CN103043815A - Method for synchronously purifying electroplating wastewater, washing wastewater and chemical organic wastewater - Google Patents
Method for synchronously purifying electroplating wastewater, washing wastewater and chemical organic wastewater Download PDFInfo
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- CN103043815A CN103043815A CN2012104983934A CN201210498393A CN103043815A CN 103043815 A CN103043815 A CN 103043815A CN 2012104983934 A CN2012104983934 A CN 2012104983934A CN 201210498393 A CN201210498393 A CN 201210498393A CN 103043815 A CN103043815 A CN 103043815A
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- wastewater
- electroplating
- washes
- hydrotalcite
- washing
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Abstract
The invention discloses a method for synchronously purifying electroplating wastewater, washing wastewater and chemical organic wastewater. The method comprises the following steps of respectively filtering the electroplating wastewater and the washing wastewater so as to remove solid grains, wherein the molar concentration of divalent ions is 2-4 times the molar concentration of trivalent ions; mixing the electroplating wastewater and the washing wastewater according to volume ratio of 3:1-5:1; dropwise adding 50-70% NaOH solution into the mixed wastewater; adjusting the pH value to 8-10; adding chemical organic wastewater of which the quantity is 1-2 times that of the washing wastewater; sufficiently stirring and mixing for 2-4h; depositing; separating and adjusting the pH to 7. Negative ions in the wastewater are all absorbed to interlayers by using the negative ion exchange characteristic of hydrotalcite, so as to form organic phase with distribution capability; organic pollutants in the chemical wastewater are all absorbed to interlayers of the hydrotalcite and are deposited to be separated from water; and the hydrotalcite can be used as a water treatment materials to be continuously used for organic wastewater treatment under the situation that the hydrotalcite is not saturated.
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, washes 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.
Tensio-active agent used in the articles for washing is take anionic as most important.Wherein the linear alkylbenzene sulfonate consumption is maximum, is aliphatic alcohol sulfate, fatty alcohol polyoxyethylene ether sulfate, alkylsulfonate etc. secondly.Anion surfactant take Sodium dodecylbenzene sulfonate as representative, responsive to the water hardness, be difficult for oxidation, foaming power is strong, cost is lower, synthesis technique is ripe, to particulate fouling, albumen dirt and oily dirt have significant clean effect, and be especially good to the cleaning function of particulate fouling on the natural fiber, detersive power strengthens with the rising of wash temperature, effect to the albumen dirt is higher than nonionogenic tenside, and foam is abundant, is very effective washing composition, be usually used in washing powder, liquid detergent and Liquid soap, consumption is very large.Sodium dodecylbenzene sulfonate also is widely used in washing and the degreasing of the industry such as process hides, weaving except being used for articles for washing.Exhibiting high surface promoting agent waste water has been discharged in the production of Sodium dodecylbenzene sulfonate, because Sodium dodecylbenzene sulfonate content is high in the waste water, if directly enter environment, not only affect hydrobiont existence, self purification of water body is obstructed, environment is caused severe contamination, and activity and the propagation of microorganism cells there is certain inhibition, animals and plants and human body there is chronic toxic action, can upset endocrine system, cause the unusual phenomenoies such as male and female one, animal immune parafunction, fetation deformity, children mental retardation.
Sodium dodecylbenzene sulfonate waste water treatment process such as coagulating sedimentation, catalyzed oxidation, foam separation, charcoal absorption, biological degradation and their combination process commonly used are realized its purifying treatment.Wherein absorption method is efficient, simple, but acticarbon is expensive.
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 provides the method for a kind of while purifying electric waste electroplating, washes and chemical industrial organic wastewater for overcoming the deficiency in treatment and purification electroplating wastewater, washes and the chemical industrial organic wastewater in the prior art.
The technical solution used in the present invention is in turn include the following steps:
1) electroplating wastewater and washes 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;
2) with electroplating wastewater and by volume 3:1 ~ 5:1 mixing of washes, in composite waste, drip 50% ~ 70% NaOH solution, regulate till pH value to 8 ~ 10, under 300 ~ 400 rpm, stirred 60～120 minutes during dropping;
3) adding the water yield is 1 ~ 2 times chemical industrial organic wastewater of washes, 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 that the negatively charged ion in the waste water (anion surfactant, polyphosphoric acid ion etc.) all is adsorbed onto interlayer.After anionic dyestuff is adsorbed to interlayer, formed again the organic phase with distribution capability, the organic pollutant in the wastewater from chemical industry all is adsorbed onto the interlayer of hydrotalcite, coprecipitation separates from water.
(2) precipitating the hydrotalcite that obtains is organic hydrotalcite, according to its size of adsorbing the amount of organic pollutant, in unsaturated situation, can be used as material for water treatment, continues on for organic waste water and administers.
Embodiment
Electroplating wastewater and washes 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, the concentration ratio of guaranteeing the two meets 2 ~ 4 times of volumetric molar concentration that bivalent ions volumetric molar concentration is trivalent ion.
Be that 3:1 ~ 5:1 mixes by volume with electroplating wastewater and washes, in composite waste, drip fast 50% ~ 70% NaOH solution, regulate the pH value, until the pH value is till 8 ~ 10, during dropping under 300 ~ 400 rpm rapid stirring 60～120 minutes.Then, add chemical industrial organic wastewater, the water yield is 1 ~ 2 times of washes, after wastewater from chemical industry adds, composite waste fully mixes 2 ~ 4 h before, and 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 washes are filtered respectively the removal solid particulate, according to analysis of Production Technology, contain Ni in the electroplating wastewater
2+And Fe
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 5:1 mixing of washes, drip fast 70% NaOH solution in the electroplating wastewater and regulate pH value to 8, during dropping under 400 rpm rapid stirring 120 minutes, the adding chemical industrial organic wastewater, the water yield is 1 times of washes, after wastewater from chemical industry adds, and composite waste before fully mixes 2 h, 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 92.8%.
Embodiment 2
Electroplating wastewater and washes are filtered respectively the removal solid particulate, according to analysis of Production Technology, contain Al in the electroplating wastewater
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 washes by volume 3:1 mix, drip fast 50% NaOH solution in the electroplating wastewater and regulate pH value to 10, during dropping under 300 rpm rapid stirring 60 minutes, precipitate and separate, add chemical industrial organic wastewater, the water yield is 2 times of washes, after wastewater from chemical industry adds, composite waste before fully mixes 4 h, precipitation is separated, and the pollutent in the composite waste can be removed along with precipitation, add at last sulfuric acid, regulate 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 93.9%.
Embodiment 3
Multiple electroplating wastewater and washes 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 4:1 mixing of washes, in electroplating wastewater, drip fast 60% NaOH solution adjusting pH value to 9, during dropping under 350 rpm rapid stirring 80 minutes, add chemical industrial organic wastewater, the water yield is 1.5 times of washes, 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 94.8%.
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 95.1%.
Claims (1)
1. method of purifying electric waste electroplating, washes and chemical industrial organic wastewater simultaneously is characterized in that in turn including the following steps:
1) electroplating wastewater and washes 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;
2) with electroplating wastewater and by volume 3:1 ~ 5:1 mixing of washes, in composite waste, drip 50% ~ 70% NaOH solution, regulate till pH value to 8 ~ 10, under 300 ~ 400 rpm, stirred 60～120 minutes during dropping;
3) adding the water yield is 1 ~ 2 times chemical industrial organic wastewater of washes, fully mixes 2 ~ 4 h, and precipitation is separated;
4) add hydrochloric acid or sulfuric acid, regulate pH to 7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481144A (en) * | 2016-01-07 | 2016-04-13 | 陕西理工学院 | Device and method for efficient treatment of copper-containing wastewater |
| 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 |
| CN108147594A (en) * | 2017-11-28 | 2018-06-12 | 苏州美源达环保科技股份有限公司 | A kind of device and method of environmental protection treatment comprehensive 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 |
| CN102336461A (en) * | 2010-07-27 | 2012-02-01 | 中国科学院过程工程研究所 | Method for removing metal ions from aqueous solution by use of hydrotalcite |
| JP2012106226A (en) * | 2010-10-29 | 2012-06-07 | Mitsubishi Materials Corp | Method and apparatus for treating harmful substance-containing water |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1506315A (en) * | 2002-12-10 | 2004-06-23 | 合肥工业大学 | Prepn of laminated dihydrogen oxide and its derivative quasi-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 |
| CN102336461A (en) * | 2010-07-27 | 2012-02-01 | 中国科学院过程工程研究所 | Method for removing metal ions from aqueous solution by use of hydrotalcite |
| JP2012106226A (en) * | 2010-10-29 | 2012-06-07 | Mitsubishi Materials Corp | Method and apparatus for treating harmful substance-containing water |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105481144A (en) * | 2016-01-07 | 2016-04-13 | 陕西理工学院 | Device and method for efficient treatment of copper-containing wastewater |
| CN108147594A (en) * | 2017-11-28 | 2018-06-12 | 苏州美源达环保科技股份有限公司 | A kind of device and method of environmental protection treatment comprehensive wastewater |
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| CN103043815B (en) | 2014-10-29 |
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