CN102976518B - Method for simultaneously purifying electroplating wastewater, printing and dyeing wastewater and chemical industrial organic wastewater - Google Patents
Method for simultaneously purifying electroplating wastewater, printing and dyeing wastewater and chemical industrial organic wastewater Download PDFInfo
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- 238000009713 electroplating Methods 0.000 title claims abstract description 37
- 238000004043 dyeing Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 title claims abstract description 31
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- 150000002500 ions Chemical class 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 15
- 229960001545 hydrotalcite Drugs 0.000 abstract description 15
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- 239000011229 interlayer Substances 0.000 abstract description 9
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- 239000005416 organic matter Substances 0.000 abstract 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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Abstract
本发明公开一种同时净化电镀废水、印染废水和化工有机废水的方法，将电镀废水和印染废水分别过滤去除固体颗粒，根据电镀生产工艺分析其中存在的离子，添加金属阳离子或将多种电镀废水混合，使二价离子的摩尔浓度是三价离子的摩尔浓度的2~4倍；将电镀废水和印染废水按体积比2∶1~4∶1混合，向混合废水中滴加50%~70%的NaOH溶液调节pH值至8~10为止，滴加时在300~400rpm下搅拌120～180分钟；加入水量为印染废水1~4倍的化工有机废水，充分搅拌混合2~4h，沉淀，分离；加入盐酸或硫酸，调节pH至7；将化工废水和印染废水中的其他有机物都吸附到水滑石的层间，一起沉淀从水中分离。The invention discloses a method for purifying electroplating wastewater, printing and dyeing wastewater and chemical organic wastewater at the same time. The electroplating wastewater and printing and dyeing wastewater are respectively filtered to remove solid particles, and the ions existing therein are analyzed according to the electroplating production process, and metal cations are added or various electroplating wastewater Mix so that the molar concentration of divalent ions is 2 to 4 times that of trivalent ions; mix electroplating wastewater and printing and dyeing wastewater in a volume ratio of 2:1 to 4:1, and add 50% to 70% % NaOH solution to adjust the pH value to 8~10, and stir at 300~400rpm for 120~180 minutes during the dropwise addition; add chemical organic wastewater whose water volume is 1~4 times that of printing and dyeing wastewater, fully stir and mix for 2~4 hours, and precipitate. Separation; add hydrochloric acid or sulfuric acid to adjust the pH to 7; absorb other organic matter in chemical wastewater and printing and dyeing wastewater to the interlayer of hydrotalcite, and precipitate together and separate from water.
Description
Technical field
The present invention relates to environmental pollution and control the exploitation of new technology, relate in particular to a kind of method of while purifying electric waste electroplating, dyeing waste water and chemical industrial organic wastewater.
Background technology
Electroplate waste water and waste liquid that factory (or workshop) discharges, as plating piece rinse water, useless tank liquor, component cooling water and the flushing surface water etc., its water quality is different because of production technique, and often oil-containing many kinds of metal ions, in general, often contains Cr
6+, Cd
2+, Ni
2+, Cu
2+, Zn
2+, Fe
2+in heavy metal; How poisonous electroplating wastewater is, endangers larger.As cyanogen can cause people and animals' acute poisoning, lethal, lower concentration long term also can cause chronic poisoning.Cadmium can make kidney generation pathology, and can cause itai-itai.Sexavalent chrome can cause lung cancer, intestines and stomach disease and anaemia, and can in bone, spleen and liver, accumulate.Therefore, electroplating wastewater must strictly be controlled, and deals carefully with.
At present, the electroplating effluent treatment method extensively adopting mainly contains 7 classes: (1) chemical precipitation method, is divided into again neutralization precipitation method and sulphide precipitation.(2) redox is processed, and is divided into chemical reduction method, ferrite process and electrolytic process.(3) solvent extraction and separation method.(4) absorption method.(5) membrane separation technique.(6) ion exchange method.(7) biologic treating technique, comprises bio-flocculation process, biosorption process, biochemical process, phytoremediation.The whole bag of tricks has relative merits separately.Such as the mishandling meeting of absorption method causes pollutent, shift, biological process onset is slow, needs the several growth cycles of microorganism just can see effect.
Textile printing and dyeing wastewater has the features such as the water yield is large, organic pollutant content is high, alkalescence large, change of water quality is large, belong to one of unmanageable trade effluent, in waste water, contain dyestuff, slurry, auxiliary agent, finish, soda acid, fiber impurity, sand class material, inorganic salt etc.In dyeing process, the reactive dyestuffs of consumption maximum are exactly anionic dyestuff, and its amount existing in waste water is also maximum, process comparatively difficulty.For the main method for the treatment of of dyeing wastewater, there is at present the treatment process of physico-chemical process, biochemical process, chemical method and several technique combinations.But whole construction investment is large, and process cost is high.
Along with rapid development of economy, the pollution aggravation of Chemicals production process to environment, also more prevalent and serious to the harm of human health, the organic substance of wherein particularly discharging in fine chemical product (as pharmacy, dyestuff, daily use chemicals etc.) production process is all the material of complex structure, poisonous and harmful and biological hard degradation mostly.Therefore, the difficulty of chemical wastewater treatment is larger.The essential characteristic of wastewater from chemical industry is high COD, high salinity, toxic to microorganism, is typical used water difficult to degradate, is research emphasis and the focus of current water technology aspect.The signature analysis of wastewater from chemical industry is as follows: (1) water-quality constituents is complicated, and by product is many, and reaction raw materials is often the compound of solvent based material or ring texture, has increased the intractability of waste water; (2) Pollutants in Wastewater content is high, this be due to raw material reaction not exclusively and raw material or produce in a large amount of solvent mediums of use to have entered waste water system caused; (3) hazardous and noxious substances is many, and in Fine Chemistry Wastewater, having many organic pollutants is poisonous and hazardous to microorganism, as halogen compounds, nitro-compound, the dispersion agent with germicidal action or tensio-active agent etc.; (4) bio-refractory material is many, and B/C is than low, and biodegradability is poor; (5) chroma in waste water is high.Wastewater from chemical industry is a kind of more unmanageable waste water.
The processing of this class waste water is at present mainly separately to process, and for the characteristic of various waste water, selects method separately to process respectively; Or various wastewater mixes, some technique of general use superposes, and gives no thought to the feature of waste water separately, take time and effort, invest large, process cost is high.
Layered di-hydroxyl composite metal oxidate (Layered Double Hydroxides is called for short LDH), claims again hydrotalcite, is the important inorganic functional material of a class.The adjustable sex change of the laminate structure that it is unique and laminate element and interlayer anion gets more and more people's extensive concerning, through ion-exchange, to interlayer, introduce new object negatively charged ion and can make laminate structure and form to produce corresponding variation, thereby can prepare the functional materials that a large class has special property.Hydrotalcite material belongs to anion type laminated compound.Lamellar compound refer to there is laminate structure, a compounds that interlayer ion has interchangeability, utilize intercalation that lamellar compound main body has under strong polar molecule effect and the interchangeability of interlayer ion, thereby some functional guest species are introduced to bedding voids and laminate distance is strutted and forms layer-pillared compound.
Hydrotalcite chemical structure of general formula is: [M
2+ 1-xm
3+x (OH)
2]
x+[(A
n-)
x/nmH
2o], M wherein
2+for Mg
2+, Ni
2+, Mn
2+, Zn
2+, Ca
2+, Fe
2+, Cu
2+deng divalent metal negatively charged ion; M
3+for Al
3+, Cr
3+, Fe
3+, Co
3+deng trivalent metal negatively charged ion; A
n-for negatively charged ion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6h
4(COO)
2 2-etc. inorganic and organic ion and complexing ion, different when interlayer inorganic anion, the interlamellar spacing of hydrotalcite is different, and after hydrotalcite absorb polluted matter, interlamellar spacing also can increase, to hold more pollutent simultaneously.
Summary of the invention
The object of the invention is the deficiency of processing for purifying electric waste electroplating, dyeing waste water and chemical industrial organic wastewater in prior art for overcoming, a kind of method of while purifying electric waste electroplating, dyeing waste water and chemical industrial organic wastewater is provided.
The technical solution used in the present invention is in turn include the following steps:
1) electroplating wastewater and dyeing waste water are filtered respectively to removal solid particulate, the ion that analysis wherein exists according to electroplate technology, add metallic cation or multiple electroplating wastewater is mixed, making bivalent ions volumetric molar concentration is 2 ~ 4 times of volumetric molar concentration of trivalent ion;
2) by electroplating wastewater and dyeing waste water by volume 2:1 ~ 4:1 mix, till regulating pH value to 8 ~ 10 to the NaOH solution that drips 50% ~ 70% in composite waste, during dropping, under 300 ~ 400 rpm, stir 120～180 minutes;
3) adding the water yield is the chemical industrial organic wastewater of 1 ~ 4 times of dyeing waste water, is fully uniformly mixed 2 ~ 4 h, precipitation, separation;
4) add hydrochloric acid or sulfuric acid, regulate pH to 7.
Advantage of the present invention is:
(1) utilize the metal ion in electroplating wastewater can generate hydrotalcite under alkaline condition, utilize the anionresin characteristic of hydrotalcite by the negatively charged ion in waste water (anionic dyestuff, CN
-etc.) be all adsorbed onto interlayer.At anionic dyestuff, be adsorbed to after interlayer, formed again the organic phase with distribution capability, other organism in wastewater from chemical industry and dyeing waste water are all adsorbed onto to the interlayer of hydrotalcite, coprecipitation is separated from water.
(2) dyeing waste water add the generation that membership has promoted hydrotalcite because the general alkalescence of dyeing waste water is stronger, pH is higher, can reduce the consumption of preparing alkali in hydrotalcite process (NaOH) after adding dyeing waste water.
(3) load making by heavy metal has the hydrotalcite of dyestuff to form organic hydrotalcite, after processing wastewater from chemical industry, according to the amount of its absorb polluted matter number, before not reaching capacity, also can be used as material for water treatment, continue on for organic waste water and administer.
Embodiment
Electroplating wastewater and dyeing waste water are filtered respectively to removal solid particulate, the ion that wherein may exist according to electroplate technology analysis, add suitable metallic cation, or multiple electroplating wastewater is mixed, guarantee that bivalent ions volumetric molar concentration is 2 ~ 4 times of volumetric molar concentration of trivalent ion.If only have divalent metal, add a small amount of trivalent metal cation (as comparatively cheap Al
3+, Fe
3+), if only have trivalent metal cation, add a small amount of divalent metal (as comparatively cheap Mg
2+, Fe
2+), if had divalent metal and trivalent metal cation, investigate concentration, guarantee that the concentration ratio of the two meets the scope of 2 ~ 4 times that bivalent ions volumetric molar concentration is the volumetric molar concentration of trivalent ion.
By electroplating wastewater and dyeing waste water by volume 2:1 ~ 4:1 mix, to the NaOH solution that drips fast 50% ~ 70% in composite waste, regulate pH value, until pH value to 8 ~ 10, during dropping under 300 ~ 400 rpm rapid stirring 120～180 minutes.Then add chemical industrial organic wastewater, the water yield is dyeing waste water 1 ~ 4 times, after wastewater from chemical industry adds, and composite waste before, fully be uniformly mixed 2 ~ 4 h, precipitation, separation, pollutent in composite waste can be removed along with precipitation, finally adds hydrochloric acid or sulfuric acid, regulates pH to 7 left and right.
3 embodiment of the present invention are below further provided:
embodiment 1
Electroplating wastewater and dyeing waste water are filtered respectively to removal solid particulate, according to analysis of Production Technology, in electroplating wastewater, contain Ni
2+and Cu
2+, add a small amount of Al
3+, making bivalent ions volumetric molar concentration is 2 times of volumetric molar concentration of trivalent ion; By electroplating wastewater and dyeing waste water 4:1 mixing by volume, to the NaOH solution that drips fast 70% in electroplating wastewater, regulate pH value to 8, during dropping under 400 rpm rapid stirring 180 minutes, add chemical industrial organic wastewater, the water yield is 4 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before is fully uniformly mixed 4 h, precipitation, separated, pollutent in composite waste can be removed along with precipitation, finally adds sulfuric acid, regulates pH to 7 left and right.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in waste water is all greater than 99%, mixed COD clearance is 91.7%.
embodiment 2
Electroplating wastewater and dyeing waste water are filtered respectively to removal solid particulate, according to analysis of Production Technology, in electroplating wastewater, contain Fe
3+and Al
3+, add a small amount of Mg
2+, making bivalent ions volumetric molar concentration is 4 times of volumetric molar concentration of trivalent ion; By electroplating wastewater and dyeing waste water 2:1 mixing by volume, to the NaOH solution that drips fast 50% in electroplating wastewater, regulate pH value to 10, during dropping under 300 rpm rapid stirring 120 minutes, add chemical industrial organic wastewater, the water yield is 1 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before is fully uniformly mixed 2h, precipitation, separated, pollutent in composite waste can be removed along with precipitation, finally adds hydrochloric acid, regulates pH to 7 left and right.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in waste water is all greater than 99%, mixed COD clearance is 92.5%.
embodiment 3
Multiple electroplating wastewater and dyeing waste water are mixed respectively, remove solid particulate, according to having Ni in analysis of Production Technology electroplating wastewater
2+, Cu
2, Fe
3+and Al
3+and bivalent ions volumetric molar concentration is 3 times of volumetric molar concentration of trivalent ion, by electroplating wastewater and dyeing waste water 3:1 mixing by volume, in electroplating wastewater, drip fast 60% NaOH solution adjusting pH value to 9, during dropping under 350 rpm rapid stirring 150 minutes, add chemical industrial organic wastewater, the water yield is 3 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before is fully uniformly mixed 3 h, precipitation, separated, pollutent in composite waste can be removed along with precipitation, finally adds sulfuric acid, regulates pH to 7 left and right.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in waste water is all greater than 99%, mixed COD clearance is 92.1%.
The hydrotalcite that precipitation is obtained is dried, pulverizes last, is used further to process the organic waste water containing the p-nitrophenyl of 10 mg/L, and every gram of handled wastewater volume corresponding to hydrotalcite is about 1 L, rapid stirring 60 minutes; Reaction product stops 30 minutes at settling tank, solid-liquid separation, and ultraviolet-visible pectrophotometer is measured supernatant liquor concentration, and pollutants removal rate is 92.8%.
Claims (1)
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| CN104355436A (en) * | 2014-10-20 | 2015-02-18 | 苏州富奇诺水治理设备有限公司 | Purifying method of industrial waste water |
| CN106477757A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of method processing plating, printing and dyeing and chemical industrial organic wastewater |
| CN107285440A (en) * | 2017-07-04 | 2017-10-24 | 中国科学院生态环境研究中心 | A kind of method that the waste water containing heavy-metal stain is handled based on coprecipitation reaction in situ |
| CN109772259A (en) * | 2019-03-18 | 2019-05-21 | 清华大学 | Method for treating electroplating wastewater with electroplating sludge and heavy metal ion adsorbent |
| CN111252945A (en) * | 2020-02-25 | 2020-06-09 | 上海电力大学 | A method for simultaneously purifying electroplating wastewater and printing and dyeing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506315A (en) * | 2002-12-10 | 2004-06-23 | 合肥工业大学 | Preparation method of layered double hydroxide and its derivatives like periclase |
| CN1569671A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Water treatment method for instant synthesis of laminated bis-hydroxide |
| CN101376537A (en) * | 2008-09-24 | 2009-03-04 | 上海大学 | Method for processing electroplating waste containing Ni2+, Zn2+ and Cr3+ |
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| WO2004108608A1 (en) * | 2003-06-11 | 2004-12-16 | Seong Soo Hong | Method and apparatus for treating wastewater containing organic compound of high concentration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506315A (en) * | 2002-12-10 | 2004-06-23 | 合肥工业大学 | Preparation method of layered double hydroxide and its derivatives like periclase |
| CN1569671A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Water treatment method for instant synthesis of laminated bis-hydroxide |
| CN101376537A (en) * | 2008-09-24 | 2009-03-04 | 上海大学 | Method for processing electroplating waste containing Ni2+, Zn2+ and Cr3+ |
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