platinum etc.；The second, with ruthenium and iridium for main material, can add other a small amount of metals, such as rhodium etc.；The third is with lead oxide for main material material；4th kind is diamond.Equations of The Second Kind anode is carbon cloth, and its cost is low, but service life is not long.This two classes anode is all effective.Negative electrode can adopt rustless steel or titanium material or graphite etc..
Electroxidation device is generally equipped with forced circulation pump.Mother liquid coming is forced flow between electrode, circulation, adds electroxidation effect.
Electro-oxidation process can add oxidant.In order to reach reuse standard, it is to avoid photosynthetic matter accumulation, the oxidant added is hydrogen peroxide.
Within the time of electroxidation is typically in 24 hours, the COD of waste water can reduce to below 500mg/L.Well matched 0.1 ~ the 2m of waste water one per ton2Anode, it is preferable that 0.5 ~ 1m2。
After two steps complete, the COD of waste water is not higher than 500mg/L, and colourity is not higher than 20, PH6 ~ 8, it is possible to reuse.
Accompanying drawing illustrates:
By reading the following drawings and description, inventive feature will be apparent from.
Accompanying drawing 1 is electroxidation treatment of printing ink wastewater process flow diagram.Water color ink waste water from printing house enters " filtering with Acid precipitation " link, and the acid of addition is oxalic acid, and the PH of waste water is modulated 4 ~ 5, is settled out part slag admittedly, is filtered out by solid slag in waste water.Gu slag is back to ink manufacturer or removes fixed-end forces.Gu the amount of slag is little, it is generally below the 1% of wastewater flow rate.The waste water COD filtered is generally below 2000mg/L, enters electroxidation link, and this link carries out in an electrolysis bath, logical unidirectional current, the time that processes less than 24 hours, chroma in waste water not higher than 20, COD not higher than 500mg/L, PH6 ~ 8, reuse.
Accompanying drawing 2 is the schematic diagram of electroxidation device.
Waste water 1L after filtering with Acid precipitation being put into electrolysis bath, inserts anode and negative electrode, area is 10*20cm, and DC source is powered to anode and negative electrode.Electro-oxidation process magnetic agitation.
Detailed description of the invention
The first step of the present invention adds oxalic acid, the anode of second step electroxidation step has four kinds, respectively titanio iridium tantalum electrode, titanio ruthenium iridium electrode, titanio lead dioxide electrode, titanio diamond electrode and carbon cloth, be respectively designated as A, B, C, D and E, and the time of electroxidation is 5 hours.
Wastewater source is in several typical ink waste water and their mixture.Electroxidation step in embodiment adopts the experimental provision of accompanying drawing 2.
Following table is the concrete condition of embodiment.
Claims (9)
1. the method that disclosed herein is water color ink waste water recycling；Water color ink waste water through step (1) add oxalic acid Acid precipitation filter after, through step (2) electro-oxidation process, waste water COD not higher than 500mg/L, colourity not higher than 20, pH value 6 ~ 8, reach reuse requirement.
2. electro-oxidation processes according to claim 1, it is characterised in that amount is waste water 0.01 ~ 0.5% of oxalic acid added by step (1), it is preferred to 0.05 ~ 0.15%.
3. electro-oxidation processes according to claim 1, it is characterised in that negative and positive the two poles of the earth potential difference of step (2) electroxidation is 0.2 ~ 10V, it is preferred to 1～3V.
4. electro-oxidation processes according to claim 1, it is characterised in that the electric current density of step (2) electroxidation is 100～10000A/m2, it is preferred to 500～3000A/m2。
5. electro-oxidation processes according to claim 1, it is characterised in that the base material of the anode of step (2) electroxidation device is titanium, coating main material is iridium and tantalum.
6. electro-oxidation processes according to claim 1, it is characterised in that the base material of the anode of step (2) electroxidation device is titanium, coating main material is ruthenium and iridium.
7. electro-oxidation processes according to claim 1, it is characterised in that the anode of step (2) electroxidation device is carbon cloth.
8. electro-oxidation processes according to claim 1, it is characterised in that the base material of the anode of step (2) electroxidation device is titanium, coating main material is lead oxide.
9. electro-oxidation processes according to claim 1, it is characterised in that the base material of the anode of step (2) electroxidation device is titanium, coating main material is diamond.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979517A (en) * | 2021-11-17 | 2022-01-28 | 辽宁大学 | Electrochemical device based on ruthenium-iridium electrode and method for advanced oxidation of anaerobic digestion solution |
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| US20020008013A1 (en) * | 1998-06-26 | 2002-01-24 | Akira Kuriyama | Method for treating colored liquid and apparatus for treating colored liquid |
| CN1834041A (en) * | 2006-03-30 | 2006-09-20 | 南京科环环境系统工程有限公司 | Aqueous ink wastewater treatment technique |
| CN103553899A (en) * | 2013-11-22 | 2014-02-05 | 昆山美淼环保科技有限公司 | Method for recovering fumaric acid from phthalic anhydride wastewater |
| CN104193051A (en) * | 2014-09-03 | 2014-12-10 | 苏州中亚油墨有限公司 | Deep purification treatment method for printing ink wastewater |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020008013A1 (en) * | 1998-06-26 | 2002-01-24 | Akira Kuriyama | Method for treating colored liquid and apparatus for treating colored liquid |
| CN1834041A (en) * | 2006-03-30 | 2006-09-20 | 南京科环环境系统工程有限公司 | Aqueous ink wastewater treatment technique |
| CN103553899A (en) * | 2013-11-22 | 2014-02-05 | 昆山美淼环保科技有限公司 | Method for recovering fumaric acid from phthalic anhydride wastewater |
| CN104193051A (en) * | 2014-09-03 | 2014-12-10 | 苏州中亚油墨有限公司 | Deep purification treatment method for printing ink wastewater |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979517A (en) * | 2021-11-17 | 2022-01-28 | 辽宁大学 | Electrochemical device based on ruthenium-iridium electrode and method for advanced oxidation of anaerobic digestion solution |
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