CN101475272A - Pretreatment process for oily watewater of cold rolling mill - Google Patents
Pretreatment process for oily watewater of cold rolling mill Download PDFInfo
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- CN101475272A CN101475272A CNA2009100606241A CN200910060624A CN101475272A CN 101475272 A CN101475272 A CN 101475272A CN A2009100606241 A CNA2009100606241 A CN A2009100606241A CN 200910060624 A CN200910060624 A CN 200910060624A CN 101475272 A CN101475272 A CN 101475272A
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Abstract
The invention relates to a process for pre-treating wastewater containing oil of a cold rolling mill, which solves the problems of poor demulsification effect, high investment, high energy consumption, low recovery rate of waste oil, mass waste residue generation and substandard treated effluent existing in the prior process for pre-treating wastewater containing oil of the cold rolling mill. Recycling of waste oil can be realized through acidification demulsification, oil reclaiming treatment, re-demulsification treatment, flocculation treatment and air floatation separation by steam introduction and the acidification demulsification, so that reclamation rate of the waste oil is improved, energy consumption and investment are reduced, the amount of the waste residue is small, and each index of the pretreated wastewater can be reduced to meet the requirement of secondary treatment so as to greatly reduce the load of the secondary treatment.
Description
Technical field
The present invention relates to the metallurgy industry waste water treatment process, specifically a kind of pretreatment technology of oily wastewater of cold rolling mill.
Background technology
Cold rolling oily(waste)water is mainly between milling train unit, grinding roller and the oil depot draining of band steel degreasing unit, smooth unit and each unit etc., is one of the most unmanageable waste water of steel industry.Oily(waste)water can be divided into oil slick, dispersed oil, oil in water emulsion, dissolving oil and oily two solidss according to the form and the stalling characteristic of oil.Wherein oil in water emulsion is the milkiness shape in sewage, oil droplet size is generally 0.1～25 μ m, the electronegative hydration shell of oil droplet appearance parcel one deck, and emulsification is steady state under the Action of Surfactant in water, the elaioleucite stable for extended periods of time is difficult to separate with the method for machinery.The principal feature of Steel Mill's oily(waste)water is: 1. organic content height is generally COD
Cr10000～25000mg/L; 2. complex chemical composition, main component has oiliness improver, rust-inhibiting additive, hydrotropy additive and emulsifying agent etc., and 3. oily sub content height is between 1%～8% quality.Tens thousand of tons of oily(waste)waters of the annual discharge of Wuhan Iron ﹠ Steel's cold rolling mill, pollution intensity is very big.
Oily(waste)water is handled finally all needs to carry out biochemical treatment with the assurance effluent quality, thereby the pre-treatment of biochemical treatment front seems particularly important.Preconditioning technique for the waste water of low oil in water emulsion content mainly comprises two classes, and (1) is the membrane filtration technique of representative with the ultrafiltration, and wherein adding the contact oxidation style with ceramic membrane filter is that the treatment process of core is used the most general at present.The maximum deficiency that adopts this method to handle oily(waste)water is the effluent quality instability after handling, and often not up to standard, the effect of each big steel enterprise is all undesirable at home.Its major cause is that the emulsion oily(waste)water that saponification deg is higher, molecular chain is long can stop up the ultra-filtration membrane surface, can't go on ultrafiltration, thereby can't remove deliquescent COD.This method floor space is big simultaneously, investment is very high.(2) with the breakdown of emulsion be the Chemical Pretreatment technology of representative, usually adopting a chemical demulsification to add air supporting handles, cold rolling oily(waste)water treatment effect for high density is also undesirable, it is main because the excessive concentration of (1) such oily(waste)water only relies on normally used emulsion splitter (as gathering aluminium etc.) to carry out a breakdown of emulsion and can't reach the ideal treatment effect with this understanding; (2) the oily(waste)water temperature is lower, generally is lower than 60 ℃, can influence separating out of oil content.Oily(waste)water oil-contg through this pretreatment technology is reduced to 30mg/L, COD at most
CrReduce to 2000mg/L at most, thereby increase the second-stage treatment load, have a strong impact on the second-stage treatment effect, directly cause discharge of wastewater not up to standard.
With regard to the cold rolling oily(waste)water of steel industry, research can be reclaimed oily substance, efficient breakdown of emulsion, and for the secondary Waste Water Treatment provides the preconditioning technique of good influent quality, for guaranteeing that the stably reaching standard discharging after cold rolling oily(waste)water is handled and the realization of steel industry target for energy-saving and emission-reduction have crucial meaning.
Summary of the invention
To the objective of the invention is in order solving the problems of the technologies described above, to provide that a kind of cost of investment is low, energy consumption is low, maintenance cost is low, demulsification is good, secondary pollution is little, the waste oil rate of recovery is high and the pretreatment technology of the oily wastewater of cold rolling mill of good influent quality is provided for biochemical secondary Waste Water Treatment.
Technical scheme comprises the steps:
(1) acidifying breakdown of emulsion, recovery of oil are handled: the oily(waste)water in the equalizing tank is heated to 60 ℃-70 ℃, and regulates pH between 3.0-4.0, preferred concentrated nitric acid is regulated pH value, reacts 3-5 hour, collects the oil content that floats over the waste water top layer by floating oil collecting device;
(2) breakdown of emulsion is handled once more: the waste water after will handling through recovery of oil is sent in the flocculation groove, regulates pH at 7.0-8.5, and the adding emulsion splitter carries out breakdown of emulsion to be handled;
(3) flocculation treatment: waste water adds flocculation agent and carries out flocculation reaction in the flocculation groove;
(4) dissolved air flotation: the waste water after the flocculation treatment is sent into air flotation slot, and the scum silica frost that the come-up effect by micro-bubble produces flocculation separates, and promptly finishes pretreatment technology after the air supporting water outlet.
Waste water in the described step (1) in the equalizing tank adopts and feeds steam heating.
Described step (2) uses sodium hydroxide to regulate pH value.
Emulsion splitter in the described step (2) is the composite demulsifying agent of bodied ferric sulfate and polymerize aluminum chloride, both mass ratio 8-12: 1, and preferred 10: 1, the concentration that adds in the waste water was 400-800mg/L, stirring reaction 10-30min.
In the described step (4), add flocculation agent in the pipeline before waste water enters air flotation slot, the concentration that adds in the waste water is 1-2mg/L, strengthens flocculation reaction by adding micro-flocculation agent, so that scum silica frost fully separates, strengthens air flotation effect.
Flocculation agent in described step (3) and the step (4) is an anion-polyacrylamide, and wherein the concentration that flocculation agent adds in the waste water in step (3) is 15-20mg/L, flocculation reaction 10-20 minute.
The present invention has adopted breakdown of emulsion twice, carries out the acidifying breakdown of emulsion when at first oily(waste)water being heated, and re-uses emulsion splitter and carries out the breakdown of emulsion processing once more, and is good especially for the oily wastewater of cold rolling mill demulsification of high density.By discovering in a large number, react by regulating between the oily(waste)water PH3.0-4.0, can make the most of oil content (comprise oil in water emulsion, oil slick and disperse wet goods) in the oily(waste)water float to the top layer, the oil content that obtains by this step is important industrial raw material, can be used for preparation and refine multiple petroleum chemicals, when pre-treatment reduction contaminated wastewater degree guarantees follow-up second-stage treatment effect, and the recycling of realization oil content.COD in the waste water after acidified breakdown of emulsion, recovery of oil are handled
CrDrop to 5000-10000mg/L, oil-contg can be reduced to 150mg/L.Described acid adjustment can be adopted acid regulators such as sulfuric acid, nitric acid, but consider that minimizing pretreatment technology and subsequent technique relevant device major part is ferrous materials, especially preferably adopt concentrated nitric acid to regulate, it can reduce the corrosion of equipment than other acid regulator, prolongs service life of equipment.
Described floating oil collecting device is the existing various equipment that can be used for the liquid level floating oil collecting, as the oil skimming machine sold on the market, strain oily device, tubular type oil receiving equipment, Float cylinder type steel band oil receiving equipment etc.
In step (2), will pump into through the waste water after acidifying breakdown of emulsion, recovery of oil are handled in the flocculation groove and further carry out the processing of secondary breakdown of emulsion.Because through acidifying breakdown of emulsion, reclaimed a large amount of oil contents, the content of oil descends in the waste water, emulsion splitter can be selected the various oily(waste)water emulsion splitters that are used for commonly used at present for use here, as polymerize aluminum chloride, bodied ferric sulfate, Tai-Ace S 150 or other emulsion splitter.But for the consideration to the demulsification optimum, the contriver has selected the composite demulsifying agent that contains bodied ferric sulfate and polymerize aluminum chloride for use through groping for many years, its mass ratio is 8-12: 1, be preferably 10: 1, the concentration in every liter of waste water is 400-800mg, stirring reaction 10-30min.Bodied ferric sulfate and polymerize aluminum chloride composite demulsifying agent are metal salt compound, add in the emulsifiable oil waste water, and its positively charged ion has removes tensio-active agent that the oil in water emulsion interface exists and the effect that suppresses electrostatic double layer, and oil droplet is removed through aggegation, absorption.The characteristics of inorganic emulsion splitter breakdown of emulsion are that effect stability, processing costs are lower, in conjunction with air-float technology, add an amount of aluminium salt and help pneumatically supported scum silica frost come-up.
Flocculation agent also can be selected for use existing as cation polypropylene phthalein amine, polyacrylonitrile in step (3), flocculation agents commonly used such as polyamine, polyethers, natural modified thing, preferred anionic polyacrylamide (PAM) uses as flocculation agent, experimental results show that its flocculating effect is best, concentration in every liter of waste water is 15-20mg, flocculation reaction 10-20 minute.
When in step (2), waste water being regulated pH value, can select alkaline conditioner commonly used at present for use, as sodium bicarbonate, oxygen potassium oxide, sodium hydroxide etc., preferred especially sodium hydroxide, mainly be because it regulates waste water pH value and when reacting, the waste residue that produces in the waste water is less, can further reduce the secondary pollution of waste residue.
After the waste water after breakdown of emulsion and the flocculation reaction enters air flotation slot carries out solid-liquid separation and handle, the scum silica frost that the come-up effect by micro-bubble produces flocculation separates, and the oil-contg in the waste water is reduced to below the 10mg/L, COD
CrBe reduced to below the 1000mg/L, final outflow water enters the subsequent disposal unit.
Pretreatment technology of the present invention adopts breakdown of emulsion twice, be that the acidifying breakdown of emulsion reclaims oil content and selects the further breakdown of emulsion of special composite demulsifying agent for use, carry out flocculation treatment and dissolved air flotation again, make the cold rolling oily(waste)water of high density after pre-treatment, oil and COD concentration reduce greatly, oil-contg is reduced to below the 10mg/L, COD
CrBe reduced to below the 1000mg/L, the every index of waste water is reduced to the requirement of second-stage treatment.Its cost of investment is low, energy consumption is low, maintenance cost is low, demulsification is good, waste residue is few, secondary pollution is little, can guarantee the efficient stable operation of follow-up second-stage treatment, alleviates the load of second-stage treatment.And waste oil rate of recovery height, 1 ton of oil content content of every processing is about about 50 kilograms of 7% the recyclable oil content of oily(waste)water, a large amount of oil contents of collecting can recycling, create economic benefit, significant aspect energy-saving and emission-reduction that promote enterprise and Sustainable development, be not only applicable to the pre-treatment of oily wastewater of cold rolling mill, be applicable to the pre-treatment of other industry mechanical cutting liquid emulsifying liquid waste water yet.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Wherein 1-equalizing tank, 2-air-floating apparatus, 3-pump, 4-flocculation groove, 5-vapour floating trough, M represent motor.
Embodiment
Below in conjunction with accompanying drawing the present invention is further explained explanation:
With reference to Fig. 1, the pretreatment technology of oily wastewater of cold rolling mill is specially following step:
(1) recovery of oil is handled; In equalizing tank 1, feed steam, heating oily(waste)water temperature to 60 ℃-70 ℃, and add concentrated nitric acid (more than concentration 30% quality) adjusting pH between 3.0-4.0, and reacted 3-5 hour, collect the oil content that floats over the waste water top layer by floating oil collecting device 2 (oil skimming machine);
(2) breakdown of emulsion is handled: the waste water after will handling through recovery of oil pumps in the flocculation groove 4, add sodium hydroxide and regulate pH at 7.0-8.5, the composite demulsifying agent that adds bodied ferric sulfate and polymerize aluminum chloride carries out breakdown of emulsion to be handled, both mass ratio 8-12:1, the concentration that adds in the waste water is 400-800mg/L, stirring reaction 10-30min.
(3) flocculation treatment: adding flocculation agent is that anion-polyacrylamide carries out flocculation reaction, and the concentration that adds in the waste water is 15-20mg/L, flocculation reaction 10-20 minute.
(4) dissolved air flotation: the waste water after the flocculation treatment is sent into air flotation slot 5, and add the flocculation agent anion-polyacrylamide that concentration is 1-2mg/L in the pipeline before entering air flotation slot 5, to strengthen air flotation effect, come-up effect by micro-bubble fully separates the scum silica frost of flocculation generation, promptly finishes pretreatment technology after the air supporting water outlet.
Claims (7)
1, a kind of pretreatment technology of oily wastewater of cold rolling mill is characterized in that, comprises the steps:
(1) acidifying breakdown of emulsion, recovery of oil are handled: the oily(waste)water in the equalizing tank is heated to 60 ℃-70 ℃, and regulates pH between 3.0-4.0, reacted 3-5 hour, collect the oil content that floats over the waste water top layer by floating oil collecting device;
(2) breakdown of emulsion is handled once more: the waste water after will handling through recovery of oil is sent in the flocculation groove, regulates pH at 7.0-8.5, and the adding emulsion splitter carries out breakdown of emulsion to be handled;
(3) flocculation treatment: the waste water in the flocculation groove adds flocculation agent and carries out flocculation reaction;
(4) dissolved air flotation: the waste water after the flocculation treatment is sent in the air flotation slot, and the scum silica frost that the come-up effect by micro-bubble produces flocculation separates, and promptly finishes pretreatment technology after the air supporting water outlet.
2, the pretreatment technology of oily wastewater of cold rolling mill as claimed in claim 1 is characterized in that, adopts concentrated nitric acid to regulate the pH value in the described step (1).
3, the pretreatment technology of oily wastewater of cold rolling mill as claimed in claim 1 or 2 is characterized in that, adopts the mode that feeds steam that the oily(waste)water in the equalizing tank is heated in the described step (1).
4, the pretreatment technology of oily wastewater of cold rolling mill as claimed in claim 1 is characterized in that, described step (2) adopts sodium hydroxide to regulate pH value.
5, as the pretreatment technology of claim 1 or 4 described oily wastewater of cold rolling mill, it is characterized in that, emulsion splitter in the described step (2) is the composite demulsifying agent of bodied ferric sulfate and polymerize aluminum chloride, both mass ratio 8-12: 1, the concentration that adds in the waste water is 400-800mg/L, stirring reaction 10-30min.
6, the pretreatment technology of oily wastewater of cold rolling mill as claimed in claim 1 is characterized in that, in the described step (4), adds the flocculation agent that concentration is 1-2mg/L in the pipeline before waste water enters air flotation slot.
7, as the pretreatment technology of claim 1 or 6 described oily wastewater of cold rolling mill, it is characterized in that, flocculation agent in described step (3) and the step (4) is an anion-polyacrylamide, wherein the concentration that flocculation agent adds in the waste water in step (3) is 15-20mg/L, flocculation reaction 10-20 minute.
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| CNA2009100606241A CN101475272A (en) | 2009-01-22 | 2009-01-22 | Pretreatment process for oily watewater of cold rolling mill |
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