CN1116448C - Method for treating waste liquor from final water washing tank used in cation electrodeposition painting - Google Patents
Method for treating waste liquor from final water washing tank used in cation electrodeposition painting Download PDFInfo
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- CN1116448C CN1116448C CN95190856A CN95190856A CN1116448C CN 1116448 C CN1116448 C CN 1116448C CN 95190856 A CN95190856 A CN 95190856A CN 95190856 A CN95190856 A CN 95190856A CN 1116448 C CN1116448 C CN 1116448C
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- water washing
- washing tank
- tank used
- final water
- filtrate
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- 238000005406 washing Methods 0.000 title claims abstract description 148
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002699 waste material Substances 0.000 title claims abstract description 62
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001768 cations Chemical class 0.000 title claims abstract description 18
- 238000010422 painting Methods 0.000 title claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002562 thickening agent Substances 0.000 claims description 30
- 238000000108 ultra-filtration Methods 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 27
- 238000005516 engineering process Methods 0.000 claims description 15
- 239000008199 coating composition Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 230000004087 circulation Effects 0.000 claims description 11
- 238000001223 reverse osmosis Methods 0.000 claims description 11
- 238000011010 flushing procedure Methods 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 240000004859 Gamochaeta purpurea Species 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241000294743 Gamochaeta Species 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000008676 import Effects 0.000 description 2
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- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- -1 sulfuric acid ester Chemical class 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
- C25D13/24—Regeneration of process liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
- B01D61/146—Ultrafiltration comprising multiple ultrafiltration steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/22—Controlling or regulating
Abstract
This invention aims at providing a method of treating a waste liquor from a final water washing tank used in the cation electrodeposition painting, which method is capable of reutilizing the waste liquor as final water washing water by recovering the waste liquor without discarding the same. A method of treating a waste liquor from a final water washing tank, characterized by the steps of separating the waste liquor, which is discharged from the final water washing tank, into a raw painting material-containing condensed liquid and a filtrate by using a semi-permeable membrane while maintaining the waste liquor pH not higher than 6.4 at all times in a condensation tank, returning the whole or a part of the filtrate to the final water washing tank, and reusing this filtrate as final water washing cleaning water.
Description
Technical field
The present invention relates to the treatment process of waste liquor from final water washing tank used in the cation electrodeposition painting.
Background technology
Features such as electro-deposition coating is easy because of its management, economy are used widely, and technical progress is also very remarkable.Wherein, it is just more through 15 years to turn to cation electrodeposition coating to amount to from the negatively charged ion electrocoating paint, and especially at automotive field, almost 100% all use cation electrodeposition coating today.Cation electrodeposition painting is not limited to automotive field, is also entering wide spectrums such as building materials, common metal goods, motor product, industrial machinery.
Cause so being suitable for the background of the painted cation electrodeposition painting development of automobile etc., be the cation electrodeposition coating of ultrafiltration (UF) excellent exploitation, be applicable to cation electrodeposition painting ultra-filtration membrane exploitation and with the exploitation of these ultrafiltration systems that made up.
In that some develop in consequent cation electrodeposition painting systems like this, after making the coated article galvanic deposit, be provided with washing process.That is, the not dry coating of coated article galvanic deposit in galvanic deposition cell is finished application by dry baking in drying oven, but is attached with coating in the groove, electronegative to ion etc. filming of mentioning from galvanic deposition cell.If be dried-toast like this, then can be referred to as to overhang, flow, the bad phenomenon in the processing such as line circle, pit.For avoiding this situation to take place, general electro-deposition coating system all is through washing process drying-baking again after galvanic deposit.
Washing process after the galvanic deposit is divided into and filters, allows the recovery liquid that contains coating composition return galvanic deposition cell and filtrate returned as washing water and the loop line water washing technology of cycling and reutilization and be further used as operation thereafter and second operation of the final washing process that is provided with in addition respectively containing a fairly large number of scrub raffinate of galvanic deposit tank liquor or coating.The former washs coated article with the filtrate of coating uf processing in the galvanic deposition cell, thereby can reclaim washing to the coating composition that adheres on the coated article.The latter is epochmaking technology for carrying out degree of depth washing, and its present situation is to carry out fine purifiation with water such as pure water, process water, tap water, cleans rare coating composition that the former fails to wash off or to ion etc., it is washed outside waste liquid discharge system.
Yet the water yield that this final washing needs is very big, and also contains a small amount of coating or foreign ion in this washing waste liquid, does not allow to be discharged to the outside, no matter from environmental still from economic angle, all need finally to wash the special treatment technology of waste liquid.
But, contain organic acid or dissolution aids hardly in this final washing process waste liquid, owing to be water nearly all, thereby be in the state that contained a small amount of coating composition is separated out easily.Therefore, this washes can utilize with the film processing is refining again, but owing to problems such as aggegation, obstruction fenestra can take place in membrane treatment appts are difficult to carry out, can't practicability.
Final washing process waste liquid is discarded and technology that utilize has again been opened in the flat 7-207495 communique open the spy.This communique is disclosed to be, is relying in the washing process of pure water as final washing process, and the ultrafiltrate that the ultrafiltration of washing water is obtained uses as final washing water.But both do not mentioned the uf processing condition in this communique, particularly proceeded the strategy of ultrafiltration long-term and stably, and do not put down in writing pH yet and adjust and to realize that ultrafiltration is stable.
Disclosure of the Invention
The present invention is intended at aforesaid liquid waste disposal difficulty, make the waste liquid of final washing process that aggegation not take place in membrane treatment appts, stop up fenestra and can handle, remaining coating residue concentrates and reaches and be easy in the depleted state in making waste liquid, a large amount of washess are made with extra care, reach the state that washing water utilize again that can be used as, make it to become not externally drained closed system, but the technology that it can be refined to hull-borne perhaps is provided.
The present invention relates to the treatment process of waste liquor from final water washing tank used, it is characterized in that, in the treatment process of the final water washing tank used effluent discharge of cation electrodeposition painting technology, make the pH of waste liquid in the thickener 6 often remain on below 6.4, by this waste liquid is circulated, it is separated into concentrated solution and the filtrate that contains coating composition in the filtration unit 9 that has been equipped with semi-permeable membranes.
The such term of final water washing tank used or final washing process in this specification sheets, mean with electro-deposition coating technology in the final finishing that independently is provided with of the general so-called loop line that constitutes by galvanic deposition cell and rinse bath of adopting wash in the washing bath or the washing process of use.
The invention is characterized in and separate the filtrate obtain by semi-permeable membranes all or part of returns final water washing tank used.
Feature of the present invention is that also the degree of enrichment of concentrated solution in the thickener of above-mentioned circulation waste liquid reaches the highest 200 times stage concentrated solution is extracted out from thickener.
Another aspect of the present invention relates to the treatment process of waste liquor from final water washing tank used, it is characterized in that, the waste liquid of the final water washing tank used discharge of cation electrodeposition painting technology by the filtration unit that has been equipped with semi-permeable membranes in circulation be separated in the waste liquor from final water washing tank used processing of the concentrated solution that contains coating composition and filtrate, semi-permeable membranes is with having added 300～3, the back flushing of 000ppm organic acid filtrate often remains on below 6.4 the pH of concentrated solution in the thickener.
In cation electrodeposition painting technology, the pH of water normally about 6.0～7.0 in the final washing process.The coating content of taking out of is to contain about 0.05～0.2% (weight) in the water after washing, and pH rises to about 6.5～7.0.If with regard to this appearance it is sent in the membrane treatment appts, then coating particles can be separated out on filtering membrane usually in aggegation.The present invention is for preventing this from occurring, and the pH regulator of water in the thickener 6 sent into to common below 6.4, better below 6.0,4.5～6.0 the state of being more preferably again be equipped with semi-permeable membranes, especially in the filtration unit 9 of ultra-filtration membrane.So just simply the pH of scrub raffinate is adjusted to below 6.4, though the coating in the waste liquid in membrane treatment appts pressure or shearing condition under also can stably exist, can not occur in aggegation in the device, stop up phenomenon such as fenestra.Carry out film like this and handle the concentrated solution obtain and can make it to concentrate, can be concentrated to about about 400 times of volumetric ratio, aggegation can not take place this moment, stop up trouble such as fenestra via the continuous circulation of symphysis.
And filtrate can all reclaim, return final water washing tank used cycling and reutilization as final washing water, therefore, can reach scrub raffinate and not discharge outside, loop line in fact completely.In addition, this filtrate also can be discharged outside with its all or part of and needn't worry meeting initial ring environment pollution.When this filtrate is used as the part of final washing water, surprisingly, stain even use the so-called pit of the fine pimple that also can on coated article, not form coating like this and to film.
On the other hand, in the filtration unit 9 that has been equipped with semi-permeable membranes, handle spissated circulation concentrated solution, other solid substance constituent concentration except that coating composition also can improve gradually, and the degree of enrichment of concentrated solution reaches the highest 200 times stage and will extract out from thickener in thickener.The concentrated solution quantity of extracting out is few, can further concentrate if necessary, thereby can carry out burning disposal safely.If as kept solution-stabilizedly, then also can return galvanic deposition cell, more favourable economically.
Above-mentioned degree of enrichment means with the start of run state to be the velocity of variation of benchmark, can compare etc. with volumetric ratio, non-volatile matter concentration ratio, electric conductivity substances content and represent, represents with volumetric ratio in this specification sheets.Volumetric ratio is defined as the ratio of sending into remaining concentrated solution volume in the waste liquid cumulative volume handled in the thickener and the thickener.
PH during the running beginning in the thickener adjusts very difficult, thereby will accumulate a certain amount of washing waste liquid in thickener, at the start of run that begins until the circulation by filtration unit, adjust to the pH of liquid in the thickener below 6.0 better 4.5～5.5.
For the filtration yield that makes the filtration unit that has been equipped with semi-permeable membranes keeps stable, also can carry out back flushing (back washing) to filtration unit with acid.Back flushing is with having added 300～3, and the organic acid filtrate about 000ppm is regularly carried out, and the pH in the thickener can be kept usually below 6.4.
Final water washing tank used both can be single groove, also can be the multi-stage type of 2～3 groove tandems configuration.Under the situation of multi-stage type, washing water better are opposite with the trend of coated article, and promptly washing water are from the countercurrent washing of last concentrated flow to first groove.In this case, the washing waste liquid is discharged from first groove, and the filtrate of coming out from filtration unit both can be used for directly washing coated article at last final water washing tank used groove, also can turn back in last final water washing tank used groove.
Semi-permeable membranes is reverse osmosis (RO) film, ultrafiltration (UF) film, secondary filter (MF) film etc., but is carrying out waste liquid ultra-filtration membrane preferably when filtering.Reverse osmosis membrane removes the ability excellence of coating composition, but the processing power of time per unit is little, and economy is bad.Otherwise, film such as secondary filter film that the above aperture of ultrafiltration is arranged, its film processing power excellence but coating composition enters in the filtrate in a large number, can't reach the required draining water quality standard of draining, washing effect was poor when filtrate was utilized as final washing water again, the so-called pit of the fine pimple that forms coating on coated article is arranged and stains the problem of filming.The composition of ultra-filtration membrane from processing power and filtrate is out of question during practical application in general.Ultra-filtration membrane can be a molecular weight ranges 3,000～1, about 000,000, and be the film of material with any materials such as polyacrylonitrile, polystyrene, polyolefine and chemical modification things thereof.The suitability of material, molecular weight ranges etc. is different because of the situation of processed liquid, thereby better studies in advance, selects.
More approached at needs also can carry out reverse-osmosis treated such shown among the figure 10 to the filtrate of uf processing again under the situation of filtrate of pure water.Like this, can obtain the lower water of BOD.
The final water washing tank used pH that discharges waste water is about 6.5～7 as mentioned above in the cation electrodeposition painting, therefore, with acid the pH of thickener is adjusted to below 6.4 among the present invention.The acid that is suitable for is organic acid, for example carboxylic-acid, sulfonic acid class, sulfuric acid ester, phosphoric acid ester, phenol etc., but good especially be the water-soluble carboxyl acids.Specifically, can enumerate formic acid, acetate, propionic acid, butyric acid, lactic acid, citric acid, toxilic acid, fumaric acid, oxalic acid, oxysuccinic acid, tartrate, oxaloacetic acid, propanedioic acid, nitrilotriacetic acid(NTA), phthalic acid, trimellitic acid, and mineral acid such as thionamic acid, carbonic acid etc.Good especially is formic acid, acetate, lactic acid etc.Also can use the electrode solution of discharging from diaphragm apparatus.That is to say that diaphragm apparatus is by being located at the ion-exchange film device in the galvanic deposition cell, will discharge outside the galvanic deposition cell as anolyte that this can be used to adjust pH by the negatively charged ion such as acid in the galvanic deposit free coating.
Waste liquor from final water washing tank used of the present invention is provided with suitable prefilter and does not also have any obstruction in handling before semi-permeable membranes.
In order to make above-mentioned explanation be easier to understand, below the present invention is described with reference to Fig. 1.
In cation electrodeposition painting, the coated article 18 that hangs on conveyer 17 moves continuously, at first enters galvanic deposition cell 1.Coated article 18 behind this electro-deposition coating reclaims the washing processing line along three grades of the ultrafiltrates of being made up of first washing bath 2, second washing bath 3 and the 3rd washing bath 4 subsequently and moves successively.Reclaim in the washing process at ultrafiltrate, the feed liquid that is coated with of galvanic deposition cell 1 enters from the 3rd washing bath 4 through the filtrate that ultra-filtration equipment 8 filtrations obtain, flow to second washing bath 3, first washing bath 2 along direction with the coated article adverse current, be back to galvanic deposition cell again, carrying out not by the recovery of electrocoating paint in the coated article with washing.In each washing bath, all be that the spray quinoline coated article of the washing lotion in its groove is circulated, superfluous washing lotion overflow is delivered in its previous stage washing bath.
Leave the coated article of the 3rd washing bath 4 and further use washings such as pure water, service water, tap water, deliver to drying, baking process then final water washing tank used 5.
The present invention is the final washing process at above general japanning one washing process, final water washing tank used 5 implements at it.For the purpose of understanding, below describe this washing bath 5 is discharged
*Waste water carry out the technology that film is handled.At this in final water washing tank used 5, owing to brought coating composition into from previous process with coated article 18, hetero-ion etc., the washing water in the groove 5 are contaminated.Contaminated washings can not continue to use as final washing water, can not discard like this, and thickener 6 is delivered in its extraction, separates in the following manner and removes tramp material.The scrub raffinate of extracting out from thickener 6 adds acid, and pH is adjusted to through being everlasting below 6.4, delivers to membrane treatment appts 9 then and handles.Concentrated solution can be concentrated to about about 400 times of volume ratio further by membrane treatment appts 9 circulations.Filtrate collection in filtrate receiver 7, its all or part of can return such as washing bath 5, or directly utilize again as coated article spray quinoline liquid.In addition, the filtrate that enters filtrate receiver 7 also can further be filtered then utilization again by reverse-osmosis treated device 10 again.On the other hand, the concentrated solution that is produced by membrane treatment appts 9 also can be as above being described in detail, and the degree of enrichment of concentrated solution reaches the highest 200 times stage and extracts out from thickener in thickener.
The waste liquor from final water washing tank used treatment process of Fig. 2 explanation under final water washing tank used situation about forming by multiple-grooved (as an example, having drawn three-flute among the figure).The coated article of electro-deposition coating, washing at first enters this first final water washing tank used groove in the technology in front.Coated article after this washing enters second groove, three-flute subsequently successively, and washing water are carried to first groove from last groove along countercurrent direction on the other hand.The filtrate of coming out from membrane treatment appts 9 or 10 enters three-flute (Fig. 2 24) and (or is directly entering three-flute behind the washing coated article, the scrub raffinate of overflow enters second groove (Fig. 2 23) behind the coated article that repeated washing is sent here from second groove, the coated article of sending here from first groove (Fig. 2 22) at this same repeated washing.Like this, the waste liquid of each groove all overflows in separately the previous groove, and the waste liquid that initial groove (Fig. 2 22) is discharged imports in the thickener, via filtration unit, makes at least a portion of filtrate return last final water washing tank used groove.
Filtrate after film is handled among Fig. 2 is returned last final water washing tank used groove (24 among Fig. 2), but under the situation of finally washing with pure water, filtrate also can not returned last groove, but returns groove in its front (for example 22 of Fig. 2,23), imports the pure water washing on three-flute.
The accompanying drawing simple declaration
Fig. 1 is the schema of waste liquor from final water washing tank used treatment scheme in the explanation electro-deposition coating technology.
Fig. 2 is to use multistage (is example with the three-flute situation) final water washing tank used final washing liquid waste disposal schema.
The implication of code name is as follows among the figure:
1. galvanic deposition cell; 2. first washing bath; 3. second washing bath; 4. the 3rd washing bath; 5. final water washing tank used; 6. thickener; 7. filtrate receiver; 8. ultra-filtration equipment; 9. be equipped with the filtration unit of semi-permeable membranes; 10. reverse osmosis unit; 11,12,13,14,15,16 represent pump; 17. conveyer; 18. coated article; 19. washing spray equipment; 20. concentrated solution; 21. filtrate; 22. final water washing tank used first groove; 23. final water washing tank used second groove; 24. final water washing tank used three-flute.
The invention example
Below with embodiment the present invention is described.
In following examples, the nonvolatile component in the so-called concentrated solution means the residual component of concentrated solution when 110 ℃ of dryings reach constant weight.
With the cation electrodeposition coating of NV (nonvolatile component concentration)=20 weight %, pH=6.5, MEQ=25 management (Japanese ペ イ Application ト Co., Ltd. system: パ ワ-ト Star プ (registered trademark) U-2500) in the 10m groove, under the japanning condition of liquid temperature=28 ℃, CV (japanning voltage)=250V, conduction time=2～3 minute, carry out electro-deposition coating, with the ultrafiltration recycle-water give a baby a bath on the third day after its birth level, finally wash one-level and implement online washing.The coated article that ultrafiltration is reclaimed after the washing washs at final water washing tank used pure water with specific conductivity 2 μ s/cm, but because the coating composition of bringing into this moment is arranged, its waste liquor from final water washing tank used becomes NV=0.1%pH=6.5.
This waste liquid is imported in the thickener, adjust to pH=5.0 with acetate after, supply with the filtration unit that has been equipped with ultra-filtration membrane (Asahi Chemical Industry Co., Ltd's system, マ イ Network ロ-ザ (registered trademark) KCV3010) and filter.
The filtration condition of this moment is: go into pressure=2.5kg/cm, go out pressure=0.5kg/cm.
Amount of filtrate is that the initial stage is 12l/min, is carried out up to be 6l/min after concentrating 100 times, filters excellent in stability.
Obtain filtrate 4950l by supplying with ultra-filtration membrane when supplying with filtering waste liquid and being 5000l, concentrated solution 50l, concentrated solution are extracted in other container.
Filtrate is NV=0.04%, pH=5.2, and concentrated solution is NV=6.2%, pH=6.3.
This filtrate is returned once more and is used as the surrogate of pure water in final water washing tank used, and washing effect is good, and the coated article result of solubility test again is also no problem.
Burn after being extracted into the concentrated solution evaporate to dryness decrement in other container.
In addition, although reused filtrate in continuing revision test, it is extremely stable to turn round, and does not also bother after 6 months, still can proceed.
Embodiment 2
The waste liquid that the pure water washing bath that uses from embodiment 1 is discharged is supplied with ultra-filtration membrane (Asahi Chemical Industry Co., Ltd's system, マ イ Network ロ-ザ (registered trademark) KCV3010) processing after adjusting to pH=5.0 with the utmost point liquid (main component is about 0.05% acetate) of galvanic deposition cell.
The filtration condition of this moment is into pressure=2.5kg/cm
2, go out pressure=0.5kg/cm
2
Amount of filtrate is initial stage 12l/min, and being implemented into and concentrating 200 times is 3l/min afterwards, filters excellent in stability.
Obtain filtrate 4975l, concentrated solution 25l by supplying with ultra-filtration membrane when supplying with filtering waste liquid and being 5000l.
Filtrate is NV=0.05%, pH=5.2, and concentrated solution is NV=10%, pH=6.4.
This filtrate is returned the final water washing tank used pure water that is used to replace once more, and washing effect is good, and the coated article result of solubility test again is also out of question.
Embodiment 3
The concentrated solution of embodiment 2 returns galvanic deposition cell.Running condition is still stable after returning galvanic deposition cell, and the bright and clean situation of product surface after baking is finished is still good.
Embodiment 4
The waste liquid that the pure water washing bath that uses from embodiment 1 is discharged is supplied with the thickener of cubic capacity 5000l, supplies with ultra-filtration membrane (Asahi Chemical Industry Co., Ltd's system: マ イ Network ロ-ザ (registered trademark) KCV3010) handle after being adjusted to pH=6.0 with acetate.
The filtration condition of this moment is into pressure=2.5kg/cm
2, go out pressure=0.5kg/cm
2And in filter operation, filtration process just carried out once 30 seconds by a definite date sour back flushing in per 30 minutes.The acid back flushing is to add 300ppm acetate in filtrate, uses solution that 15l forms thus as counter-flushing liquid at every turn.Consequently, the pH of concentrated solution adjusts to through being everlasting 6.0～6.3 scope.Amount of filtrate is that the initial stage is 12l/min, is implemented into to be 10l/min after concentrating 10 times, further is implemented into to be 6l/min after concentrating 100 times, filters excellent in stability.In addition, filter and carried out continuously 4 days, respectively obtain 5000l filtrate every day, one side is sent to washing bath, and one side is often added the pure water washing bath waste liquid that quantity is equivalent to amount of filtrate to thickener.By the 5th day, stop to add pure water washing bath waste liquid, the 5000l concentrated solution is carried out the intermittent type concentration, make it further to be concentrated to 250l.When adding up to 25000l, the filtering waste liquid of (concentration rate is 100 times) supply obtains filtrate 24750l, concentrated solution 250l by supplying with ultra-filtration membrane.
It is NV=0.04%, pH=5.9 that the 5th day intermittent type concentrates the filtrate (when concentrating 5 times) at initial stage, and final concentrated solution (when concentrating 100 times) is NV=6.1%, pH=6.2.This filtrate is still often returned and final water washing tank usedly is used to replace pure water, but washing effect is good, and the coated article result of solubility test again is also no problem.
Embodiment 5
Carry out the test the same with embodiment 4, a resulting ultrafiltrate part is supplied with reverse osmosis membrane (eastern レ (strain) system: SU-700) handle.Reverse osmosis filtrate is used to spray final water washing tank used coated article when going out groove, the water that drenches be recovered in final water washing tank used in, but washing effect is good, the coated article result of solubility test again is also no problem.
Wherein, osmosis filtration is with working pressure 15kg/cm
2Carry out, reverse osmosis filtrate is collected with the speed of 3l/min, and reverse osmosis concentrated liquid is transmitted back to washing bath.The water quality of reverse osmosis filtrate is below the NV=0.001%, pH=6.4, specific conductivity=2 μ s/cm.
Comparative example 1
The waste liquor from final water washing tank used of embodiment 1 is not any pH and is adjusted, with embodiment 1 the same ultra-filtration membrane (the Asahi Chemical Industry Co., Ltd's system: マ イ Network ロ-ザ (registered trademark) KCV3010) it is separated into concentrated solution and filtrate of supplying with.The pH of concentrated solution rises to 7.0 from 6.5.The amount of filtrate of ultra-filtration membrane generation is 12l/min at first, and circulation is concentrated just slowly to be reduced along with continuing, and has been reduced to below the 1l/min during to concentrated 5 times, filters stability poorly.
Comparative example 2
Under the condition identical, move, add acetate from the waste liquid of NV=0.1%, the pH=6.5 of final water washing tank used discharge and it is transferred to pH=6.0, this solution and the embodiment 1 the same uf processing of carrying out with embodiment 1.The amount of filtrate that ultrafiltration produces is initially 12l/min, but concentrates along with continuing circulation, and the pH of concentrated solution just slowly rises, amount of filtrate then slowly descends on the other hand, reach 50 times of pH6.5 when concentrated, amount of filtrate drops to below the 1l/min, and in fact uf processing can not be proceeded.
Claims (9)
1. waste liquor from final water washing tank used treatment process, it is characterized in that, in the treatment process of the final water washing tank used institute of cation electrodeposition painting technology effluent discharge, make the pH of the interior waste liquid of thickener (6) often remain on below 6.4, allow this waste liquid in the filtration unit that has been equipped with semi-permeable membranes (9), circulate, make it to be separated into the concentrated solution and the filtrate that contain coating composition.
2. the waste liquor from final water washing tank used treatment process described in the claim 1 is characterized in that, all or part of returns and utilizes with washing water as final washing in final water washing tank used again to separate the filtrate obtain by semi-permeable membranes.
3. the waste liquor from final water washing tank used treatment process described in the claim 1 or 2, it is characterized in that, accumulate a certain amount of washing waste liquid in the thickener (6),, add acid the pH of liquid in the thickener is adjusted to below 6.0 until start of run by filtration unit (9) circulation beginning.
4. any one described waste liquor from final water washing tank used treatment process in the claim 1～3 is characterized in that the degree of enrichment of concentrated solution reaches the highest 200 times stage in the thickener of above-mentioned circulation waste liquid, and concentrated solution is extracted out from thickener.
5. any one described waste liquor from final water washing tank used treatment process in the claim 1～4, it is characterized in that, use multiple-grooved as final water washing tank used situation under, the waste liquid of final water washing tank used each groove all returns in separately the last groove, the waste liquid of final water washing tank used initial groove is sent into thickener to supply with filtration unit, and at least a portion of filtrate is returned final water washing tank used final groove and utilized with washing water as final washing again.
6. any one described waste liquor from final water washing tank used treatment process in the claim 1～5, it is characterized in that, during the waste liquor from final water washing tank used that the waste liquid of final water washing tank used discharge is separated into the concentrated solution that contains coating composition and filtrate by the filtration unit circulation that has been equipped with semi-permeable membranes in the cation electrodeposition painting technology is handled, semi-permeable membranes is with having added 300～3, the back flushing of 000ppm organic acid filtrate keeps through being everlasting below 6.4 the pH of concentrated solution in the thickener.
7. any one described waste liquor from final water washing tank used treatment process in the claim 1～6, wherein the pH value of waste liquor from final water washing tank used is adjusted with electrode solution or organic acid or thionamic acid, carbonic acid and is carried out.
8. any one described waste liquor from final water washing tank used treatment process in the claim 1～7, wherein semi-permeable membranes is a ultra-filtration membrane.
9. any one described waste liquor from final water washing tank used treatment process in the claim 1～7, wherein to separate be the filtrate that ultra-filtration and separation is handled to be carried out reverse osmosis isolation again handle to semi-permeable membranes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21270794 | 1994-09-06 | ||
| JP212707/1994 | 1994-09-06 | ||
| JP212707/94 | 1994-09-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135241A CN1135241A (en) | 1996-11-06 |
| CN1116448C true CN1116448C (en) | 2003-07-30 |
Family
ID=16627103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95190856A Expired - Lifetime CN1116448C (en) | 1994-09-06 | 1995-09-05 | Method for treating waste liquor from final water washing tank used in cation electrodeposition painting |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2873095B2 (en) |
| KR (1) | KR100392214B1 (en) |
| CN (1) | CN1116448C (en) |
| TW (1) | TW363943B (en) |
| WO (1) | WO1996007775A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107109680A (en) * | 2014-12-26 | 2017-08-29 | 旭化成株式会社 | System for recovery of electrodeposition paint and method |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7179376B2 (en) | 2003-11-24 | 2007-02-20 | Ppg Industries Ohio, Inc. | Method and system for removing residual water from excess washcoat by ultrafiltration |
| JP4536482B2 (en) * | 2004-10-25 | 2010-09-01 | 旭化成ケミカルズ株式会社 | Operation method of membrane filtration device |
| KR101321228B1 (en) * | 2009-01-29 | 2013-10-23 | 아사히 가세이 케미칼즈 가부시키가이샤 | System for recovery of electrodeposition paint and apparatus for recovery of electrodeposition paint |
| CN102115904B (en) * | 2009-12-30 | 2015-04-01 | 北京中科三环高技术股份有限公司 | Device for coating electrophoretic paint on cathode made of neodymium-iron-boron magnetic material under condition of zero emission and electrophoretic coating method |
| KR101413397B1 (en) * | 2012-07-20 | 2014-07-02 | 나윤환 | Sealing plug for electrodeposition coating and electrodeposition coating method using the same |
| KR101565947B1 (en) | 2014-03-28 | 2015-11-05 | 주식회사 필텍이엔지 | waste water recycling apparatus for electro painting |
| CN106917130B (en) * | 2017-03-07 | 2018-07-13 | 安徽江淮汽车集团股份有限公司 | A kind of recycling of electrophoretic paint and spray washing system |
| CN110129861A (en) * | 2019-06-26 | 2019-08-16 | 吉安特膜分离设备(长春)有限公司 | Bi-membrane method electrophoretic painting cleans Sewage treatment technology |
| KR102431734B1 (en) | 2022-03-10 | 2022-08-10 | 김태환 | Electrodeposition coating system and electrodeposition coating method using the same |
| CN114538691B (en) * | 2022-03-14 | 2023-04-07 | 宏源防水科技集团有限公司 | Water-based waterproof coating wastewater treatment process |
| CN115432839A (en) * | 2022-07-29 | 2022-12-06 | 广汽乘用车有限公司 | Surface coating waste solvent treatment device and process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5091639A (en) * | 1973-12-18 | 1975-07-22 | ||
| JPS53118435A (en) * | 1977-03-25 | 1978-10-16 | Honda Motor Co Ltd | Recovery method of bath solution for powder electrodeposition |
| JPS5952240B2 (en) * | 1981-11-13 | 1984-12-18 | 旭化成株式会社 | Ultrafiltration method |
-
1995
- 1995-09-05 WO PCT/JP1995/001759 patent/WO1996007775A1/en active Application Filing
- 1995-09-05 TW TW084109250A patent/TW363943B/en not_active IP Right Cessation
- 1995-09-05 CN CN95190856A patent/CN1116448C/en not_active Expired - Lifetime
- 1995-09-05 JP JP8509372A patent/JP2873095B2/en not_active Expired - Lifetime
- 1995-09-05 KR KR1019960702342A patent/KR100392214B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107109680A (en) * | 2014-12-26 | 2017-08-29 | 旭化成株式会社 | System for recovery of electrodeposition paint and method |
| CN107109680B (en) * | 2014-12-26 | 2019-04-26 | 旭化成株式会社 | System for recovery of electrodeposition paint and method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996007775A1 (en) | 1996-03-14 |
| KR100392214B1 (en) | 2003-11-28 |
| KR960705968A (en) | 1996-11-08 |
| TW363943B (en) | 1999-07-11 |
| JP2873095B2 (en) | 1999-03-24 |
| CN1135241A (en) | 1996-11-06 |
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