CN101381133B - Method for treating electrophoretic paint waste water - Google Patents
Method for treating electrophoretic paint waste water Download PDFInfo
- Publication number
- CN101381133B CN101381133B CN200710076988XA CN200710076988A CN101381133B CN 101381133 B CN101381133 B CN 101381133B CN 200710076988X A CN200710076988X A CN 200710076988XA CN 200710076988 A CN200710076988 A CN 200710076988A CN 101381133 B CN101381133 B CN 101381133B
- Authority
- CN
- China
- Prior art keywords
- waste water
- laccase
- electrophoretic paint
- handling
- paint waste
- 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.)
- Expired - Fee Related
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating electrophoretic paint waste water, which utilizes laccase as flocculant to process the electrophoretic paint waste water, wherein the laccase is a kind of copper-containing hydroquinone dioxygen redoxase, with a class number of EC 1.10.3.2. Water-soluble lacquer compositions in laccase catalytic wastewater are quickly polymerized to form deposit, so as to clarify the wastewater, thereby decolorizing and reducing the COD content of the wastewater; and the water-soluble electrophoretic paint is quickly polymerized through the laccase, so that the method is simple and highly-efficiency and reduces the cost, thereby effectively treating the electrophoretic paint waste water and protecting the environment.
Description
Technical field
The present invention relates to field of waste water treatment, especially about handling the method for electrophoretic paint waste water.
Background technology
Electrophoretic painting is an important technology field of metal finishing, is widely used in the application processing of body of a motor car bottom and the application of various automobile component, and electric parts, the application of toy and building material.At the used electrocoating paint of electrophoresis coating technique is water-soluble high-molecular material, mostly is resene coating greatly, epoxide resin, acrylic resin and the resol etc. of comprising commonly used.These water soluble paints often produce a large amount of waste water in coating process, its COD (chemical oxygen demand (COD)) may be up to 4, and more than the 000mg/l, its colourity may be up to more than 1,000 times.The discharging of these waste water all is subjected to the strict control of national governments, handles and could discharge after up to standard.Yet, all there is the big and too high problem of cost of technical difficulty for a long time in the improvement of electrophoretic paint waste water.Adopting more treatment process at present is chemical precipitation method and membrane ultrafiltration partition method.When adopting chemical precipitation method, often be used in combination other method, as biology aerobic, physical sedimentation, air supporting and filtration etc. form integrated conduct method.Though these methods are used in combination effectively, length consuming time is taken up an area of greatly, the loaded down with trivial details and expense height of technology.The membrane ultrafiltration partition method is the novel method of using this year, and this method can efficient recovery electrocoating paint and purified liquid waste, but investment is big, expense is high, so be difficult to large-scale promotion application.Other treatment process also has the exchange of semi-permeable membranes coupled ion.This adaptation of methods and reliability are not ideal.Biological process is used for the existing many successful examples of wastewater treatment.Biological process in the wastewater treatment generally be by living microorganism or certain plants to toxic substance, heavy metal or organism transform, thereby reach the purpose of purifying liquid waste.But the prior biological method is seldom independently used, and normally uses together in conjunction with other method, and the application of biology aerobic method in electrophoretic paint waste water is handled is exactly an example.Biological enzyme yet there are no report as an independent processing method in the electrophoretic paint waste water process field.Important member-laccase as polyphenoloxidase series is attempted in dyeing waste water and technological process for the treatment of papermaking, and shows its good prospects for application.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiencies in the prior art, provides a kind of simple efficient, the treatment process of the low electrophoretic paint waste water of cost.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method of handling electrophoretic paint waste water, and utilize laccase to handle electrophoretic paint waste water for flocculation agent.
Described laccase is a kind of copper bearing to diphenol dioxy oxydo-reductase, and classification number is EC1.10.3.2.
Described laccase is to make by bio-fermentation process.
The rapid polymerization of water soluble paint composition in the described laccase catalysis waste water and form precipitation makes the waste water clarification, thus decolouring and reduce the COD content of waste water.
Described laccase can be a crude enzyme liquid, also can be to solidify enzyme.
Described curing enzyme is to solidify by the sodium alginate parcel to form.
The consumption of crude enzyme liquid is 0.08% (w/v is 0.08 grams at 100 milliliters of useless subaqueous crude enzyme liquids promptly), the treatment time be half an hour or more than; The consumption that solidifies enzyme is 0.2% (w/v is 0.2 grams at 100 milliliters of useless subaqueous curing enzymes promptly), the treatment time be 1 hour or more than.
During processing, the pH value of waste water is: PH＞8.
Add gac when using laccase treatment waste water, the consumption of gac is 0.15% (w/v is 0.15 grams at 100 milliliters of useless subaqueous gacs promptly); Treatment time is: it is 5 minutes that crude enzyme liquid adds the activated carbon treatment time; Solidifying the enzyme interpolation activated carbon treatment time is 20 minutes.
A kind of method of handling electrophoretic paint waste water comprises the steps:
A). the preparation of laccase;
B). handle the waste water pH value and be adjusted into alkalescence;
C). utilize laccase and will handle waste water and leave standstill, and add gac;
D). reclaim laccase (be applicable to and solidify enzyme), recycle.
The invention has the beneficial effects as follows that wadding is poly-rapidly to make water miscible electrocoating paint by laccase, and is simple efficient, reduces cost, thereby handles electrophoretic paint waste water effectively, the protection environment.
Embodiment
A kind of method of handling electrophoretic paint waste water of embodiment of the present invention is to utilize laccase that water miscible electrocoating paint is wadded a quilt with cotton rapidly to gather, and is easy to the electrocoating paint that remains in the waste water is removed by simple precipitation or filtration.Most of electrocoating paints are resene coating, comprise epoxide resin, acrylic resin and resol etc.The waste water intractable that these water soluble paints produce in technology is used.The biological enzyme that is called laccase can make water miscible electrocoating paint, and wadding is poly-rapidly, is easy to the electrocoating paint that remains in the waste water is removed by simple precipitation or filtration.The laccase crude enzyme liquid that comes out by fungi fermentation (activity:＞1,200IU/ml) can be directly used in electrophoretic paint waste water and handle, under the condition of pH value＞8, minimum amount is that 800ppm handled 1 hour, it is nearly 98% to reduce its colourity, reduction COD nearly 50%.If making with the sodium alginate parcel, crude enzyme liquid solidifies enzyme (activity:＞1,500IU/g), 0.2% consumption is handled waste water under same pH value condition, can reduce its COD more than 75%, reduce colourity more than 90%, and can reuse more than ten times under the prerequisite that does not reduce effect.Add the effect of a spot of activated carbon (0.15%) as the remarkable enhancement process of sorbent material energy in laccase treatment, the COD clearance is reached more than 97%, chroma removal rate reaches 99.5%, far reaches national specified discharge standard.
A kind of method of handling electrophoretic paint waste water of the specific embodiment of the invention, the feature of this method is to be the flocculation catalyzer with the laccase, normal temperature condition and partially alkali condition (pH＞more than 8) handled waste water 0.5-1 hour down, water-soluble grey black electrocoating paint composition in the waste water produces poly-reaction of wadding rapidly and forms wadding polymers precipitation under the catalysis of laccase, just can be removed by clarification or filtration.Through laccase treatment and after filtering, the colourity of waste water reduces by 90%, and COD reduces more than 75%.
A kind of method of handling electrophoretic paint waste water of the specific embodiment of the invention, wherein used laccase is a kind of polyphenol oxidase reductase enzyme (EC 1.10.3.2), the principal character of its structure is to contain four metal copper ions in the zymoprotein structure, as the neccessary composition of catalytic active center.Laccase also has the function of catalysis macromolecular polymerization reaction, thereby can be used for synthesizing as resin one family macromolecule compound.Laccase is the water miscible electrocoating paint of energy catalysis under normal temperature condition, macromolecule mixture polymerization reaction take place in paint or the printing ink forms water-fast wadding polymers, therefore can pass through the effect of laccase with electrocoating paint residual in the waste water, paint or printing ink are removed, thereby reduce its COD and colourity.
A kind of method of handling electrophoretic paint waste water of the specific embodiment of the invention, wherein used laccase derives from fungi, belongs to the fungi of wood-decay fungi one class.This fungi can produce and secrete in extracellular laccase, therefore can make the crude enzyme liquid product by the deep layer liquid state fermentation of fungi.These product can be directly used in the processing of waste water.Also can the curing enzyme be made in its embedding, be handled waste water with solidifying enzyme again with sodium alginate.When handling electrocoating paint class waste water with crude enzyme liquid, laccase content is 1, and the crude enzyme liquid minimum amount of 200IU/ml (IU is an international enzyme unit alive) is 0.08% (w/v).The enzyme liquid and the waste water thorough mixing that earlier the pH value of waste water are transferred to during use more than 8 then dosage left standstill 1-3 hour again, and water miscible paint vehicle can be completed into precipitation, and the waste water of grey black is clarified immediately.Also can be before the natural sedimentation clarification by filtering clarification.If the employing filter method, handling the back only needs just can filter clarification half an hour.In specific embodiment 3, it is nearly 50% that the processing of crude enzyme liquid can make the COD of electrophoretic paint waste water reduce, and colourity reduces nearly 98% (seeing Table 1).When containing electrophoretic paint waste water with the processing of curing enzyme, laccase content is 1, and the curing enzyme minimum amount of 500IU/g is 0.2% (w/v) of wastewater flow rate, and usage is basic identical with crude enzyme liquid, but natural sedimentation clarification required time is much longer, needs more than 4 hours approximately.If the employing filter method then only need handle to filter in back 1 hour just to make the waste water clarification at enzyme.The curing enzyme made from sodium alginate parcel crude enzyme liquid is a particulate state, and diameter is about 0.5 millimeter under the dry condition, and suction back diameter is the 2-3 millimeter.Therefore can easily it be reclaimed from solid slag by 20 eye mesh screens.The curing enzyme that reclaims must any processing just can not be used for the processing of electrophoretic paint waste water once more, and can reuse more than ten times.With solidifying enzyme processing electrophoretic paint waste water the COD reduction of waste water is reached more than 75%, the colourity reduction reaches more than 90% and (sees Table 2).Aspect reduction COD index, solidify enzyme and obviously be better than crude enzyme liquid, but aspect decolouring, solidify enzyme not as crude enzyme liquid.Owing to solidify that enzyme can be repeatedly used thereby also more economical than crude enzyme liquid on use cost.
No matter handle electrophoretic paint waste water, as treatment agent, be crude enzyme liquid curing enzyme with laccase, though it is up to standard to decolour, but fails to make COD to reach the emission standard of country.In with laccase treatment, add the action effect that a spot of activated carbon can significantly strengthen laccase.Activated carbon is a kind of physical absorbent commonly used, is widely used in food, medicine and environmental protection industry (epi).Inoperative substantially with gac merely when handling electrophoretic paint waste water, but in laccase treatment, add gac, not only shorten the treatment time greatly but also total treatment effect is strengthened greatly.Concrete consumption and usage are: crude enzyme liquid 0.08%+0.15% gac, and, handled 5 minutes waste water ph＞8, filters clarification then; Or solidify enzyme 0.2%+0.15%, handle after 20 minutes with 20 eye mesh screen filtered and recycled curing enzyme waste water ph＞8, and then with filter cloth or filter paper filtering clarified wastewater.The curing enzyme that reclaims is repeatedly reusable.The processing that adds activated carbon through above laccase can reach following effect: colourity 370 times before handle are reduced to 2 times; COD before handle 1,600mg/l reduces to 50mg/l following (seeing Table 3).
Specific embodiment 1: the preparation of crude enzyme liquid: the laccase crude enzyme liquid is to prepare by bottle liquid fermenting approach that shakes that produces laccase bacterial strain RA20.The prescription of liquid nutrient medium is: glucose 1%, ammonium sulfate 0.25%, corn steep liquor 1%, methyl catechol 0.04%, dipotassium hydrogen phosphate 0.5%, sal epsom 0.02%, manganous sulfate 0.01% and copper sulfate 0.01%.In temperature is that 28 ℃ and rotating speed are to cultivate 910 days under 200 rev/mins the condition.By filtering the nutrient solution that obtains is required crude enzyme liquid just.Laccase activity detects by the ABTS method.
Specific embodiment 2: the sodium alginate laccase solidifies the preparation of enzyme: prepare 1 liter of concentration be 1.5% sodium alginate soln and place 80 ℃ of water-baths, adds 4 gram glutaraldehyde, stirred 2 hours, then adds 25 milliliters of crude enzyme liquids and continuation stirring 2 hours.Splash in 1% calcium chloride solution by the sodium alginate mixed solution that No. 5 syringe needles will wrap up laccase with peristaltic pump, the mixed solution that drips therein into solidify to form bead rapidly, after 30 minutes by filtering to isolate bead and, bead being rinsed well and drying for standby under 30 ℃ of conditions with physiological saline with its bubble in 0.2% glutaraldehyde solution 2 hours.
Specific embodiment 3: handle electrophoretic paint waste water: in 52 liters of beakers, add 1 liter of electrophoretic paint waste water respectively with crude enzyme liquid, adding 0.8 gram, 1.5 grams, 2.0 grams, 2.5 grams, 3.0 gram enzyme work then respectively is 1, the laccase crude enzyme liquid of 200IU/ml: make its consumption reach 0.08%, 0.15%, 0.2%, 0.25%, 0.3% (w/v).It leaves standstill half an hour to stir 1 minute relief.With filter flask it is filtered, to filtrate sampling and detect its COD and colourity respectively.The results are shown in Table 1.
Specific embodiment 4: handle electrophoretic paint waste water with solidifying enzyme: in 52 liters of beakers, add 1 liter of electrophoretic paint waste water respectively, adding 1 gram, 2 grams, 3 grams, 4 grams, 5 gram enzyme work then respectively is 1, the laccase of 500IU/g-sodium alginate solidifies enzyme, makes its consumption reach 0.1%, 0.2%, 0.3%, 0.4%, 0.5% (w/v).It left standstill 3 hours to stir 1 minute relief.With filter flask it is filtered, to filtrate sampling and detect its COD and colourity respectively.The results are shown in Table 2.
Specific embodiment 5: add the activated carbon treatment electrophoretic paint waste water with laccase: experiment divides 5 treatment group:
1) .0.08% crude enzyme liquid+0.15% gac; 2) .0.08% crude enzyme liquid+0.3% gac;
3) .0.2% solidifies enzyme+0.15% gac; 4) .0.2% solidifies enzyme+0.3% gac.Every group of wastewater treatment capacity is 1 liter, ph value＞8, the treatment time: 1), 2) group be 5 minutes, 3), 4) group be 20 minutes.With filter flask it is filtered, to filtrate sampling and detect its COD and colourity respectively.The results are shown in Table 3.
Table 1 crude enzyme liquid is handled the variation of back swimming paint waste water COD content and colourity
Table 2 solidifies the variation that enzyme is handled back swimming paint waste water COD content and colourity
Table 3 laccase adds the variation of swimming paint waste water COD content and colourity after the activated carbon treatment
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Preservation information:
Laccase was Split-gill (Schizophyllum commune), and bacterial strain called after CA20 was preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center (being called for short CGMCC) on 08 17th, 2006, and preserving number is CGMCC № 1781.
Claims (9)
1. method of handling electrophoretic paint waste water, it is characterized in that: utilize laccase to handle electrophoretic paint waste water for flocculation agent, the pH value of waste water is during processing: pH＞8.
2. according to the described a kind of method of handling electrophoretic paint waste water of claim 1, it is characterized in that: described laccase is a kind of copper bearing to diphenol dioxy oxydo-reductase, and classification number is EC1.10.3.2.
3. a kind of method of handling electrophoretic paint waste water according to claim 2, it is characterized in that: described laccase is to make by bio-fermentation process.
4. according to any described a kind of method of handling electrophoretic paint waste water among the claim 1-3, it is characterized in that: the rapid polymerization of water soluble paint composition in the described laccase catalysis waste water and form precipitation, make the waste water clarification, thus the chemical oxygen demand (COD) content of decolouring and reduction waste water.
5. a kind of method of handling electrophoretic paint waste water according to claim 4, it is characterized in that: described laccase is a crude enzyme liquid, or solidifies enzyme.
6. a kind of method of handling electrophoretic paint waste water according to claim 5 is characterized in that: described curing enzyme is to solidify by the sodium alginate parcel to form.
7. a kind of method of handling electrophoretic paint waste water according to claim 5 is characterized in that: the consumption of crude enzyme liquid is 0.08%, and the treatment time is more than half an hour; The consumption that solidifies enzyme is 0.2%, and the treatment time is more than 1 hour.
8. a kind of method of handling electrophoretic paint waste water according to claim 1 is characterized in that: add gac when using laccase treatment waste water, the consumption of gac is 0.15%; Treatment time is: it is 5 minutes that crude enzyme liquid adds the activated carbon treatment time; Solidifying the enzyme interpolation activated carbon treatment time is 20 minutes.
9. a method of handling electrophoretic paint waste water is characterized in that: comprise the steps:
A). the preparation of laccase;
B). handle waste water ph and be adjusted into alkalescence;
C). utilize laccase and will handle waste water and leave standstill, and add gac;
D). reclaim laccase, described laccase recycles for solidifying enzyme.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710076988XA CN101381133B (en) | 2007-09-07 | 2007-09-07 | Method for treating electrophoretic paint waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710076988XA CN101381133B (en) | 2007-09-07 | 2007-09-07 | Method for treating electrophoretic paint waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381133A CN101381133A (en) | 2009-03-11 |
| CN101381133B true CN101381133B (en) | 2010-10-13 |
Family
ID=40461218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710076988XA Expired - Fee Related CN101381133B (en) | 2007-09-07 | 2007-09-07 | Method for treating electrophoretic paint waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101381133B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638253B (en) * | 2009-09-08 | 2011-03-30 | 北京师范大学 | Method for treating waste water polluted by composite chlorophenol with coordination of visible light-laccase |
| CN102115264B (en) * | 2010-12-15 | 2013-01-02 | 陕西科技大学 | Technological method for deeply treating papermaking wastewater by biological enzyme |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023165A (en) * | 2004-09-21 | 2007-08-22 | 生化酶股份有限公司 | Novel laccase enzyme and use thereof |
-
2007
- 2007-09-07 CN CN200710076988XA patent/CN101381133B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023165A (en) * | 2004-09-21 | 2007-08-22 | 生化酶股份有限公司 | Novel laccase enzyme and use thereof |
Non-Patent Citations (6)
| Title |
|---|
| JP特开2000-64185A 2000.02.29 |
| JP特开2004-41124A 2004.02.12 |
| 张爱萍等.漆酶在制浆造纸中的应用研究进展.中国造纸学报19 2.2004,19(2),161-165. |
| 张爱萍等.漆酶在制浆造纸中的应用研究进展.中国造纸学报19 2.2004,19(2),161-165. * |
| 苏振华.酶在制浆造纸废水处理中的应用.上海造纸36 2.2005,36(2),47-50. |
| 苏振华.酶在制浆造纸废水处理中的应用.上海造纸36 2.2005,36(2),47-50. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101381133A (en) | 2009-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102976552B (en) | Method for deep treatment on difficultly-degraded organic nitrogen-containing industrial wastewater | |
| CN206580707U (en) | A kind of coking chemical waste water total system | |
| CN114272897B (en) | Magnetic biochar adsorbent based on Qiya seed gum and preparation method | |
| CN101381133B (en) | Method for treating electrophoretic paint waste water | |
| CN107473546A (en) | A kind of special repair materials of mercury and its preparation technology | |
| CN101746919A (en) | Method for processing waste water of biological pharmacy | |
| CN102417224B (en) | Biological flocculation and inorganic flocculation complexing agent and application thereof | |
| CN102531251A (en) | Wastewater treatment method for potato product processing | |
| CN102633405B (en) | Treatment method of papermaking black liquor | |
| CN107337249A (en) | A kind of adsorption treatment method of heavy metal ion-containing waste water | |
| CN111559813A (en) | Micro-electrolysis photo-Fenton treatment process for papermaking industrial wastewater | |
| CN208234725U (en) | System for handling dyeing wastewater | |
| CN206538316U (en) | A kind of combined type printing and dyeing wastewater treatment system | |
| CN115872572A (en) | Method for treating cleaning degumming wastewater and redundant slicing wastewater | |
| CN107164425A (en) | A kind of preparation method of flocculation decoloration dyeing waste water bacteria cellulose based composites | |
| CN111499103B (en) | Alcohol wastewater recycling system based on membrane technology | |
| CN108083450A (en) | A kind of RE waste water complexing agent | |
| CN107324589A (en) | A kind of processing method of sanitary sewage | |
| CN207405027U (en) | A kind of pharmaceutical wastewater processing system | |
| CN102826721A (en) | Method for treating wastewater being generated during vitamin C production | |
| CN111559833A (en) | Method for treating pulping wastewater by using enzyme membrane reactor | |
| CN208071537U (en) | A kind of lithium battery Wastewater zero-discharge treatment system | |
| CN106277365A (en) | A kind of Powdered Activated Carbon preparation method of granules with biodegradation and denitrification functions | |
| CN112456663A (en) | Method for treating antibiotics in livestock and poultry breeding sewage | |
| JPH09187774A (en) | Method for processing high concentration distillation waste liquid accompanied with producing alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: MO SIYUAN Owner name: HE SUXIA Free format text: FORMER OWNER: BIO SCIENTIFIC (SHENZHEN) LIMITED Effective date: 20110609 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518000 YONGXING BUILDING, NO. 222, BAOSHI EAST ROAD, SHUITIAN VILLAGE, SHIYAN TOWN, SHENZHEN CITY, GUANGDONG PROVINCE TO: 523000 13A, TOWER D, CUIJINGXUAN, FUMIN GARDEN, HUMEN TOWN, DONGGUAN CITY, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110609 Address after: 523000 Guangdong province Dongguan city Humen town gate Fumin garden Cui Jingxuan block D 13A Co-patentee after: Mo Siyuan Patentee after: He Suxia Address before: 518000 Yongxing building, 222 precious stone road east, Shiyan Town, Shiyan City, Guangdong, Shenzhen Patentee before: Bio Scientific (Shenzhen) Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101013 Termination date: 20170907 |