CN102974309A - Method for simultaneously processing industrial pickling waste water and washing waste water - Google Patents
Method for simultaneously processing industrial pickling waste water and washing waste water Download PDFInfo
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- CN102974309A CN102974309A CN2012104916003A CN201210491600A CN102974309A CN 102974309 A CN102974309 A CN 102974309A CN 2012104916003 A CN2012104916003 A CN 2012104916003A CN 201210491600 A CN201210491600 A CN 201210491600A CN 102974309 A CN102974309 A CN 102974309A
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Abstract
The invention discloses a method for simultaneously processing industrial pickling waste water and washing waste water in the field of environmental pollution control. The method for simultaneously processing the industrial pickling waste water and washing waste water comprises the following steps of: collecting acid pickling dust removal waste water, filtering solid particles in the acid pickling dust removal waste water, analyzing the concentration of Fe<2+> ions and the concentration of Fe<3+> ions, and adding other trivalent metal salt and divalent metal salt to adjust the molar concentration of divalent ions and trivalent ions so as to enable the molar concentration of divalent ions to be 2-4 times of the molar concentration of trivalent ions; mixing the acid pickling dust removal waste water and the washing waste water according to the volume ratio of (3:1)-(6:1), dripping a 50%-70% NaOH solution into mixed waste water, adjusting the pH value to 8-10, stirring the mixed waste water for 60-120 minutes at 300-400 rpm in the dripping process, and precipitating and separating the mixed waste water; and adding hydrochloric acid or sulfuric acid to adjust the pH until the pH is 7. Organic hydrotalcite obtained by synthesis can be used as an absorbent material to be used in environmental management.
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 and washes.
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 Machining processing of steel rolling member, need to remove component surface rustization layer.The steel rolling component surface is processed processing, can strengthen its tolerance, prolong its service life.The removing of steel rolling component surface rustization layer mainly contains physical method, chemical method 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 method 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 method is processed still unsatisfactory part, such as pollution surrounding environment such as pickle liquors.Along with expanding economy, steel and iron industry and iron and steel manufacturing industry 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 constituent 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 acid cleaning process produces
2+And Fe
3+Therefore ion, can be used as resource and uses.Absorption method mainly contains Vacuum Concentration freeze crystallization (reduction vaporization freeze crystallization), acid adding freeze crystallization (without the evaporative freezing crystallisation), spontaneous nucleation diffusive dialysis method, polymeric ferrous sulphate process, adds iron filings production ferrous sulfate Lung biopsy at present, front four kinds of methods exist mostly that equipment investment is large, complex process, the demanding shortcoming of operating technology, the applicable larger enterprise of spent acid amount that processes.Add iron filings and produce the ferrous sulfate method for the waste water that contains multiple other metal ions because the Crystallization Separation weak effect can affect product purity.
Contain surfactant (mainly being that anion surfactant is such as long alkyl chain length sulfonate) in the washes, sodium phosphate trimer, the auxiliary agents such as carboxymethyl cellulose, greasy dirt, dust particle and various microorganisms etc., outward appearance is muddy, COD is 300～800mg/l, pH is 6.5～7.5, and suspension content is higher, generally at 500～1200mg/l.Phosphate enters the eutrophication that water body can cause water body.After surfactant enters water body, aquatic animal,plants is poisoned cause death, make some micropollutants solubilising in the water, thereby increase the difficulty that water supply plant is processed; When entering washing agent in municipal sewage plant's sewage and reaching finite concentration, can affect many processes such as aeration, precipitation, sludge digestion.
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 layer structure that it is unique and laminate element and interlayer anion gets more and more people's extensive concerning, introduce new object anion through ion-exchange to interlayer and can make layer structure and composition produce corresponding the variation, thereby can prepare the functional material that a large class has special nature.Hydrotalcite material belongs to anion type laminated compound.The compounds that lamellar compound refers to have layer 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 anion; M
3+Be Al
3+, Cr
3+, Fe
3+, Co
3+Deng the trivalent metal anion; A
N-Be anion, 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 complex ion, different when the interlayer inorganic anion, the interlamellar spacing of hydrotalcite is different, and after hydrotalcite adsorption fouling thing, interlamellar spacing also can increase, to hold more pollutant simultaneously.
At present, the synthetic method of hydrotalcite-like material mainly contains salt-alkaline process, salt-conventional ceramic technique and ion-exchange, also derives Hydrolyze method, hydro-thermal method, the again hydration method of heat treatment etc. of inducing.Wherein the most frequently used method is coprecipitation, namely with the metallic ion mixed liquor that consists of the hydrotalcite layer co-precipitation occurs under the effect of alkali at a certain temperature and prepares.The method is simple to operation, is the preparation method who commonly uses, and needs to utilize a certain amount of bivalent metal ion and trivalent metal ion in the method, has increased input from the angle of economy; From the synthetic process of the angle of administering environment, increased the generation of waste water, environmental improvement has been proposed new problem.
Summary of the invention
The objective of the invention is to prepare the deficiency that organic hydrotalcite also is used for wastewater treatment in the prior art for overcoming, a kind of method of processing simultaneously industrial acid-washed waste water and washes is provided.
The technical solution used in the present invention is in turn include the following steps:
1) collects acid pickling and rust removing waste water and filtration removal solid particle 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 molar concentration is 2 ~ 4 times of molar concentration of trivalent ion;
2) be that 3:1 ~ 6:1 mixes by volume with acid pickling and rust removing waste water and washes, drip 50% ~ 70% NaOH solution in composite waste, regulate till pH value to 8 ~ 10, stirred under 300 ~ 400 rpm 60～120 minutes during dropping, precipitation is separated;
3) 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 anion in the washes are prepared into organic hydrotalcite, precipitation is separated from water, and the synthetic organic hydrotalcite that obtains can also as sorbing material, be used for environmental improvement.
The specific embodiment
With the acid pickling and rust removing wastewater collection, survey its pH value, if pH is excessively low, some scrap iron of input as much as possible wherein acid consume, and increase on the one hand Fe
2+And Fe
3+The concentration of ion can reduce the addition of follow-up alkali on the other hand.Filter and remove acid pickling and rust removing wastewater solids particle, analyze wherein Fe
2+And Fe
3+The concentration of ion, and by adding other trivalent metal salts (such as comparatively cheap Al
3+, Fe
3+) and divalent metal salt (such as comparatively cheap Mg
2+, Fe
2+) regulate, guarantee that the divalent ion molar concentration is 2 ~ 4 times of trivalent ion molar concentration; With acid pickling and rust removing waste water and by volume 3:1 ~ 6:1 mixing of washes, in composite waste, drip fast 50% ~ 70% NaOH solution, be till 8 ~ 10 until be adjusted to the pH value, during dropping under 300 ~ 400 rpm rapid stirring 60～120 minutes, precipitation is separated, and the pollutant in the composite waste can be removed along with precipitation, add at last hydrochloric acid or sulfuric acid, regulate about pH to 7.
3 embodiment of the present invention below further are provided:
Embodiment 1
With the acid pickling and rust removing wastewater collection, survey its pH value, pH is 3.2, some scrap iron of input as much as possible and rust iron, wherein acid consumes, and increases on the one hand Fe
2+And Fe
3+The concentration of ion can reduce the addition of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particle, analyze wherein Fe
2+And Fe
3+The concentration of ion adds a small amount of AlCl
3, guarantee that the divalent ion molar concentration is 4 times of trivalent ion molar concentration; With acid pickling and rust removing waste water and by volume 6:1 mixing of washes, in composite waste, drip fast 70% NaOH solution adjusting pH value to 10, during dropping under 400 rpm rapid stirring 120 minutes, precipitation, separate, pollutant in the composite waste can be removed along with precipitation, adds at last hydrochloric acid or sulfuric acid, regulates 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 96.1%, 98.6% and 98.4%.
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 addition of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particle, analyze wherein Fe
2+And Fe
3+The concentration of ion adds a small amount of MgCl
2, guarantee that the divalent ion molar concentration is 2 times of trivalent ion molar concentration; With acid pickling and rust removing waste water and by volume 3:1 mixing of washes, in composite waste, drip fast 50% NaOH solution adjusting pH value to 8, during dropping under 300 rpm rapid stirring 60 minutes, precipitation, separate, pollutant in the composite waste can be removed along with precipitation, adds at last hydrochloric acid or sulfuric acid, regulates 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 95.6%, 97.5% and 98.6%.
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 addition of follow-up alkali on the other hand; Filter and remove the pickling waste waters solid particle, analyze wherein Fe
2+And Fe
3+The concentration of ion, divalent ion molar concentration are 2 times of trivalent ion molar concentration; With acid pickling and rust removing waste water and by volume 5:1 mixing of washes, in composite waste, drip fast 60% NaOH solution adjusting pH value to 9, during dropping under 350 rpm rapid stirring 90 minutes, precipitation, separate, pollutant in the composite waste can be removed along with precipitation, adds at last hydrochloric acid or sulfuric acid, regulates 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 95.7%, 97.6% and 98.8%.
The organic hydrotalcite that precipitation is obtained is for the treatment of the organic wastewater of the nitrobenzene that contains 15 mg/L, and the handled wastewater volume that every gram organic hydrotalcite is corresponding is about 1 L, rapid stirring 60 minutes; Product stopped 30 minutes at sedimentation basin, Separation of Solid and Liquid, and ultraviolet-uisible spectrophotometer is measured supernatant concentration, and pollutants removal rate is 92.7%.
Claims (2)
1. method of processing simultaneously industrial acid-washed waste water and washes is characterized in that in turn including the following steps:
1) collects acid pickling and rust removing waste water and filtration removal solid particle 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 molar concentration is 2 ~ 4 times of molar concentration of trivalent ion;
2) be that 3:1 ~ 6:1 mixes by volume with acid pickling and rust removing waste water and washes, drip 50% ~ 70% NaOH solution in composite waste, regulate till pH value to 8 ~ 10, stirred under 300 ~ 400 rpm 60～120 minutes during dropping, precipitation is separated;
3) add hydrochloric acid or sulfuric acid, regulate pH to 7.
2. a kind of method of processing simultaneously industrial acid-washed waste water and washes according to claim 1 is characterized in that: in the step 1), the pH value of the acid pickling and rust removing waste water of measurement collection if pH is excessively low, drops into scrap iron.
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|---|---|---|---|
| CN2012104916003A CN102974309A (en) | 2012-11-28 | 2012-11-28 | Method for simultaneously processing industrial pickling waste water and washing waste water |
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|---|---|---|---|
| CN2012104916003A CN102974309A (en) | 2012-11-28 | 2012-11-28 | Method for simultaneously processing industrial pickling waste water and washing waste water |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-11-28 CN CN2012104916003A patent/CN102974309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20130320 |