CN102976515A - Method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater - Google Patents
Method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater Download PDFInfo
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- CN102976515A CN102976515A CN2012104915161A CN201210491516A CN102976515A CN 102976515 A CN102976515 A CN 102976515A CN 2012104915161 A CN2012104915161 A CN 2012104915161A CN 201210491516 A CN201210491516 A CN 201210491516A CN 102976515 A CN102976515 A CN 102976515A
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- wastewater
- waste water
- pickling
- dyeing
- acid
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Abstract
The invention discloses a method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater. The method comprises the following steps of: collecting the pickling wastewater, filtering to remove solid particles from the pickling wastewater, analyzing the concentration of Fe<2+> and Fe<3+> in the pickling wastewater, and adding other trivalent metal salts and divalent metal salts so as to enable the molar concentration of divalent ions to be 2-4 times that of trivalent ions; mixing the de-rusted pickling wastewater with the printing and dyeing wastewater in a volume ratio of (3:1) to (4:1), and dropwise adding NaOH liquid of 50%-70% to the mixed wastewater until the pH value reaches 8-10; adding the chemical industrial organic wastewater with a water volume which is 1-4 times that of the printing and dyeing wastewater, fully stirring and mixing for 2-4 hours, and carrying out sedimentation and separation; and adding hydrochloric acid or sulphuric acid to adjust the pH value to be 7. According to the method, the metallic ions and organic anions in the wastewater are utilized, thereby treating the waste by using the waste.
Description
Technical field
The present invention relates to the exploitation of environmental pollution control new technology, relate in particular to a kind of method of processing simultaneously industrial acid-washed waste water, dyeing waste water and chemical industrial organic wastewater.
Background technology
Because the steel rolling member is exposed in the air and is oxidized by oxygen easily, is commonly called as and gets rusty.When carrying out the surface working processing of steel rolling member, need to remove component surface rustization layer.The steel rolling component surface is carried out processing treatment, can strengthen its tolerance, prolong its work-ing life.The removing of steel rolling component surface rustization layer mainly contains physical method, chemical process and electrochemical method etc.Physical mainly relies on mechanical force to peel off rusty scale, and the method shortcoming mainly is that the rusty scale removal is not thorough, and the rust cleaning process produces a large amount of dust, answers land used fewer in the steel derusting field at present; It is the widest that chemical process is used, mainly be to rely on acid and rusty scale reaction to reach the purpose of rust cleaning, the chemical method rust cleaning has the advantages such as quality that speed is fast, rust cleaning is thorough, the follow-up steel surface of assurance is processed, but, chemical process is processed still unsatisfactory part, such as pollution surrounding environment such as spent pickle liquors.Along with expanding economy, Iron And Steel Industry and iron and steel production be constantly development also, and the problem that steel chemical pickling rust cleaning process produces becomes increasingly conspicuous, and becomes one of research emphasis in the waste water treatment.
Steel surface is owing to the rusty scale moiety that corrosion produces mainly contains: Fe
2O
3, FeO, Fe
3O
4, hydration iron rust compound etc.Rusty scale is loose, porous state, easily infiltration, surface area ratio is larger.Acid cleaning process mainly is that acid is carried out chemical reaction with iron rust, makes rusty scale break away from the iron-based body, and the reaction of sour dissolved iron matrix occurs simultaneously in the acid pickling and rust removing process.The reaction that the rust cleaning process occurs is mainly as follows:
6H
+＋Fe
2O
3＝2Fe
3+＋3H
2O，
2H
+＋FeO＝Fe
2+＋H
2O，
8H
+＋Fe
3O
4＝2Fe
3+＋Fe
2+＋4H
2O，
2Fe
3+＋Fe＝3Fe
2+，
2H
+＋Fe＝Fe
2+＋H
2。
The a large amount of Fe of oil-containing in the waste water that the acid pickling and rust removing process produces
2+And Fe
3+Therefore ion, can be used as resource and uses.
Synthetic dyestuff have complicated aromatic hydrocarbon molecular structure, and are of a great variety, are difficult to biological degradation.Some dyestuff or its degraded product have strong carcinogenic, teratogenesis, mutagenic effect, thereby the water body of dye discoloration is processed to have become one of difficult problem to be solved is arranged.It is reported that commercial dyes has 10,000 kinds approximately, the ultimate production of annual dyestuff is 600,000 tons, and China's annual production has reached 150,000 tons, and nearly 10% ~ 20% dyestuff can directly enter environment with water in the production process.Waste water from dyestuff often has the characteristics such as colourity height, toxicity be large.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.
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 not consider the separately deficiency of the characteristics of waste water for overcoming when various wastewater needs individual curing or various wastewater to mix stack in the prior art, a kind of method of processing simultaneously industrial acid-washed waste water, 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) collects pickling waste waters and filtration removal solid particulate wherein, analyze wherein Fe
2+And Fe
3+The concentration of ion is regulated by adding other trivalent metal salts and divalent metal salt, so that bivalent ions volumetric molar concentration is 2 ~ 4 times of volumetric molar concentration of trivalent ion;
2) be that 3:1 ~ 4:1 mixes by volume with acid pickling and rust removing waste water and dyeing waste water, in composite waste, drip 50% ~ 70% NaOH solution, until stirred 60～120 minutes during dropping pH value to 8 ~ 10 under 300 ~ 400 rpm;
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 to utilize the preparation principle of organic hydrotalcite, metal ion in the acid pickling and rust removing waste water and the dyestuff ion in the dyeing waste water are prepared into organic hydrotalcite, and be directly used in the organic pollutant that adsorbs in the chemical industrial organic wastewater, by precipitation pollutent is separated from water at last.The present invention has utilized metal ion and organic anion in the waste water according to the characteristic of waste water, and the treatment of wastes with processes of wastes against one another is simple, inexpensive easy popularization.
Embodiment
Pickling waste waters is collected, surveyed its pH value, if pH is excessively low, some scrap iron of input that can be as much as possible wherein acid consume, and one side increases Fe
2+And Fe
3+The concentration of ion can reduce the add-on of follow-up alkali on the other hand.Filter and remove the pickling waste waters solid particulate, analyze wherein Fe
2+And Fe
3+The concentration of ion, and regulate trivalent metal salt such as comparatively cheap Al by adding other trivalent metal salts and divalent metal salt
3+, Fe
3+Deng, divalent metal salt such as comparatively cheap Mg
2+, Fe
2+Deng, guarantee that bivalent ions volumetric molar concentration is 2 ~ 4 times of volumetric molar concentration of trivalent ion.With acid pickling and rust removing waste water and dyeing waste water by volume 3:1 ~ 4:1 mix, in composite waste, drip fast 50% ~ 70% NaOH solution, until regulate till pH value to 8 ~ 10, during dropping under 300 ~ 400 rpm rapid stirring 60～120 minutes.Add chemical industrial organic wastewater, the water yield is 1 ~ 4 times of dyeing waste water, after wastewater from chemical industry adds, composite waste before fully mixes 2 ~ 4 h, 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
Pickling waste waters is collected, surveyed its pH value, pH is 3.2, some scrap iron of input as much as possible and rust iron, and wherein acid consumes, and increases on the one hand Fe
2+And Fe
3+The concentration of ion can reduce the add-on of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particulate, analyze wherein Fe
2+And Fe
3+The concentration of ion, and by adding a small amount of AlCl
3, guarantee that the divalent ion volumetric molar concentration is 2 times of trivalent ion volumetric molar concentration; In pickling waste waters, drip fast 70% NaOH solution adjusting pH value to 10, during dropping under 400 rpm rapid stirring 120 minutes, add chemical industrial organic wastewater, the water yield is 1 times (volume ratio) of dyeing waste water, after wastewater from chemical industry adds, composite waste before fully mixes 2 h, precipitation is separated, and the pollutent in the composite waste can be removed along with precipitation, add at last hydrochloric acid, regulate about pH to 7.
Measure the water quality of processed waste water, by analysis Fe in the composite waste
2+And Fe
3+The concentration of ion and COD, clearance are respectively 97.2%, 98.5% and 96.9%.
Embodiment 2
Pickling waste waters is collected, surveyed its pH value, pH is 3.8, some scrap iron of input as much as possible and rust iron, and wherein acid consumes, and increases on the one hand Fe
2+And Fe
3+The concentration of ion can reduce the add-on of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particulate, analyze wherein Fe
2+And Fe
3+The concentration of ion, and by adding a small amount of MgCl
2Regulate, guarantee that the divalent ion volumetric molar concentration is 4 times of trivalent ion volumetric molar concentration; In pickling waste waters, drip fast 50% NaOH solution adjusting pH value to 8, during dropping under 300 rpm rapid stirring 60 minutes, add chemical industrial organic wastewater, the water yield is 4 times (volume ratios) for dyeing waste water, 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.
With the water quality of this aquametry processed waste water, Fe in the composite waste by analysis
2+And Fe
3+The concentration of ion and COD, clearance are respectively 96.2%, 97.9% and 95.5%.
Embodiment 3
Pickling waste waters is collected, surveyed its pH value, pH is 2.8, some scrap iron of input as much as possible and rust iron, and wherein acid consumes, and increases on the one hand Fe
2+And Fe
3+The concentration of ion can reduce the add-on of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particulate, analyze wherein Fe
2+And Fe
3+The concentration of ion guarantees that the divalent ion volumetric molar concentration is 3 times of trivalent ion volumetric molar concentration; In pickling waste waters, drip fast 60% NaOH solution adjusting pH value to 9, during dropping under 350 rpm rapid stirring 90 minutes, add chemical industrial organic wastewater, the water yield is 3 times (volume ratios) for dyeing waste water, after wastewater from chemical industry adds, composite waste before fully mixes 3 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.
With the water quality of this aquametry processed waste water, Fe in the composite waste by analysis
2+And Fe
3+The concentration of ion and COD, clearance are respectively 96.9%, 98.7% and 97.2%.
Claims (2)
1. method of processing simultaneously industrial acid-washed waste water, dyeing waste water and chemical industrial organic wastewater is characterized in that in turn including the following steps:
1) collects pickling waste waters and filtration removal solid particulate wherein, analyze wherein Fe
2+And Fe
3+The concentration of ion is regulated by adding other trivalent metal salts and divalent metal salt, so that bivalent ions volumetric molar concentration is 2 ~ 4 times of volumetric molar concentration of trivalent ion;
2) be that 3:1 ~ 4:1 mixes by volume with acid pickling and rust removing waste water and dyeing waste water, in composite waste, drip 50% ~ 70% NaOH solution, until stirred 60～120 minutes during dropping pH value to 8 ~ 10 under 300 ~ 400 rpm;
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.
2. the method for processing simultaneously industrial acid-washed waste water, dyeing waste water and chemical industrial organic wastewater according to claim 1 is characterized in that: in the step 1), measure the pH value of collected pickling waste waters, if pH is excessively low, drop into scrap iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104915161A CN102976515A (en) | 2012-11-28 | 2012-11-28 | Method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104915161A CN102976515A (en) | 2012-11-28 | 2012-11-28 | Method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater |
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|---|---|
| CN102976515A true CN102976515A (en) | 2013-03-20 |
Family
ID=47850932
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|---|---|---|---|
| CN2012104915161A Pending CN102976515A (en) | 2012-11-28 | 2012-11-28 | Method for simultaneously treating industrial pickling wastewater, printing and dyeing wastewater and chemical industrial organic wastewater |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272806A (en) * | 1997-10-02 | 2000-11-08 | 水农业德国有限公司 | Method for producing anion-exchanging mineral and use of said mineral |
| 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 |
| WO2010105303A1 (en) * | 2009-03-20 | 2010-09-23 | Commonwealth Scientific And Industrial Research Organisation | Treatment or remediation of natural or waste water |
-
2012
- 2012-11-28 CN CN2012104915161A patent/CN102976515A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272806A (en) * | 1997-10-02 | 2000-11-08 | 水农业德国有限公司 | Method for producing anion-exchanging mineral and use of said mineral |
| 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 |
| WO2010105303A1 (en) * | 2009-03-20 | 2010-09-23 | Commonwealth Scientific And Industrial Research Organisation | Treatment or remediation of natural or waste water |
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Application publication date: 20130320 |