CN101172743A - Combination technique for processing and recycling high-cyanogen high-ammonia high-salt organic waste water - Google Patents
Combination technique for processing and recycling high-cyanogen high-ammonia high-salt organic waste water Download PDFInfo
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- CN101172743A CN101172743A CNA2007101672580A CN200710167258A CN101172743A CN 101172743 A CN101172743 A CN 101172743A CN A2007101672580 A CNA2007101672580 A CN A2007101672580A CN 200710167258 A CN200710167258 A CN 200710167258A CN 101172743 A CN101172743 A CN 101172743A
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Abstract
The invention relates to a combined technique of treating and reusing the organic sewage which is rich in cyanogen, ammonia and salt, and adopts the combined techniques of acidified decyanation (with the sodium cyanide recollected), basified ammonia blowing (with ammonium salt recollected), oxidation by adding chlorine, biological treatment, precipitation and clarification, deep oxidation, biological active carbon filtering, one-time brine refining, microstraining film, and other combined techniques, and then the chlorine alkali is produced after the secondary brine refining in the chlorine alkali industry and the entrance into the ionic membrane electrobath. The combined technique can be used for treating the industrial sewage in the tricyanogen chloride, chlorine alkali, gold mine, galvanization and other industries and conduct recovery of the resources, thereby overcoming the disadvantages that the prior art has narrow applicability and treatment function and disappointing treatment result, cannot recollect the resources, and has high treatment cost and unobvious economical benefit. The combination of the technique is scientific and reasonable, the technique is novel, unique and mature, the treatment is good, and the combined technique has a plurality of functions, strong applicability, wide use range and remarkable environmental and economical benefit.
Description
Technical field
The present invention relates to a kind of Industrial Wastewater Treatment of high cyanogen, high ammonia nitrogen, high salt, high organic concentration and combination process that resource reclaims of containing, for example processing and the resource to chemical industry trade effluents such as cyanuric chloride, chlor-alkalis reclaims.
Background technology
The production technique waste water of cyanuric chloride, water quality is abominable, COD:1500～3500mg/L, total cyanide is (with CN
-Meter) content is 200～800mg/L, ammonia nitrogen (NH
3-N) content is 400～1000mg/L, sodium formiate (HCOONa): 3500～4200mg/L, total organic charcoal (TOC): 500～1500mg/L, sodium-chlor (NaCl): 18%～20%.This trade effluent that has sodium-chlor, organism, ammonia nitrogen and the highly toxic prussiate of high density simultaneously, handle up to standard, and accomplish that resource (as sodium-chlor, ammoniacal liquor, sodium cyanide etc.) reclaims, and handle standard (Fe:＜1mg/L, SiO that back water quality reaches a refined brine of chlor-alkali industry ion-exchange membrane electrolyzer
2:＜11mg/L, SO
4 2-:＜7g/L, ClO
3 -:＜15g/L, SS:＜2mg/L, CN
-:＜0.5mg/L, Fe (CN)
6 4:＜55 μ g/L, TOC:＜10mg/L, total ammonium (NH
4):＜4mg/L),, can't accomplish by traditional single sewage treatment process.So the processing and the reuse of cyanuric chloride production technique waste water also do not have engineering example at present.This also is the initiative and mystique of combination process of the present invention.In view of there not being case history and the related background art handle high density chlorination sodium, organism, ammonia nitrogen and highly toxic prussiate trade effluent simultaneously, the patent that the present invention can only retrieve some single or above-mentioned pollutents of partially disposed is technology as a setting.
Chinese patent " process for treatment of waste water containing cyanogen by acidifying precipitation method " (notification number CN1144194) discloses a kind of process for treatment of waste water containing cyanogen by acidifying precipitation method, is suitable for handling the cyanide wastewater in the cyanidation gold-extracted production.It is by the waste water acidifying is generated copper, zinc, iron, plumbous plasma the indissoluble throw out and removes from waste water, again with in the milk of lime and sulfate radical is formed calcium sulfate precipitation from waste water, separate, prussiate still exists in the waste water with the form that can discharge cryanide ion, and circulation is used for cyaniding and leaches.This technology makes that processed waste water recycles, less investment, technology is simple to operation, processing cost is low.But this technology there is no the decyanation function, just removes impurity metal ion, and with the prussiate recycling use of purifying; The use of organic floculant polyacrylamide, it is residual will to cause increasing of TOC, and neutralize with liming, will cause exceeding standard of calcium ion, and these all can increase the difficulty of follow-up salt refining.
Chinese patent " cyan-containing waste water treatment by iron blue method " (notification number CN85100375) discloses a kind of waste water that cyanide content is 30～5000 mg/litre of handling, cyanide wastewater is in the scope of pH4～10, add ferrous salt, remove impurity such as sulfide, cyanide wastewater through purifying adds the soluble ferrite decyanation in the scope of pH value 6～10, the yellow prussiate that decyanization reaction generates obtains being used for the clean of production barba hispanica with strong acid dissolving impurity wherein and starches in vain.This method can make the cyanide content in the cyanide wastewater drop to 0.5～4 mg/litre, and can produce qualified barba hispanica.But this technology water outlet cryanide ion still exceeds standard (national standard of＞0.5mg/L); By product barba hispanica industrial use is little, is worth lowlyer, and cost for purification is higher, and purifying technique is more numerous and diverse.
Chinese patent " a kind of electroplating effluent treatment method " (notification number CN1199872C) discloses a kind of method of handling electroplating wastewater, be characterized in cyaniding plating bath waste water, chromium plating nickel-plating waste water are mixed, add NaOH solution to pH＞8.5, adding its available chlorine then is the oxidizer containing chlorine of cyanogen root quintuple in the solution, be stirred to a large amount of chocolate throw outs precipitation, prussiate decomposes fully, add the ferrous sulfate reductive agent by 28～32 times of amounts of sexavalent chrome in the waste water again, leave standstill out throw out after the stirring and get clear water up to standard.This method technological process is simple, and equipment and structures are few, invests lowly, save to handle medicament, and no burn into treatment capacity is big, can carry out automatization, serialization production.But this technology is deposited the dosage of hypochlorite oxidation agent if control is bad, to there be free chlorine remaining, and free chlorine will be fought for the reductive agent ferrous sulfate with sexavalent chrome, cause the bad calculating of ferrous sulfate dosage to be grasped, thereby cause the waste of material or the decline of treatment effect; Flocculating settling must have the cosedimentation effect of metal ions such as copper, better treatment effect is just arranged, this just must mix copper plating wastewater, nickel-plating waste water and chromium plating wastewater by a certain percentage, better effects is just arranged, this also brings certain limitation (electroplating wastewater not necessarily produces above-mentioned whole three kinds of waste water in the reality, and dosage that perhaps can be is by a certain percentage supplied with) to wastewater treatment.
Chinese patent " a kind of purification process of cyanide-contained solution " (notification number CN1142109C) discloses a kind of purification process of cyanide-contained solution and the recovery method of valence component has been arranged, be to transfer to the tart cyanide-contained solution with activated carbon filtration, because the absorption of gac in acid cyanide-contained solution, filter, adhewsive action, can be effectively with heavy metal, precious metal separates with undesired impurities, realization has the highly enriched of valence component, utilize dilute sulphuric acid acidifying magnesium oxide/absorbent charcoal surface attachments again, carbon surface is broken away from fully because of the epiphragma that adheres to formation, make gac obtain recycling, reach simultaneously and reclaim the purpose that valence component is arranged in the cyanide-contained solution, and making cyanide-contained solution be purified the back reuses, therefore can reduce the prussiate consumption, reduce source of pollution, reduce production costs.But in this technology, metal cyanate salt such as lead, mercury, gold and silver, copper, thiocyanate-are water insoluble, form suspension by charcoal absorption, and the prussiate of basic metal, alkaline-earth metal are dissolved in water, they will enter next procedure through active carbon layer, will be unfavorable for that follow-up brinish is refining; This technology is just purified prussiate and is reclaimed, and there is no the decyanation function; Gac has certain loading capacity, if concentration of metal ions is higher, may cause that active carbon layer penetrates, and causes water quality deterioration; Activation after charcoal absorption is saturated and Treatment for Reuse is more numerous and diverse again, adsorptive power is understable.
Chinese patent " a kind of treatment Methods of Cyanide Wastewater and treatment system thereof " (notification number CN1283568C) discloses a kind of treatment Methods of Cyanide Wastewater and treatment system thereof.This invention is adopted and add acid in the solution of hydrogeneous cyanic acid ion, the pH value of regulator solution, make hydrocyanic ion be converted into prussic acid, with the method for air stripping the prussiate of aqueous phase is transferred in the gas phase again and gone, then the air behind the stripping is handled with hot coke; On treatment system, adopt the method for recirculated air stripping, thereby reduced the air handling amount, reduced processing cost.It only is dilution, diffusion when concentrating the pollutent of discharging to transfer in the gas phase aqueous phase at present that this invention has overcome, and does not reduce the shortcoming of the quantity discharged of pollutent in fact.In addition since the method that has adopted gas-holder the stripping air cycle is used, thereby reduced follow-up treatment of waste gas amount, reduced the cost of investment of enterprise.But this technology can not reclaim prussiate; The design of hot coke pyrolyzer and run parameter are complicated, when going into furnace gases cyanogen fluctuation of concentration or furnace temperature when not enough, may influence treatment effect, and produce new exhaust emission.
Patent " reducing the method for concentration of metal ions in the salt brine solution " (notification number CN99814905.5) discloses the method for multivalent metal cation (as calcium, magnesium, iron, nickel and chromium) concentration in the salt brine solution that a kind of reduction contains water-soluble metal sequestrant (as gluconic acid sodium salt).This method comprises: make salt solution stand elementary brine treatment, the pH that regulates salt brine solution then is to about 1.5～5.5, allow salt brine solution contact with at least a resin bed that contains chelating ion exchange resin, general contact temperature is about 10 ℃～90 ℃, flow velocity is per hour about 4～32 resin bed volumes, recovered brine solution again.But this technology can not remove prussiate and ammonia nitrogen, can not remove organism such as TOC, and the chelating resin gets dependence on import.
Chinese patent " method of organic pollutant in the water is removed in a kind of efficient catalytic ozonize " (notification number CN03150148.6) discloses the method that organic pollutant in the water is removed in a kind of efficient catalytic ozonize.This method with ozone as oxygenant, with a kind of loaded Cu/Al
2O
3Material is as catalyzer, and the ozone gas of finite concentration and flow feeds in the water that contains Persistent organic pollutants continuously and stably, under dynamic or static conditions, make in the water organism under the effect of catalyzer with O
3Fully reaction is thoroughly to remove the Persistent organic pollutants in the water.Utilize the alachlor in the method treating water of the present invention, clearance can reach more than 99%, and corresponding mineralising percentage (TOC clearance) can reach more than 90%, and non-secondary pollution is a kind of safe, treatment process of organic pollutant in the water efficiently.But this technology can only be removed organism (clearance is lower) such as TOC, does not have to remove prussiate, ammonia nitrogen and metal ion function; The non-general purpose material of catalyzer, its making, supply, regeneration are more numerous and diverse.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of combination process that the Industrial Wastewater Treatment and the resource of high cyanogen, high ammonia nitrogen, high salt, high organic concentration are reclaimed is provided.
Purpose of the present invention is achieved through the following technical solutions: adopt acidifying decyanation, alkalization to blow ammonia, add oxychlorination, combination procesies such as biological treatment, precipitation clarification, deep oxidation, biologic active carbon filtration, salt solution are once refining, micro-filtrate membrane filtration, through conventional chlor-alkali industry salt solution secondary refining process, go into ion-exchange membrane electrolyzer and produce chlor-alkali again.It is characterized in that: cyanuric chloride waste water is delivered to strainer with utilidor and is filtered; The strainer water outlet enters acidifying decyanation pond decyanation, the prussic acid of arranging absorb to reclaim sodium cyanide with alkali; The water outlet of decyanation tower enters alkalization and blows ammonia tower deamination, and the acid recovery ammonium salt is reclaimed or used to institute's ammonia excretion with the ammoniacal liquor form; Blow the water outlet of ammonia tower and go into the chlorination oxidation pond, ammonia nitrogen, prussiate, sodium formiate organism are carried out preliminary oxidation, clear up (the oxychlorination agent can utilize factory's byproduct clorox, and also can utilize chlorine such as dioxide peroxide is oxygenant); The water outlet of chlorination oxidation pond enters biological treatment system, through A/O (anaerobism, aerobic series connection) art breading, and inoculation separation screening comes out from the on-the-spot sewage of factory " Natrinema altunense sp " reaches " efficiently falling the cyanogen bacterium ", to pollutent (as ammonia nitrogen, prussiate, organism etc.) biodegrade; The biological treatment system water outlet enters settling pond, carries out preliminary solid-liquid separation; The settling pond water outlet enters the deep oxidation pond, further with remaining pollutent (as ammonia nitrogen, prussiate, organism etc.) oxidation, clear up, be the oxygenation of follow-up biologic active carbon filtration system simultaneously; The water outlet of deep oxidation pond enters the biologic active carbon filtration device, the purification of water quality process of adsorbing-microbiological degradation regeneration-adsorbing; The water outlet of biologic active carbon filtration device enters refining system of salt solution, and process for refining of chlor-alkali industry salt solution carries out routinely, to remove impurity such as calcium, magnesium, sulfate radical, free chlorine; A refining system water outlet of salt solution enters micro-filtrate membrane filtration system (membrane module can with tubular fibre or ceramic film component), further filtering residual impurity (ammonia nitrogen, prussiate, organism, suspended substance etc.); Refined brine of gained can enter ion-exchange membrane electrolyzer and produce chlor-alkali behind conventional secondary brine rectification.Should be understood that in the combination process of the present invention that exquisite technologies of those conventional salt solution (, secondary refining process once refining as salt solution) are the existing more perfect technology of factory, not at the row of claim of the present invention and protection.
Method of the present invention is applicable to handle and anyly contains the trade effluent of high cyanogen, high ammonia nitrogen, high salt, high organic concentration and reclaim related resource, for example processing and the resource to chemical industry trade effluents such as cyanuric chloride, chlor-alkalis reclaims, also can adjust slightly technology, handle gold mine waste, electroplating wastewater, carry out resource and reclaim.
In the preferred embodiment of the invention, its combination process comprises as the lower section:
1, acidifying decyanation
Cyanuric chloride waste water is delivered to strainer with utilidor and is filtered; The strainer water outlet enters acidifying decyanation pond decyanation, the prussic acid of arranging absorb to reclaim sodium cyanide with alkali.Adding hydrochloric acid accent wastewater pH before the pump is 2～4, makes sodium cyanide be converted into hydrocyanic acid, so that stripping.The surplus temperature of temperature graywater (30～80 ℃); Vapour-liquid ratio: 300～2000m
3/ m
3, the stripping time: 0.5～3h.Stripping gas is mainly hydrocyanic acid, and available caustic lye of soda absorbs, and generates sodium cyanide and reclaims.
After the acidifying decyanation, the residual CN of effluent brine
-: 30～100mg/L, NH
3-N:400～1000mg/L.
2, ammonia is blown in alkalization
Waste water after the acidifying decyanation is entered alkalization blow the ammonia tower, transferring pH with caustic lye of soda is 8～12, makes solid-state ammonium salt be converted into free ammonia, so that stripping.Temperature: 30～70 ℃ (utilizing the surplus temperature of waste water); Vapour-liquid ratio: 300～2000m
3/ m
3The stripping time: 0.5～3h.Stripping gas absorbs with sulfuric acid liquid, and the reclaim(ed) sulfuric acid ammonium.
After ammonia is blown in alkalization, the residual CN of effluent brine
-: 20～80mg/L, residual NH
3-N:80～200mg/L, TOC:300～600mg/L.
Under alkaline condition, residual prussic acid is converted into sodium cyanide.
3, add oxychlorination
Blow the water outlet of ammonia tower and also have organism such as higher prussiate, ammonia nitrogen and sodium formiate, available chlorine is that oxygenant is cleared up in the preliminary oxidation of chlorination oxidation pond.Chlorine is that oxygenant is optional with factory's byproduct clorox, utilizes the oxygenizement of the reactive chlorine in the hypochlorite, under certain pH condition, makes cyanide oxidation become cyanate, and cyanate further is oxidized to nontoxic carbonic acid gas and nitrogen then.According to the difference of alkaline chlorination process broken cyanide degree, can be divided into two kinds of location oxidation of silicon process and complete oxidation technologies.
1., selective oxidation method cyanogen breaking process
The principle of this technology is under alkaline condition, with hypochlorite (ClO
-) cyanide oxidation is become cyanate (CNO
-).
CN
-+ClO
-+H
2O＝CNCl+20H
- (1)
CNCl+20H
-＝CNO
-+Cl
-+H
2O (2)
(1) formula and (2) formula are merged,
CN
-+ClO
-＝CNO
-+Cl
- (3)
Cyanate radical (the CNO that the reaction of selective oxidation method broken cyanide generates
-), its toxicity is CN
-Thousandth, still, CNO
-Be toxic substance after all, very easily hydrolysis generates ammonia (NH under acidic conditions
3).
CNO
-+2H
2O＝CO
2+NH
3+OH
- (4)
Ammonia is polluted-water not only, and becomes the chloramines of toxicity not second to chlorine with the chlorination symphysis easily, so should be further with CNO
-Handled.
2., complete oxidation cyanogen breaking process
On the basis that the selective oxidation method is handled, regulate the pH of waste water, add a certain amount of oxygenant again, make CNO through stirring
-Complete oxidation is N
2And CO
2Its reaction formula is as follows:
2CNO
-+3ClO
-＝CO
2+N
2+3Cl
-+CO
3 2- (5)
3., oxidation processing technique parameter control
Under high pH value, the utmost point poisonous gas (CNCl) that reaction formula (1) produces is the cyanate (CNO of hydrolysis generation low toxicity rapidly
-); The pH value of selective oxidation broken cyanide should be controlled at 9～12; The pH of complete oxidation broken cyanide should be controlled at 7～9; Total clorox (in pure product) additive capacity is 100～30000mg/L.
Also can select for use dioxide peroxide to make oxygenant.Compare with clorox broken cyanide method, dioxide peroxide broken cyanide method has that cost is moderate, power consumption is moderate, danger is low, produce that the quantity of slag is low, oxidation capacity strong, broken cyanide power height, can a step broken cyanide etc. characteristics.Its reaction mechanism is: sodium cyanide and chlorine dioxide reaction generate carbonic acid gas, nitrogen, sodium-chlor etc.
2?NaCN+2?ClO
2＝2?CO
2↑+N
2↑+2?NaCl
Dioxide peroxide broken cyanide step is:
1., transferring pH with caustic lye of soda is 9～12;
2., stability chlorine dioxide liquid is activated;
3., getting above-mentioned activatory ClO 2 solution stirs and adds that (convert pure product dioxide peroxide additive capacity 1～50mg/L), 2～5h gets final product in the stirring at normal temperature reaction in the waste water.
Add the residual CN of effluent brine behind the oxychlorination
-: 10～30mg/L, NH
3-N:20～50mg/L, TOC:100～300mg/L.
In this step, dioxide peroxide also can be with yellow prussiate Fe (CN)
6 4-Be converted into hexacyanoferrate Fe (CN)
6 3-, and further clear up NH
3-N, COD, sodium formiate.
4, biological treatment
The water outlet of chlorination oxidation pond enters biological treatment system, through A/O (UASB anaerobism, aerobic series connection) art breading, and inoculation separation screening comes out from the on-the-spot sewage of factory " Natrinema altunense sp " reaches " efficiently falling the cyanogen bacterium ", to pollutent (as ammonia nitrogen, prussiate, organism etc.) biodegrade.
The collection of " Natrinema altunense sp " and " efficiently falling the cyanogen bacterium " is the winter in cold, and the place is in cyanuric chloride workshop water port, and therefore, this bacterial classification is also cold-resistant.Biological treatment system is divided into two portions--and anaerobic and aerobic, having a liking for salt product methagen JZTM is the main force of anaerobic digestion.Its diameter 0.3～0.5 μ m, long 3～6 μ m have crooked and the little curved two kinds of forms of straight-bar, Dan Sheng, paired, minority bunchiness.It can utilize H
2/ CO
2Grow with formate." efficiently fall the cyanogen bacterium " and belong to Penicillium, Trichoderma and yeast belong respectively, can the free cyanogen root of efficient degradation, under optimal condition, remove the cyanogen rate up to more than 90%.
Experiment showed, and work as biological treatment system organic loading rate at 0.5～2.0kgCOD/m
3D, pH are 5～9,25～35 ℃, and under the condition of hydraulic detention time 18～30h, " Natrinema altunense sp " reaches " efficiently falling the cyanogen bacterium " degradation capability of organism in the waste water and prussiate is reached 80%～95% and 85%～98% respectively.
The biosystem water outlet, after the settling pond solid-liquid separation, residual CN
-: 3～10mg/L, NH
3-N:5～15mg/L, TOC:30～90mg/L.
5, precipitation clarification
The biological treatment system water outlet enters the precipitation clarification, and technology is carried out routinely, carries out preliminary solid-liquid separation.
6, deep oxidation
Biosystem water outlet ammonia nitrogen has reached lower level, but the concentration of prussiate, TOC still exceeds standard, especially also have certain distance apart from a purified salt quality standards for water, do further deep oxidation processing so the present invention enters the deep oxidation pond with the biosystem water outlet after the precipitation clarification.
Advanced treatment technology at present commonly used comprises coagulation, precipitation, filtration etc., but these technology are not fine to the treatment effect of hardly degraded organic substance.Fenton reagent is by H
2O
2And Fe
2+Mixing is by a certain percentage formed, the organism that oxidation at normal temperatures and pressures is difficult to degrade, and it mainly is to utilize Fe
2+To the catalytic decomposition of H2O2, produce organism in the OH free-radical oxidn water.The Fenton technical fee is cheap, and is easy to operate, and security is higher.Therefore adopt the Fenton oxidation style, mainly utilize the organism in the highly active OH oxidative degradation waste water, realize at short notice organic degraded fully, and be not subjected to the restriction of kind of waste water, composition and concentration, be applicable to the processing of the reluctant organic waste water of biochemical process.So the present invention adopts the oxygenant of Fenton reagent as deep oxidation.
The processing condition of Fenton reagent deep oxidation are: H
2O
2/ COD is 0.5～3: 1 (mass ratio), H
2O
2/ Fe
2+Be 5～15: 1 (mol ratio), the pH value is 2～6, and oxidization time is 1～5h.
7, biologic active carbon filtration
The water outlet of deep oxidation pond enters the biologic active carbon filtration device and is for further processing.Gac cooperates coupling with the strong oxidizer that the deep oxidation operation is brought, and can improve the oxygenolysis efficient (chemical reaction) of part hardly degraded organic substance, and can improve the shock-resistant ability and the decoloring ability of gac, stabilizing water quality.Utilize gac as microbe carrier, utilize its excellent absorption property that the organism enrichment is concentrated, to reach the matrix condition that microbial metabolism is decomposed.By taming the microorganism system that forms naturally, realize the purification of water quality process that absorption-microbiological degradation is regenerated-adsorbed.In addition, gac tower inside alternately forms anaerobism or oxygen-starved area, forms specific anerobe, amphimicrobe and aerobic bacteria and the microbial balance system of depositing.So the present invention obtains treatment effect preferably with deep oxidation and biologic active carbon filtration coupling.
The processing condition of biological activated carbon adsorption filtration are: 5～60 minutes time, pH value 6～9.
Effluent brine after deep oxidation and biologic active carbon filtration combination treatment, residual CN
-:＜0.5mg/L, NH
3-N:＜5mg/L, TOC:10～20mg/L.
8, salt solution is once refining
The water outlet of biologic active carbon filtration device enters refining system of salt solution, and process for refining of chlor-alkali industry salt solution carries out routinely, to remove impurity such as calcium, magnesium, sulfate radical, free chlorine.Quote just integrity and the continuity for combination process of the present invention is described of this operation, this operation is not claim of the present invention and key protection point, so this ominous stating.
9, micro-filtrate membrane filtration
A refining system water outlet of salt solution, available hollow-fibre membrane or ceramic film component filter.Ceramic cross-flow microfiltration membrane filtration is adopted in the outstanding consideration of the present invention, membrane pore size 0.01 μ m～0.2 μ m, cross-flow filtering velocity 1～5m/s, working pressure: 0.1～0.8Mpa, membrane permeation flux 0.2～1m
3/ m
2H.
Salt solution should reach following index behind the micro-filtrate membrane filtration:
SS：＜2mg/L，CN
-：＜0.5mg/L，Fe(CN)
6 4-：＜55μg/L，
TOC:＜10mg/L, total ammonium (NH4):＜4mg/L, inorganic ammonium:＜1mg/L
Organic amine:＜3mg/L.
10, salt solution secondary refining
Chlor-alkali industry salt solution secondary refining process carries out routinely, further to remove impurity such as calcium, magnesium, sulfate radical, free chlorine, reaches ion-exchange membrane electrolyzer salt water quality standard.Once refining as salt solution, quote just integrity and continuity of this operation for combination process of the present invention is described, this operation is not claim of the present invention and key protection point, so this ominous stating.
Behind the salt solution secondary refining, just can go into the ion-exchange membrane electrolyzer electrolysis and produce chlorine-alkali product.
The present invention compared with prior art has following advantage:
1, process combination science, reasonable
Elder generation's acidifying decyanation, ammonia is blown in the back alkalization, has avoided first alkalization to blow the prussic acid that ammonia causes and has escaped and pollute the amine salt of recovery with ammonia, and after first acidifying removes most cyanogen, will significantly reduce the agent of subsequent chemistry broken cyanide (as ClO
2, NaCIO, H
2O
2Deng) consumption, saved reagent cost, also the raising for the broken cyanide effect of follow-up broken cyanide operation provides guarantee.
Biological treatment system adopts A/O (UASB anaerobism, aerobic series connection) art breading, makes biosystem flora kind abundant, plays a role under each comfortable optimal condition, has improved biological treatment effect.
Deep oxidation technology and the coupling of biologic active carbon filtration technology, the oxygenant that can utilize deep oxidation technology to be brought, for follow-up biologic active carbon filtration technology provides certain oxygen, help growth, the breeding of aerobic bacteria, improve the oxygenolysis efficient (chemical reaction) of part hardly degraded organic substance, and can improve the shock-resistant ability and the decoloring ability of gac, stabilizing water quality.
The use of micro-filtrate membrane filtration system plays total water quality and checks on, and utilizes its high cutoff performance, can get water quality preferably, for follow-up salt solution secondary refining and electrolysis with ion-exchange film lay the foundation.
2, technology novelty, uniqueness
The obligate engineering strain of biological treatment system separation screening from the on-the-spot sewage of factory come out " Natrinema altunense sp " reach " efficiently falling the cyanogen bacterium ", salt tolerant, cold-resistant, anti-poison have good biological degradation effect to pollutent (as ammonia nitrogen, prussiate, organism etc.).Above-mentioned these engineering strains are the present invention's distinctive (declaring patent of invention separately), have any different with the biological inoculum of conventional Sewage treatment systems.
Adopt ceramic cross-flow microfiltration membrane filtration system, can reduce the micro-filtration membrane module cost, improve filter effect, filter material is difficult for stopping up, and membrane permeation flux height can be simplified brine rectification process.
3, function is many, and adaptability is strong, and use range is wide
But magazines such as the decyanation of this combination process, deamination, removing heavy metals ion (as calcium, magnesium, iron, copper, chromium, nickel etc.), organic matter removal, so its adaptability is strong, use range wide (wastewater treatment and the resource that can be used for cyanuric chloride, chlor-alkali, gold mine, the contour cyanogen of plating, high ammonia, high salt, high organic concentration reclaim).
4, technology maturation, treatment effect is good, and effluent quality is excellent
Levy (Yingkou) Fine Chemical Co., Ltd and test on the spot and middle trial run through second-biggest-in-the-world, the largest cyanuric chloride in Asia manufacturing enterprise Degussa three, show this Technology maturation, treatment effect is good, effluent quality excellent (SS:＜2mg/L, CN
-:＜0.5mg/L, Fe (CN)
6 4-:＜55 μ g/L, TOC:＜10mg/L, total ammonium (NH
4):＜4mg/L).It is contemplated that, make water quality reach above-mentioned technical indicator, is impossible realize by traditional sewage treatment process and method.Because the traditional waste water treatment process main purpose is a qualified discharge, and the present invention will accomplish the salt refining reuse.
5, environmental benefit and remarkable in economical benefits, waste water treatment and resource reclaim doulbe-sides' victory
Because the present invention can make waste water all reclaim, reach zero release, so environmental benefit and remarkable in economical benefits.To handle cyanuric chloride waste water is example, the present invention's waste water operational and administrative expenses per ton adds up to 18.25 yuan, and by reclaiming sodium-chlor, sodium cyanide, ammonium salt products such as (or ammoniacal liquor), it is 64.88 yuan that waste water resource per ton reclaims economic worth, expense adds up to 18.25 yuan, but 46.63 yuan of 1 ton of waste water incomes of promptly every processing.To handle 500 tons of waste water every day, every day, income was 23315 yuan, and 8,510,000 yuan of annual earnings have really been accomplished the harmony of environmental benefit and economic benefit.
Description of drawings
Fig. 1 is the schema of combined sewage treating process of the present invention.
1 is utilidor among the figure, and 2 is strainer, and 3 is acid proof pump, 4 are acidifying decyanation pond, and 4-1 is for inhaling the cyanogen device, and 5 is brinepump, 6 is that the ammonia tower is blown in alkalization, and 6-1 is an ammonia absorber, and 7 is the chlorination oxidation pond, 8 is brinepump, and 9 is the UASB anaerobic reation pool, and 10 is the aerobic aeration pond, 11 is settling pond, and 12 is the deep oxidation pond, and 13 is biological activated charcoal filter, 14 is salt dissolving tank, and 15 is refining system of salt solution, and 16 is brinepump, 17 is microporous filtration, 18 is brinepump, and 19 is salt solution secondary refining system, and 20 is ion-exchange membrane electrolyzer, 21 is salt slurry, 22 is hydrochloric acid, and 23 is caustic soda, 24 for chlorine be oxygenant (clorox, dioxide peroxide etc.), 25 is gas blower, 26 is the Fenton oxygenant, and 27 is caustic soda, and 28 is the sodium-chlor of adding.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further concrete description.
It is as follows that Degussa three is levied (Yingkou) Fine Chemical Co., Ltd cyanuric chloride technology effluent brine (from extraction-container) water quality: the pH value: 5～6, and COD:3500mg/L, total cyanide (in CN) content is 600mg/L, ammonia nitrogen (NH
3-N) content is 1000mg/L, sodium formiate (HCOONa): 3800～4200mg/L, sodium-chlor (NaCl): 18%～20%.
In accompanying drawing 1, cyanuric chloride waste water is delivered to strainer 2 with utilidor 1 and is filtered; Strainer salt slurry 21 focuses on separately, and the strainer water outlet is introduced acidifying decyanation pond 4 decyanations through acid proof pump 3, institute's prussic acid of arrange in inhaling cyanogen device 4-1 with the alkali absorption, and recovery sodium cyanide.Adding hydrochloric acid 22 accent wastewater pH before the acid proof pump 3 is 2.5, makes sodium cyanide be converted into hydrocyanic acid, so that stripping.The surplus temperature of temperature graywater (75 ℃); Vapour-liquid ratio: 500
3/ m
3, the stripping time: 0.5h.Stripping gas is mainly hydrocyanic acid, can absorb with 30% caustic lye of soda in inhaling cyanogen device 4-1, generates sodium cyanide and reclaims.
After the acidifying decyanation, the residual CN of effluent brine
-: 81.73mg/L, NH
3-N:874.16mg/L.
Waste water after the acidifying decyanation is introduced alkalization with brinepump 5 blow in the ammonia tower 6, and be 9.5, make solid-state ammonium salt be converted into free ammonia, so that stripping with 30% caustic lye of soda 22 accent pH.Blow the ammonia temperature: 65 ℃ (utilizing the surplus temperature of waste water); Vapour-liquid ratio: 650m
3/ m
3The stripping time: 1h.Stripping gas absorbs with 5% sulfuric acid liquid in ammonia absorber 6-1, and the reclaim(ed) sulfuric acid ammonium.
After ammonia is blown in alkalization, the residual CN of effluent brine
-: 69.47mg/L, NH
3-N:131.19mg/L.TOC：488.5mg/L。
The water outlet that ammonia tower 6 is blown in alkalization also has organism such as higher prussiate, ammonia nitrogen and sodium formiate, and available chlorine is that oxygenant 24 preliminary oxidation in chlorination oxidation pond 7 is cleared up.Chlorine is that oxygenant selects for use three to levy company's byproduct clorox in the present embodiment, utilizes the oxygenizement of the reactive chlorine in the hypochlorite, under the pH9 condition, makes cyanide oxidation become cyanate, and cyanate further is oxidized to nontoxic carbonic acid gas and nitrogen then.Total clorox (in pure product) additive capacity is 10000mg/L.
Add the residual CN of effluent brine behind the oxychlorination
-: 27.29mg/L, NH
3-N:39.36mg/L, TOC:234.8mg/L.
The water outlet of chlorination oxidation pond 7 is introduced in the UASB anaerobic reation pool 9 through brinepump 8, and inoculation " Natrinema altunense sp " (producing methagen JZTM to have a liking for salt) enters the anerobe biological degradation.Inoculum size 3%, UASB anaerobic reation pool hydraulic detention time 24h.
The water outlet of UASB anaerobic reation pool 9, from flowing into aerobic aeration pond 10, utilize gas blower 25 to carry out aeration (gas blower 25 also blows ammonia tower 6 for acidifying decyanation pond 4 and alkalization simultaneously provides air), and inoculation " Natrinema altunense sp " (aerobic bacteria) and " efficiently falling the cyanogen bacterium " (aerobic bacteria, Penicillium, Trichoderma and yeast belong), total inoculum size 5%, the hydraulic detention time in aerobic aeration pond 10 is 6h.
The biosystem water outlet, after settling pond 11 solid-liquid separation, residual CN
-: 8.34mg/L, NH
3-N:12.4mg/L, TOC:30mg/L.The salt slurry 21 that settling pond 11 is regularly discharged can merge with 2 salt discharge mud of strainer to be handled.
The water outlet of settling pond 11 enters deep oxidation pond 12 and does further deep oxidation processing.In the deep oxidation pond, add Fenton reagent (H
2O
2/ Fe
2+) 26, H
2O
2/ COD is 1: 1 (mass ratio), H
2O
2/ Fe
2+Be 6: 1 (mol ratio), the pH value is 3, and oxidization time is 1.5h.
The water outlet in deep oxidation pond 12 enters biologic active carbon filtration device 13 and is for further processing after 30% caustic soda soln, 27 adjusting pH values are 8.The processing condition of biological activated carbon adsorption filtration are: 30 minutes time, pH value 8.
Effluent brine after deep oxidation and biologic active carbon filtration combination treatment, residual CN
-:＜0.5mg/L, NH
3-N:＜5mg/L, TOC:11.94mg/L.
The water outlet of biologic active carbon filtration device enters salt dissolving tank 14, add sodium-chlor 28, make it to become saturated brine, enter then in refining system 15, process for refining of chlor-alkali industry salt solution carries out salt refining routinely, to remove impurity such as calcium, magnesium, sulfate radical, free chlorine.Quote just integrity and the continuity for combination process of the present invention is described of this operation, this operation is not claim of the present invention and key protection point, so this ominous stating.
The water outlet of a refining system 15 of salt solution is squeezed in the ceramic micro filter film filter 17 through special-purpose salt water pump 16, carries out cross flow filter.Membrane pore size 0.1 μ m, cross-flow filtering velocity 3.5m/s, working pressure: 0.5Mpa, membrane permeation flux 0.9m
3/ m
2H.
Salt solution index behind the ceramic micro filter membrane filtration:
SS:0.5mg/L, CN
-: 0.2mg/L, Fe (CN)
6 4-:＜55 μ g/L, TOC:9mg/L, total ammonium (NH
4): 0.1mg/L.
Water outlet behind the ceramic micro filter membrane filtration, introduce in the salt solution secondary refining system 19 through brinepump 18, chlor-alkali industry salt solution secondary refining process carries out routinely, further to remove impurity such as calcium, magnesium, sulfate radical, free chlorine, reaches ion-exchange membrane electrolyzer salt water quality standard.Once refining as salt solution, quote just integrity and continuity of this operation for combination process of the present invention is described, this operation is not claim of the present invention and key protection point, so this ominous stating.
Behind the salt solution secondary refining, just can go into ion-exchange membrane electrolyzer electrolysis 20 and produce chlorine-alkali product.
Claims (8)
1. a high-cyanogen high-ammonia high-salt organic waste water is handled and the combination process of reuse, adopt acidifying decyanation, alkalization to blow ammonia, add oxychlorination, combination procesies such as biological treatment, precipitation clarification, deep oxidation, biologic active carbon filtration, salt solution are once refining, micro-filtrate membrane filtration, through conventional chlor-alkali industry salt solution secondary refining process, go into ion-exchange membrane electrolyzer and produce chlor-alkali again.It is characterized in that: waste water is delivered to strainer with utilidor and is filtered; The strainer water outlet enters acidifying decyanation pond decyanation, the prussic acid of arranging absorb to reclaim sodium cyanide with alkali; The water outlet of decyanation tower enters alkalization and blows ammonia tower deamination, and the acid recovery ammonium salt is reclaimed or used to institute's ammonia excretion with the ammoniacal liquor form; Blowing the water outlet of ammonia tower and go into the chlorination oxidation pond, is that oxygenant carries out ammonia nitrogen, prussiate, sodium formiate organism preliminary oxidation, clears up with chlorine; The water outlet of chlorination oxidation pond enters biological treatment system, through A/O (anaerobism, aerobic series connection) art breading, and the inoculation " Natrinema altunense sp " reach " efficiently falling the cyanogen bacterium ", to pollutent (as ammonia nitrogen, prussiate, organism etc.) biodegrade; The biological treatment system water outlet enters settling pond, carries out preliminary solid-liquid separation; The settling pond water outlet enters the deep oxidation pond, with the Fenton oxygenant further with remaining pollutant oxidation, clear up, be the oxygenation of follow-up biologic active carbon filtration system simultaneously; The water outlet of deep oxidation pond enters the biologic active carbon filtration device, the purification of water quality process of adsorbing-microbiological degradation regeneration-adsorbing; The water outlet of biologic active carbon filtration device enters refining system of salt solution, and process for refining of chlor-alkali industry salt solution carries out routinely, to remove impurity such as calcium, magnesium, sulfate radical, free chlorine; A refining system water outlet of salt solution enters the micro-filtrate membrane filtration system, further filtering residual impurity (ammonia nitrogen, prussiate, organism, suspended substance etc.); Refined brine of gained can enter ion-exchange membrane electrolyzer and produce chlor-alkali behind conventional secondary brine rectification.In the aforesaid combination technology, exquisite technologies of those conventional salt solution (, secondary refining process once refining as salt solution) are not at the row of claim of the present invention and protection.
2. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: waste water is delivered to strainer with utilidor and is filtered, the strainer water outlet enters acidifying decyanation pond decyanation, the prussic acid of arranging absorb to reclaim sodium cyanide with alkali.Adding hydrochloric acid accent wastewater pH before the pump is 2～4, makes sodium cyanide be converted into hydrocyanic acid, so that stripping.The surplus temperature of temperature graywater (30～80 ℃); Vapour-liquid ratio: 300～2000m
3/ m
3, the stripping time: 0.5～3h.The hydrocyanic acid gas of stripping absorbs with caustic lye of soda, and reclaims sodium cyanide.
3. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: the waste water after the acidifying decyanation is entered alkalization blow the ammonia tower, transferring pH with caustic lye of soda is 8～12, makes solid-state ammonium salt be converted into free ammonia, so that stripping.Temperature: 30～70 ℃ (utilizing the surplus temperature of waste water); Vapour-liquid ratio: 300～2000m
3/ m
3The stripping time: 0.5～3h.The ammonia of stripping absorbs with sulfuric acid liquid, and the reclaim(ed) sulfuric acid ammonium.
4. a kind of high-cyanogen high-ammonia high-salt organic waste water according to claim 1 is handled and the combination process of reuse, it is characterized in that: blowing the water outlet of ammonia tower and enter the chlorination oxidation pond, is that oxygenant carries out preliminary oxidation and clears up impurity with chlorine.Chlorine is that oxygenant can be selected clorox or dioxide peroxide for use.Hypochlorite oxidation pH value is 7～12, and hypochlorous acid sodium pure product additive capacity is 100～30000mg/L; Dioxide peroxide oxidation pH value is 9～12, and the pure product additive capacity of dioxide peroxide is 1～100mg/L.
5. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: the water outlet of chlorination oxidation pond enters biological treatment system, through A/O (UASB anaerobism, aerobic series connection) art breading, and inoculation separation screening comes out from the on-the-spot sewage of factory " Natrinema altunense sp " reaches " efficiently falling the cyanogen bacterium ", to pollutent (as ammonia nitrogen, prussiate, organism etc.) biodegrade.Biological treatment system organic loading rate is at 0.5～2.0kgCOD/m
3D, pH are 5～9,25～35 ℃, hydraulic detention time 18～30h.
6. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: the biosystem water outlet enters the deep oxidation pond and does further deep oxidation processing with the Fenyon oxygenant after the preliminary solid-liquid separation of settling pond.The deep oxidation processing condition are: H
2O
2/ COD is 0.5～3: 1 (mass ratio), H
2O
2/ Fe
2+Be 5～15: 1 (mol ratio), the pH value is 2～6, and oxidization time is 1～5h.
7. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: the water outlet of deep oxidation pond enters the biologic active carbon filtration device and is for further processing, and realizes deep oxidation and biologic active carbon filtration coupling.The processing condition of biological activated carbon adsorption filtration are: 5～60 minutes time, pH value 6～9.
8. the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water processing according to claim 1 and reuse, it is characterized in that: the water outlet of biologic active carbon filtration device, after refining system of salt solution is handled, use micro-filtrate membrane filtration again, but micro-filtration membrane module hollow-fibre membrane or ceramic film component.Ceramic cross-flow microfiltration membrane filtration is adopted in the outstanding consideration of the present invention, membrane pore size 0.01 μ m～0.2 μ m, cross-flow filtering velocity 1～5m/s, working pressure: 0.1～0.8Mpa, membrane permeation flux 0.2～1m
3/ m
2H.
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