CN102976518A - 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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- CN102976518A CN102976518A CN2012104916361A CN201210491636A CN102976518A CN 102976518 A CN102976518 A CN 102976518A CN 2012104916361 A CN2012104916361 A CN 2012104916361A CN 201210491636 A CN201210491636 A CN 201210491636A CN 102976518 A CN102976518 A CN 102976518A
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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 at 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 the exploitation of environmental pollution control new technology, relate in particular to the method for a kind 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, such 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 in general the oil-containing many kinds of metal ions, often contains Cr
6+, Cd
2+, Ni
2+, Cu
2+, Zn
2+, Fe
2+In heavy metal; How poisonous electroplating wastewater is, endangers larger.Can cause people and animals' acute poisoning such as cyanogen, cause death that the 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 accumulate in bone, spleen and liver.Therefore, electroplating wastewater must strictly be controlled, and deals carefully with.
At present, the electroplating effluent treatment method that extensively adopts 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.Cause pollutent to shift such as the mishandling meeting of absorption method, the biological process onset is slow, needs the several growth cycles of microorganism just can see effect.
Textile printing and dyeing wastewater has the characteristics such as the water yield is large, organic pollutant content is high, alkalescence is large, change of water quality is large, belong to one of unmanageable trade effluent, contain dyestuff, slurry, auxiliary agent, finish, soda acid, fiber impurity, sand class material, inorganic salt etc. in the waste water.The reactive dyestuffs of consumption maximum are exactly anionic dyestuff in the dyeing process, and its amount that exists in waste water is also maximum, process comparatively difficulty.The main method that is used at present treatment of dyeing wastewater has 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 Chemicals production process is to the pollution aggravation of environment, harm to human health is also more prevalent and serious, the organic substance of wherein particularly discharging in fine chemical product (such as pharmacy, dyestuff, the daily use chemicals etc.) production process all is 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 present 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 the compound of solvent based material or ring texture often, has increased the intractability of waste water; (2) Pollutants in Wastewater content is high, this be since raw material reaction not exclusively and raw material or produce in a large amount of solvent mediums of use to have entered the waste water system caused; (3) hazardous and noxious substances is many, and it is poisonous and hazardous to microorganism that many organic pollutants are arranged in the Fine Chemistry Wastewater, such as halogen compounds, nitro-compound, the dispersion agent with germicidal action or tensio-active agent etc.; (4) the 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 mainly is separate treatment at present, selects method separately to process respectively for the characteristic of various waste water; Perhaps various wastewater mixes, and some technique of general usefulness superposes, and gives no thought to the separately characteristics of waste water, 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, introduce new object negatively charged ion through ion-exchange to interlayer and can make laminate structure and composition produce corresponding the variation, thereby can prepare the functional materials that a large class has special property.Hydrotalcite material belongs to anion type laminated compound.The compounds that lamellar compound refers to have laminate structure, interlayer ion has interchangeability, utilize intercalation that the lamellar compound main body has and the interchangeability of interlayer ion under strong polar molecule effect, form layer-pillared compound thereby some functional guest species are introduced bedding voids and the laminate distance strutted.
The hydrotalcite chemical structure of general formula is: [M
2+ 1-xM
3+X (OH)
2]
X+[(A
N-)
X/nMH
2O], M wherein
2+Be Mg
2+, Ni
2+, Mn
2+, Zn
2+, Ca
2+, Fe
2+, Cu
2+Deng the divalent metal negatively charged ion; M
3+Be Al
3+, Cr
3+, Fe
3+, Co
3+Deng the trivalent metal negatively charged ion; A
N-Be negatively charged ion, such 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 the interlayer inorganic anion, the interlamellar spacing of hydrotalcite is different, and after the hydrotalcite absorb polluted matter, interlamellar spacing also can increase, to hold more pollutent simultaneously.
Summary of the invention
The objective of the invention is the deficiency processed for purifying electric waste electroplating, dyeing waste water and chemical industrial organic wastewater for overcoming in the prior art, the method for a kind 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 the 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) with electroplating wastewater and dyeing waste water by volume 2:1 ~ 4:1 mix, drip 50% ~ 70% NaOH solution in the composite waste and regulate till pH value to 8 ~ 10, under 300 ~ 400 rpm, stirred 120～180 minutes during dropping;
3) adding the water yield is the chemical industrial organic wastewater of 1 ~ 4 times of dyeing waste water, fully mixes 2 ~ 4 h, and precipitation is separated;
4) add hydrochloric acid or sulfuric acid, regulate pH to 7.
Advantage of the present invention is:
(1) utilizes the metal ion in the electroplating wastewater under alkaline condition, can generate hydrotalcite, utilize the anionresin characteristic of hydrotalcite with the negatively charged ion in the waste water (anionic dyestuff, CN
-Etc.) all be adsorbed onto interlayer.After anionic dyestuff is adsorbed to interlayer, formed again the organic phase with distribution capability, other organism in wastewater from chemical industry and the dyeing waste water all are adsorbed onto the interlayer of hydrotalcite, coprecipitation separates from water.
(2) affiliation that adds of dyeing waste water has promoted the generation of hydrotalcite, because the general alkalescence of dyeing waste water is stronger, pH is higher, adds the consumption that can reduce alkali (NaOH) in the preparation hydrotalcite process behind the dyeing waste water.
(3) load that makes 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 what, also can be used as material for water treatment before not reaching capacity, and continues on for organic waste water and administers.
Embodiment
Electroplating wastewater and dyeing waste water are filtered respectively the removal solid particulate, the ion that wherein may exist according to the 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, then add a small amount of trivalent metal cation (such as comparatively cheap Al
3+, Fe
3+), if only have trivalent metal cation, then add a small amount of divalent metal (such as comparatively cheap Mg
2+, Fe
2+), if divalent metal and trivalent metal cation have been arranged, then investigate concentration, guarantee that the concentration ratio of the two meets 2 ~ 4 times the scope that bivalent ions volumetric molar concentration is the volumetric molar concentration of trivalent ion.
With electroplating wastewater and dyeing waste water by volume 2:1 ~ 4:1 mix, drip fast 50% ~ 70% NaOH solution in the composite waste and regulate the 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 1 ~ 4 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before, fully mix 2 ~ 4 h, precipitation is separated, pollutent in the composite waste can be removed along with precipitation, adds at last hydrochloric acid or sulfuric acid, regulates about pH to 7.
3 embodiment of the present invention below further are provided:
Embodiment 1
Electroplating wastewater and dyeing waste water are filtered respectively the removal solid particulate, according to analysis of Production Technology, contain Ni in the electroplating wastewater
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; With electroplating wastewater and by volume 4:1 mixing of dyeing waste water, drip fast 70% NaOH solution in the electroplating wastewater and regulate pH value to 8, during dropping under 400 rpm rapid stirring 180 minutes, the adding chemical industrial organic wastewater, the water yield is 4 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before fully mixes 4 h, precipitation, separate, pollutent in the composite waste can be removed along with precipitation, adds at last sulfuric acid, regulates about pH to 7.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in the waste water is all greater than 99%, and mixed COD clearance is 91.7%.
Embodiment 2
Electroplating wastewater and dyeing waste water are filtered respectively the removal solid particulate, according to analysis of Production Technology, contain Fe in the electroplating wastewater
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; With electroplating wastewater and by volume 2:1 mixing of dyeing waste water, drip fast 50% NaOH solution in the electroplating wastewater and regulate pH value to 10, during dropping under 300 rpm rapid stirring 120 minutes, the adding chemical industrial organic wastewater, the water yield is 1 times of dyeing waste water, after wastewater from chemical industry adds, and composite waste before fully mixes 2h, precipitation, separate, pollutent in the composite waste can be removed along with precipitation, adds at last hydrochloric acid, regulates about pH to 7.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in the waste water is all greater than 99%, and 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 the 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, with electroplating wastewater and by volume 3:1 mixing of dyeing waste water, 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 fully mixes 3 h, precipitation, separate, pollutent in the composite waste can be removed along with precipitation, adds at last sulfuric acid, regulates about pH to 7.Measure composite waste supernatant liquor water quality, after measured: the clearance of the metal ion in the waste water is all greater than 99%, and mixed COD clearance is 92.1%.
It is last that the hydrotalcite that precipitation obtains is dried, pulverized, and is used further to process the organic waste water of the p-nitrophenyl that contains 10 mg/L, and the handled wastewater volume that every gram hydrotalcite is corresponding is about 1 L, rapid stirring 60 minutes; Reaction product stopped 30 minutes at settling tank, solid-liquid separation, and ultraviolet-visible pectrophotometer is measured supernatant liquor concentration, and pollutants removal rate is 92.8%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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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2012
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Patent Citations (4)
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| 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 |
| WO2004108608A1 (en) * | 2003-06-11 | 2004-12-16 | Seong Soo Hong | Method and apparatus for treating wastewater containing organic compound of high concentration |
| 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+ |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Publication date |
|---|---|
| CN102976518B (en) | 2014-04-30 |
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