CN106007167A - Endocrine disruptor-containing pickling wastewater treatment method - Google Patents

Endocrine disruptor-containing pickling wastewater treatment method Download PDF

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Publication number
CN106007167A
CN106007167A CN201610139186.8A CN201610139186A CN106007167A CN 106007167 A CN106007167 A CN 106007167A CN 201610139186 A CN201610139186 A CN 201610139186A CN 106007167 A CN106007167 A CN 106007167A
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water
tank
pump
regulating reservoir
staying
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CN106007167B (en
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鲁逸人
陈鹏
张洁
王建伟
童银栋
刘宪华
朱璟
魏树龙
张立红
徐尚源
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Tianjin University
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Tianjin University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes

Abstract

The invention provides an endocrine disruptor-containing pickling wastewater treatment method. Components of pickling wastewater from China National Offshore Oil Corporation mainly comprise acids, metal ions and organic matters; an endocrine disruptor is polyoxyethylene nonyl phenyl ether, is a surface active substance, is a common organic matter used in a coating process of offshore oilfields, and can cause a certain amount of damage on the ecology. The wastewater undergoes foam separation, a Fenton oxidation reaction, flocculation precipitation, A2/O biochemical treatment, a CMF reaction and active carbon filtration to remove harmful substances in the wastewater, and the treated effluent reaches first-stage B standards of ''discharge standard of pollutants for municipal wastewater treatment plant'', and can be used for pipeline spray cooling again. The automation degree is high, the reaction flow can be flexibly adjusted, different inlet and outlet water quality requirements can be adapted, and the process has the advantages of COD up-to-standard discharge, reduction of wastewater treatment costs, and realization of high effectiveness and economy of wastewater treatment.

Description

Processing method containing incretion interferent pickling waste waters
The present patent application is the division of parent application " a kind of processing means containing incretion interferent pickling waste waters and process " Application, the Application No. 2015101401704 of parent application, the filing date of parent application on March 27th, 2015.
Technical field
The invention belongs to the environmental technology field of acid treatment waste liquid, more specifically, for ocean engineering association pickle For, contained incretion interferent is as the processing means of a kind of persistent organism and process.
Background technology
It is presently available for pickling waste waters process main method to be classified as follows:
Sulfuric acid washing waste water treatment process mainly have neutralisation, sulphate of iron method, organic extractant solution method, dialysis, from The methods such as sub-exchange process.Three kinds of methods next are still in the experimental study stage.In addition with iron oxide red sulfur ammonium method, wetland Method, bioanalysis.In recent years, waste water zero emission is mentioned the most continually at industrial circle, also becomes every profession and trade on rule Draw the important indicator in examining.Along with progress of research, abroad have begun to enforcement diffusion dialysis-diaphragm electrolysis, biology The PROCESS FOR TREATMENT such as adsorption technology, the micelle enhanced ultrafiltration method pickling waste waters containing incretion interferent.
Main technique is introduced
(1) foam separation technique: foam separation, according to the principle of surface adsorption, utilizes ventilation bubbling to be formed in the liquid phase Bubble be carrier, the solute in liquid phase or granule are separated, therefore also known as steel foams separate.
Foam separating technology is one of new separation technology of growing up the nearly more than ten years.Foam separation is former according to adsorb Reason, aeration in the liquid containing surfactant, make the surfactant in liquid be gathered in gas-liquid interface (bubble Surface) on, above main body of liquid, form froth bed, by froth bed and liquid phase main body separately, it is possible to reach to concentrate Surfactant (at froth bed) and the purpose of purification liquid phase main body.
Foam separation is made up of two basic processes: (1) solute to be separated is adsorbed on liquid-vapor interface;(2) right It is collected by the material of steel foams to solution-air circle and uses method chemical, thermally or mechanically to destroy foam, solute is extracted Out.Therefore its capital equipment is foaming tower and demister.
Foam separating technology has the advantage that
(1) foam separation structure is relatively easy, it is easy to amplify;
(2) simple to operate, consume energy low;
(3) can the most also can intermittently operated;
(4) initial stage at biological Downstream processing uses, and processes bulky diluent;
(5) as long as operating condition is reasonable in design, the highest separation efficiency can be obtained.
Feature at the acid waste water analyzed containing incretion interferent and the research of the possibility research to foam separation technique After carried out experiment after, pickling waste waters is after foam separation processes, and COD concentration, total P concentration has and significantly lowers.
(2) Fenton oxidation technique: Fenton's reaction is with ferrous ion (Fe2+) it is catalyst hydrogen peroxide (H2O2) carry out The method of wastewater treatment of chemical oxidation.The system being made up of ferrous ion and hydrogen peroxide, also referred to as Fenton reagent, it can be given birth to Become the hydroxyl radical free radical of strong oxidizing property, generate organic free radical with hardly degraded organic substance in aqueous and be allowed to structural deterioration, Final oxidation Decomposition.
Fenton's reaction is a series of radical reactions with ferrous ion as catalyst.Dominant response approximately as:
Fe2++H2O2==Fe3++OH-+HO·
Fe3++H2O2+ OH-==Fe2++H2O+HO·
Fe3++H2O2==Fe2++H++HO2
HO2+H2O2==H2O+O2↑+HO·
Fenton reagent, by above reaction, constantly produces HO (hydroxyl radical free radical, electrode potential 2.80EV are only second to F2), Make whole system have strong oxidizing property, chlorobenzene, benzyl chloride, oils and fats etc. can be aoxidized and be difficult to by general oxidant (chlorine Gas, sodium hypochlorite, chlorine dioxide, ozone, the electrode potential of ozone only has 2.23EV) material that aoxidizes.At hydroxyl certainly By under the effect of base, in sewage, the organic matter degradation of part difficult degradation is degradable Organic substance, improves giving birth to of sewage The property changed.
(3) A2/ O technique: A2/ O technique is mainly made up of hydrolysis acidification pool, anaerobic pond, aerobic nitrification pond.Such as Fig. 1 Shown in.Each reactor unit function:
1. anaerobic reactor, raw sewage is Tong Bu with the phosphorous returned sludge discharged from sedimentation tank to be entered, the main merit of this reactor Can be release phosphorus, partial organic substances aoxidizes simultaneously;
2. anoxic reacter, premiere feature is denitrogenation, and nitrate nitrogen is sent here by aerobic reactor by interior circulation, circulation Mixing liquid measure relatively big, generally 2Q (Q is raw sewage flow);
3. aerobic reactor Aeration tank, this reaction member is multi-functional, removes BOD, and nitrification and absorption phosphorus etc. are all Herein carry out.Flow is that the mixed liquor of 2Q is back to anoxic reacter from here;
4. sedimentation tank, function is mud-water separation, and a mud part is back to anaerobic reactor, and supernatant is as processing water row Put.
Process characteristic:
1. this technique is properly termed as simplest synchronous denitrogen dephosphorus technology in system, and total hrt is less than other Class technique;This PROCESS FOR TREATMENT efficiency typically can reach: BOD5 and SS is 90%-95%, and total nitrogen is more than 70%, and phosphorus is 90% Left and right;
2. under the conditions of anaerobism (anoxia), aerobic alternate run, filamentous bacteria can not be bred in a large number, is not susceptible to mud silk Shape expands, and SVI value is generally less than 100;
3. the phosphorous height of mud, has higher fertilizer efficiency;
4. run in do not need dispensing, two A sections only with being gently mixed, with do not increase dissolved oxygen for spend, operating cost is low;
5. anaerobism, anoxia, aerobic three kinds of different environmental conditions and organic cooperation of different types of microorganisms flora, simultaneously There is the function of organics removal, denitrogenation dephosphorizing.
(4) CMF technique: continuous membrane filter (Continuous Membrane Filtration is called for short CMF) technology It is a kind of novel membrane separation process process, is designed by modular structure, use cross flow filter mode and batch (-type) certainly The dynamic system cleaning (gas and water washes technique), a whole set of being combined into closes continuous print membrane filtration system.
CMF systems technology feature:
1. using polypropylene hollow fiber micro-filtration membrane or ultrafilter membrane, resistance to oxidation, the easy cleaning of high intensity, service life is long;
2. due to the elasticity that PP hollow-fibre membrane is exclusive, micropore can be expanded, and uses compressed air backwash technique so that this Plant film and there is good membrane flux response rate;
3. pair raw water quality requires low, produces water as clear as crystal, SDI is stable≤and 3, it is better than the inflow requirement of RO system;
4. system auto-control degree is high, simple to operate, effectively reduces labor intensity;
5. compact equipment, take up an area little, modular combination design be applicable to various scale water process;
6. equipment investment and operating cost are cheap, the highest with cost performance in type equipment at home and abroad.
Summary of the invention
Present invention firstly discovers that and propose during ocean engineering is built (drilling well, oil recovery, submarine pipeline anticorrosion pretreatment, former The oil necessary production link such as demulsifier, the cleaning of drilling equipment, oil recovery additive) incretion interferent that uses is to life The impact of state particularly on ecological impact, on the basis of research Internet of Things monitoring, proposes efficient, economic solution work Skill scheme, makes great efforts to overcome the shortcomings such as conventional processes difficult for biological degradation, treatment cost are high, difficulty is big, efficiency is low, real The removal of existing endocrine disruptor is enriched and recycled, and reduces discharge, has the recycling economy advantage of uniqueness.From length Remote angle analysis, uses this technique, is possible not only to make its COD qualified discharge, and can reduce the handling of waste water With, it is achieved the high efficiency of waste water process and economy.
The purpose of the present invention is achieved by following technical proposals.
A kind of processing means containing incretion interferent pickling waste waters, including the first regulating reservoir, foam separator, Fenton Oxidation reaction tank, reaction precipitation tank, the second regulating reservoir, A2/ O biochemical treatment apparatus, sedimentation tank, intermediate water tank, CMF Device, activated carbon filtering tank and product water tank, wherein:
Described first regulating reservoir is connected with described foam separator, and described first regulating reservoir is connected with wastewater outlet, described First regulating reservoir is connected with described CMF device and described active carbon filtering device;
Described foam separator is connected with demister, and described foam separator is connected with described Fenton oxidation tank;
Ferrous sulfate grug feeding jar is connected with described Fenton oxidation tank, and hydrogen peroxide grug feeding jar is connected with described Fenton oxidation tank, institute State Fenton oxidation tank to be connected with described reaction precipitation tank;
Calcium chloride grug feeding jar is connected with described reaction precipitation tank, and PAC grug feeding jar is connected with described reaction precipitation tank, PAM dosing Tank is connected with described reaction precipitation tank, and described reaction precipitation tank is connected with storage basin, described reaction precipitation tank and described second Regulating reservoir is connected, and arranges the first online pH and detect device, to detect the acid in reaction precipitation tank in described reaction precipitation tank Property pH environment;
Described A2/ O biochemical treatment apparatus includes anaerobic reactor, anoxic reacter and aerobic reactor;Described anaerobic reaction Device is connected with described anoxic reacter, and described anoxic reacter is connected with described aerobic reactor, described aerobic reactor with Described sedimentation tank is connected;
Described second regulating reservoir is connected with nutrient substance grug feeding jar, described second regulating reservoir and described A2/ O biochemical treatment apparatus Described in anaerobic reactor be connected, arrange in described second regulating reservoir second online pH detection device, to detect the second tune Acid ph value environment in joint pond;
Described sedimentation tank and described A2Anaerobic reactor described in/O biochemical treatment apparatus is connected, described sedimentation tank and storage basin Being connected, described storage basin is connected with filter press, and described sedimentation tank is connected with described intermediate water tank;
Described intermediate water tank is connected with described CMF device, and described CMF device is connected with described active carbon filtering device, institute Stating active carbon filtering device to be connected with described product water tank, described product water tank is connected with chlorine tablets grug feeding jar;
Described pickling waste waters is passed directly into the first regulating reservoir by entering waste pipe, enters to arrange intake pump on waste pipe described;
It is connected with described foam separator top by the first outlet pipe bottom described first regulating reservoir, goes out described first First elevator pump is set on water pipe;
By the 5th outlet pipe and described A bottom described second regulating reservoir2Anaerobic reactor top described in/O biochemical treatment apparatus Portion is connected, and arranges the second elevator pump on described 5th outlet pipe;
By reflux sludge tube and described A bottom described sedimentation tank2Anaerobic reactor top phase described in/O biochemical treatment apparatus Even, described reflux sludge tube arranges sludge pump;
It is connected with described filter press by sludge discharging pipe bottom described storage basin, described sludge discharging pipe arranges screw rod Pump;
It is connected with described CMF bottom of device, on described 8th outlet pipe by the 8th outlet pipe bottom described intermediate water tank Arranging force (forcing) pump and self-cleaning filter, described force (forcing) pump is connected with described self-cleaning filter;
Described active carbon filtering device is connected with described product water tank by the tenth outlet pipe, described tenth outlet pipe is arranged anti- Wash water pump;
Select pipeline as the connection unit of each ingredient.
Arranging agitating device in described storage basin, described agitating device is QJB diving mixer, to realize solid-liquid two-phase flow Homogenizing, the technological requirement of flowing with solid-liquid-gas three phase stream.
Described A2Described in/O biochemical treatment apparatus, aerobic reaction pond is connected with aerator, and described aerator is Roots blower, To realize removing the effects such as BOD, nitrification and absorption phosphorus.
Described first elevator pump, described second elevator pump, described sludge pump, described screw pump, described force (forcing) pump and institute The quantity stating backwash water pump is all two.
When the above-mentioned processing means using the present invention carries out pickling waste waters process, select whole processing means (the most whole Plant the processing means containing incretion interferent pickling waste waters) be fixed in moveable device, such as in mobile container, To realize movable type work, meet movable type and process the requirement of pickling waste waters.
A kind of process process containing incretion interferent pickling waste waters, is carried out as steps described below:
Step 1, regulates described intake pump, and controlling pickling waste waters flow is 2-5m3/ h, preferably 3m3/h;
Step 2, staticly settles, and described regulating reservoir carries out the regulation of water quality and quantity to waste water, makes waste water reach steady statue, PH value is at 0.5-1.5 (free acid 0.5-2%), and in highly acid, waste water residence time in described regulating reservoir is 44-50h, Preferably 48h;
Step 3, waste water residence time in described foam separator is 10-40min, preferably 20-30min, passes through Described demister removes the incretion interferent of 60%-70%, the water outlet after the process of described demister, also needs at further concentration Reason, described demister water outlet contains high concentration and shows that active substance can be as low side abluent;
Step 4, in described Fenton oxidation device, the time of staying of waste water is 4-10h, preferably 6-8h, described Fenton oxidation The medicine added in tank includes ferrous sulfate (FeSO4·7H2And hydrogen peroxide (H O)2O2), wherein Fe2+With hydrogen peroxide ratio For 1-4:1, preferably 3:1, FeSO4·7H2The mass percent of O is 2wt%-20wt%, preferably 5wt%-15wt%, peroxide The mass percent changing hydrogen is 20-40wt%, preferably 30-35wt%, and the general dosage of hydrogen peroxide is intended to the twice of the COD removed;
Step 5, in described reaction precipitation tank, the time of staying of waste water is 1-9h, preferably 3-7h, described reaction precipitation tank In the medicine that adds include polyacrylamide (PAM), aluminium polychlorid (PAC) and calcium chloride (CaCl2), flocculant Addition can remove 10%-17% through Fenton oxidation small organic molecule formed precipitation, by the described first online pH Detection device is connected with described reaction precipitation tank, with guarantee the water quality in described reaction precipitation tank reach pH as 9-10 about;
Step 6, in described second regulating reservoir, the time of staying of waste water is 20-26h, preferably 24h, and adds nutrient substance, Water sample is further regulated, be suitable for growth of microorganism water environment, by described second online pH detection device and Described second regulating reservoir is connected, with guarantee the water quality in described second regulating reservoir reach pH as 6-8 about;
Step 7, when carrying out pickling waste waters biochemical treatment, regulates described second elevator pump, and control flow is 1-5m3/ h, excellent Select 2-3m3/h;
Step 8, at described A2In/O biochemical treatment apparatus, the total residence time of waste water is 20-24h, preferably 23h, in institute Stating the time of staying in anoxic reacter is 2-6h, preferably 4-5h, and the time of staying in described anaerobic reactor is 3-9h, Preferably 6-8h, the time of staying in described aerobic reactor is 9-15h, preferably 10-13h, at described aerobic reactor During middle aeration, selecting the air mass flow being adjusted aeration by described Roots blower is 0.5-1.8m3/ min, preferably 1.0-1.3 m3/min;
Step 9, in described sedimentation tank, the time of staying of waste water is 1-8h, preferably 2-6h, and function is mud-water separation, dirty A mud part is back to described anaerobic reactor, and supernatant flows into described intermediate water tank, institute as processing water by outlet pipe The excess sludge stated in sedimentation tank is entered in described storage basin by sludge pipe;
Step 10, regulates described force (forcing) pump, adjusts flow and does not exceeds 2.4m3/ h, preferably 1.5-2.2m3/ h, at warp Crossing described active carbon filtering device to process, after CMF processes in a word, water outlet i.e. can reach " urban wastewater treatment firm pollutant row Put standard " one-level B class standard in (GB18918-2002), it is re-used for the spraying cooling of pipeline.
In the inventive solutions, various wastewater is used to process the method effectively combined, foam separator reasonable Using, can remove the incretion interferent of 60%-70%, the collocation of Fenton oxidation device and reaction precipitation device uses, and can go Except the incretion interferent of 10%-17%, and by aerator, further have adjusted the pH value of waste water, create more Be conducive to the environment of growth of microorganism, create condition for biochemical reaction through row, save the medicine adding regulation pH simultaneously, Save old of process.Consumption and owner is provided to provide money by outsourcing medicament, fuel and power cost by relevant specialty Material calculates: waste water reagent cost per ton is 30.04 yuan, and total rate of electricity is 0.80 yuan/kW h, than the acid of same type Wash old of waste water to have declined.Automaticity of the present invention is high, it is possible to flexible reaction process, and adapts to different Inlet and outlet water water quality requirement, is a kind of efficient incretion interferent pickling wastewater processing equipment.
Accompanying drawing explanation
Fig. 1 is the attachment structure schematic diagram of apparatus of the present invention.
In figure: 1 is intake pump, 2 is the first regulating reservoir, and 3 is the first elevator pump, and 4 is vacuolar membrane knockout drum, and 5 is device of vanishing, 6 is Fenton oxidation tank, and 7 is ferrous sulfate holding vessel, and 8 is hydrogen peroxide holding vessel, and 9 is reaction precipitation tank, and 10 is PAM Holding vessel, 11 is PAC holding vessel, and 12 is calcium oxide holding vessel, and 13 is the second regulating reservoir, and 14 is nutrient substance dosing Tank, 15 is the second elevator pump, and 16 is A2/ O biochemical treatment apparatus, 17 is sludge pump, and 18 is sedimentation tank, and 19 is storage mud Pond, 20 is screw pump, and 21 is filter press, and 22 is intermediate water tank, and 23 is force (forcing) pump, and 24 is CMF device, 25 For active carbon filtering device, 26 is backwash water pump, and 27 for producing water tank, and 28 is chlorine tablets storage tank;A for entering waste pipe, B Being the first outlet pipe, C is that foam goes out pipe, C0For demister outlet pipe, D is the second outlet pipe, and E is ferrous sulfate dosing Pipe, F is hydrogen peroxide chemical feed pipe, and G is the 3rd outlet pipe, and H is calcium chloride chemical feed pipe, and I is PAC chemical feed pipe, and J is PAM Chemical feed pipe, K is the 4th outlet pipe, and L is nutrient substance chemical feed pipe, and M is the 5th outlet pipe, and N is the 6th outlet pipe, O For reflux sludge tube, P is that excess sludge goes out pipe, and Q is for being settled out pipe, and R is sludge discharging pipe, R0Going out pipe for mud cake, S is 7th outlet pipe, T is the 8th outlet pipe, U the 9th outlet pipe, V the tenth outlet pipe, and W is chlorine tablets chemical feed pipe, and X is first Backflow water pipe, Y is the second backflow water pipe, Z the 11st outlet pipe, Z0It it is the 3rd backflow water pipe.
Detailed description of the invention
Below by specific embodiment, technical scheme is further described.
The pickling waste waters containing incretion interferent used in the present embodiment derives from the pickling of China National Offshore Oil Corporation (CNOOC) and gives up Water, the secretion chaff interference in the said firm's pickling waste waters is mainly NPE.
As it is shown in figure 1, wherein, 1 is intake pump, and 2 is the first regulating reservoir, and 3 is the first elevator pump, and 4 separate for vacuolar membrane Tank, 5 is device of vanishing, and 6 is Fenton oxidation tank, and 7 is ferrous sulfate holding vessel, and 8 is hydrogen peroxide holding vessel, and 9 is heavy for reaction Shallow lake tank, 10 is PAM holding vessel, and 11 is PAC holding vessel, and 12 is calcium oxide holding vessel, and 13 is the second regulating reservoir, 14 For nutrient substance grug feeding jar, 15 is the second elevator pump, and 16 is A2/ O biochemical treatment apparatus, 17 is sludge pump, and 18 is heavy Pond, shallow lake, 19 is storage basin, and 20 is screw pump, and 21 is filter press, and 22 is intermediate water tank, and 23 is force (forcing) pump, 24 For CMF device, 25 is active carbon filtering device, and 26 is backwash water pump, and 27 for producing water tank, and 28 is chlorine tablets storage tank;A For entering waste pipe, B is the first outlet pipe, and C is that foam goes out pipe, C0For demister outlet pipe, D is the second outlet pipe, E For ferrous sulfate chemical feed pipe, F is hydrogen peroxide chemical feed pipe, and G is the 3rd outlet pipe, and H is calcium chloride chemical feed pipe, and I is PAC Chemical feed pipe, J is PAM chemical feed pipe, and K is the 4th outlet pipe, and L is nutrient substance chemical feed pipe, and M is the 5th outlet pipe, N Being the 6th outlet pipe, O is reflux sludge tube, and P is that excess sludge goes out pipe, and Q is for being settled out pipe, and R is sludge discharging pipe, R0 Going out pipe for mud cake, S is the 7th outlet pipe, and T is the 8th outlet pipe, U the 9th outlet pipe, V the tenth outlet pipe, and W is chlorine tablets Chemical feed pipe, X is the first backflow water pipe, and Y is the second backflow water pipe, Z the 11st outlet pipe, Z0It it is the 3rd backflow water pipe.
Water inlet pipe A is connected with the first regulating reservoir 2 by the first pump 1, and the first outlet pipe B is divided with foam by the second pump 3 Being connected from device 4, foam is gone out pipe C and is connected with demister 5 by foam separator 4, first steeps pickling waste waters Foam separates, and can effectively reduce the concentration of influent COD and P.
Second outlet pipe D is connected with Fenton oxidation tank 6 by foam separator 4, and ferrous sulfate stores in grug feeding jar 7 That store is the ferrous (FeSO of the first catalyst sulfuric acid4·7H2O) aqueous solution, and by ferrous sulfate chemical feed pipe E with fragrant The oxidation tank 6 that pauses is connected, and that store in hydrogen peroxide holding vessel 8 is the first oxidants hydrogen peroxide (H2O2) solution, and by double Oxygen water chemical feed pipe F is connected with Fenton oxidation tank 6.Ferrous ion can generate strong oxidizing property with the system of hydrogen peroxide composition Hydroxyl radical free radical (HO), generates organic free radical with hardly degraded organic substance in aqueous and is allowed to structural deterioration, finally Oxidation Decomposition.
3rd outlet pipe G is connected with reaction precipitation tank 9 by Fenton oxidation tank 6, and PAM stores storage in grug feeding jar 10 It is a kind of macromolecule water treatment flocculant polyacrylamide ((C3H5NO)n), and by PAM chemical feed pipe J and reaction precipitation tank 9 are connected;Store in PAC storage grug feeding jar 11 is a kind of inorganic polymer coagulant aluminium polychlorid (Al2(OH)nCl6-nm), and be connected with reaction precipitation tank 9 by PAC chemical feed pipe I;Calcium chloride stores grug feeding jar 12 Middle storage is calcium chloride (CaCl2), and be connected with reaction precipitation tank 9 by calcium chloride chemical feed pipe H;First online pH Detection device is connected with reaction precipitation tank 9, to ensure that the water quality in reaction precipitation tank 9 reaches predetermined pH value.
4th outlet pipe K is connected with the second regulating reservoir 13 by reaction precipitation tank 9, stores in nutrient substance grug feeding jar 14 Be the nutrient substance being suitable for growth of microorganism, and be connected by nutrient substance chemical feed pipe L and the second regulating reservoir 13, second Online pH detection device and the second regulating reservoir 13 connect, to ensure that the water quality in the second regulating reservoir 13 reaches predetermined pH Value.
It is provided with the 5th outlet pipe M of the 3rd pump 15 by the second regulating reservoir 13 and A2Anaerobism in/O biochemical treatment apparatus 16 Reactor is connected, and the 6th outlet pipe N passes through A2In/O biochemical treatment apparatus 16, aerobic reactor is connected with sedimentation tank 18, It is provided with the reflux sludge tube O of sludge pump 17 by sedimentation tank 18 and A2Anaerobic reactor in/O biochemical treatment apparatus 16 It is connected.
Excess sludge is gone out pipe P and is connected with storage basin 19 by sedimentation tank 18, be settled out pipe Q by reaction precipitation tank 9 and Storage basin 19 is connected, and the sludge discharging pipe R being provided with screw pump 20 is connected with filter press 21 by storage basin 19, And be provided with mud cake and go out pipe R0It is connected with filter press 21.
7th outlet pipe S is connected with intermediate water tank 22 by sedimentation tank 18, is provided with the 8th outlet pipe T of force (forcing) pump 23 Being connected with CMF device 24 by intermediate water tank 22, the 9th outlet pipe U passes through CMF device 24 and active carbon filtering device 25 are connected, and the tenth outlet pipe V being provided with backwash water pump 26 is connected with producing water tank 27 by active carbon filtering device 25.
Store in chlorine tablets storage grug feeding jar 28 is new and effective sterilization, bleach chlorine tablets, and by chlorine tablets chemical feed pipe W Being connected with producing water tank 27, the first backflow water pipe X is by producing water tank 27 respectively at CMF device 24 and active carbon filtering device 25 be connected, second backflow water pipe Y by the first regulating reservoir 2 respectively with CMF device 24 and active carbon filtering device 25 phase Even.
3rd backflow water pipe Z0It is connected with the second regulating reservoir 13 by producing water tank 27, works as damp production, produce waste water no longer When supplying continuously, the 3rd backflow water pipe Z0Just open operation.
When the above-mentioned processing means using the present invention carries out pickling waste waters process, select whole processing means (the most whole Plant the processing means containing incretion interferent pickling waste waters) be fixed in moveable device, such as in mobile container, To realize movable type work, meet movable type and process the requirement of pickling waste waters.
Utilize the ventilation bubble that formed in the liquid phase of bubbling for carrier to the solute in liquid phase or granule in foam separator Separate, the correctness of technique selected by the results show present invention.Pickling waste waters through foam separation process after, COD It is down to about 3000mg/L, total P from original 9871mg/L and is down to 33mg/L by original 8000mg/L.At sweet smell With Fenton reagent ferrous sulfate and hydrogen peroxide reaction in oxidation tank, produce the hydroxyl radical free radical with strong oxidizing property, at hydroxyl Under the effect of base free radical, in sewage, the organic matter degradation of part difficult degradation is degradable Organic substance, improves sewage Biodegradability.Fe2+Being 3:1 with hydrogen peroxide ratio, the general dosage of hydrogen peroxide is intended to the twice of the COD removed.Through Fenton After reagent oxidation, recycling macromolecule water treatment flocculant polyacrylamide, inorganic polymer coagulant aluminium polychlorid and Calcium chloride can remove the organic pollution becoming short chain so that the pH=10 after reaction precipitation, substantially increases biodegradability Energy.Through A2After/O processes, COD clearance is about 93.1%, and water outlet COD drops to 112mg/L from 1617mg/L; Ammonia nitrogen removal frank about 81.3%, water outlet ammonia nitrogen is down to 5.7mg/L from 30.5mg/L.In above-mentioned one containing incretion interferent In the processing means of pickling waste waters, described A2In/O biochemical treatment apparatus, aerobic reaction pond is connected with aerator, described air blast Machine is Roots blower, to realize removing the effects such as BOD, nitrification and absorption phosphorus.Use the first online pH detection arranged Water environment in device and the second online pH detection device close inspection retort, uses the stirring dress being arranged in storage basin Putting QJB diving mixer to be stirred, to realize solid-liquid two-phase flow and the homogenizing of solid-liquid-gas three phase stream, the technique of flowing wants Ask.
Aeration experiment: by Air Exposure, the preliminary COD content reduced in water sample, also remove the total nitrogen content in water sample.
Experimental procedure:
(1) water sampling 800ml, air supporting 1h, remain 761ml water after reaction, front and back volume of water sample difference is 4.88%.
(2) water sampling 800ml adds the H of volume of water sample 1%2O2(adding 8.0mL), after reaction, remain 758ml water, front Rear volume of water sample difference is 5.25%.During air supporting, obvious ratio does not adds H2O2Water sample produce foam few, have white after air supporting Flocculent deposit.
(3) water sampling 800ml adds the H of volume of water sample 0.5%2O2(adding 4.0mL), after reaction, remain 760ml water, Front and back volume of water sample difference is 5%.
(4) water sampling 800ml adds the H of volume of water sample 2%2O2(adding 16.0mL), after reaction, remain 764ml water, Front and back volume of water sample difference is 4.5%.
Coagulation experiment: by coagulating treatment, reduces the COD content in water sample, also removes the total phosphorus content in water sample.
Experimental procedure:
(1) take remaining No. 2 water samples of 100ml and add 2.95ml Ca (OH)2, pH is 10.20, stands mistake after 30min Filter, as No. 6 water samples.
(2) take remaining No. 3 water samples of 100ml and add 3.6ml Ca (OH)2, pH is 10.18, stands mistake after 30min Filter, as No. 7 water samples.
Interpretation:
(1) former water COD is relatively big, can remove part COD after air supporting, and clearance is 17.79% and 24.09%;Coagulation sinks Behind shallow lake, COD clearance is 22.29% and 31.15%, shows have part COD can be removed by precipitation, and this is probably part has Machine thing be attached to precipitation on get rid of after filtering, it is also possible to some in water sample to COD produce interference reproducibility without Machine material is removed through precipitation.
(2) residue H of water sample2O2COD can be produced great interference effect, owing to potassium dichromate oxidation is better than H2O2, So when there being potassium dichromate H2O2Just consume potassium dichromate as reducing agent, cause COD result higher.If therefore added Excessive H2O2Water sample should first decompose remaining H measuring before COD2O2, rule of thumb can add a small amount of manganese sulfate and place Overnight.
After coagulation No. 4 and No. 5 water samples are carried out aeration 6h, then analyzes the parameters such as pH, BOD, COD, TN, TP. Experiment purpose is checking aeration, the coagulation experiment treatment effect to the pickling waste waters containing incretion interferent, goes including COD Except effect, biodegradability promotes effect, total nitrogen total phosphorus removal effect, and analyzes continuous aeration and must affect water sample pH value.
(1) BOD, COD, TN, TP are according to " water and effluent monitoring analyze method " (fourth edition):
BOD uses activated sludge aeration edman degradation Edman;CODcr uses potassium dichromate method to measure;
TN uses potassium persulfate oxidation, determined by ultraviolet spectrophotometry;
TP uses potassium peroxydisulfate method to clear up, and molybdenum-antimony anti-spectrophotometric method measures.
(2) pH, electrical conductivity use Sai Duolisi pH meter to measure.
Confirmatory experiment interpretation of result
(1) through preliminary Air Exposure, utilize the easy characteristic foamy of surfactant, first directly hang up, Ke Yishi The most tentatively reduce the COD in water body, lighten the load for later stage biochemical treatment.
(2) aeration has certain effect to regulation pH value, it is possible to reduce the consumption of regulation pH value medicine.
(3) former water sample biodegradability is relatively low, adds a certain amount of hydrogen peroxide, and lucky and water sample ferrous ions forms Fenton Reagent, degradation of organic substances, increase biodegradability, in order to carry out next step biochemical treatment.
(4) through the first step, second step processes, and can effectively reduce the concentration of TN, TP.The water sample not adding hydrogen peroxide goes out Water TN drops to 38.2mg/L from 321.5mg/L, and clearance is about 88.1%;TP drops to 19.0 from 1183.6mg/L Mg/L, clearance is about 98.4%.The water sample water outlet TN adding 1% hydrogen peroxide drops to 37.3mg/L from 321.5mg/L, Clearance is about 88.4%;TP drops to 4.6mg/L from 1183.6mg/L, and clearance is about 99.6%.
Implement experimental provision equipment
(1)A2/ O reactor: anaerobic reactor, anoxic reacter, aerobic reactor, sedimentation tank all use lucite The capped cylinders processed.Specification is high 90cm, external diameter 20cm, internal diameter 19cm.Reactor both sides differing heights If water inlet, sample tap, outlet, mud discharging mouth.Anaerobic pond top is that evacuation seals, and anoxic pond is half uncovered, good Oxygen pond is aeration pump pressurization.
(2) aerator: use nautical mile electromagnetic type air compressor, connects latex tubing, and end adds bar-shaped micro porous aeration head Supply to aerobic reactor, control tolerance size by screw clamp and control the dissolved oxygen of oxygen reactor well.
(3) heater: use good precious 2010 type heating rods that aerobic reactor is heated and automatically control its temperature Degree.
(4) thermometer: the temperature of water in employing mercurial thermometer (scope 0~100 DEG C) mensuration reactor.
After system stable operation, experiment wastewater is through A2After/O process, the COD of water outlet drops to 112mg/L from 1617mg/L, Clearance is about 93.1%;Ammonia nitrogen drops to 5.7mg/L from 30.5mg/L, and clearance is about 81.3%.
Through A2After a series of process such as/O (anoxia, anaerobism, good support) and precipitation, the big portion such as COD, ammonia nitrogen, total P in water Dividing and be removed, now water outlet i.e. can reach the relevant emission standards that Tianjin specifies.The follow-up depth plus CMF technique Reason, water quality improves further.Through CMF process after water outlet can with through A2Water outlet after/O processes mixes with certain proportion, Also the one-level B class standard in " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) can be reached, this Sample can reduce operating cost.
To sum up, through early stage aeration, coagulating treatment, A2After/O technique and CMF PROCESS FOR TREATMENT, water outlet COD and ammonia nitrogen reach Arrive relevant emission standards.Prove that this experimental technique can ensure that the effect that effluent quality is up to standard, there is actual application potential.
Above the present invention is done exemplary description, it should explanation, in the case of without departing from the core of the present invention, Any simple deformation, amendment or other those skilled in the art can not spend the equivalent of creative work all to fall Enter protection scope of the present invention.

Claims (10)

1. the processing method containing incretion interferent pickling waste waters, it is characterised in that: utilize and give up containing incretion interferent pickling The device of water as steps described below carry out process pickling waste waters:
Step 1, regulates described intake pump, and controlling pickling waste waters flow is 2-5m3/h;
Step 2, staticly settles, and described regulating reservoir carries out the regulation of water quality and quantity to waste water, makes waste water reach steady statue, PH value is 0.5-1.5, and in highly acid, waste water residence time in described regulating reservoir is 44-50h;
Step 3, waste water residence time in described foam separator is 10-40min, is removed by described demister The incretion interferent of 60%-70%, the water outlet after the process of described demister, also need to focus on further, described demister Water outlet contains high concentration and shows that active substance can be as low side abluent;
Step 4, in described Fenton oxidation device, the time of staying of waste water is 4-10h, adds in described Fenton oxidation tank Medicine includes FeSO4·7H2O and hydrogen peroxide (H2O2), wherein Fe2+It is 1-4:1, FeSO with hydrogen peroxide ratio4·7H2O Mass percent be 2wt%-20wt%, the mass percent of hydrogen peroxide is 20-40wt%, and the addition of hydrogen peroxide is intended to The twice of the COD removed;
Step 5, in described reaction precipitation tank, the time of staying of waste water is 1-9h, the medicine added in described reaction precipitation tank Product include polyacrylamide, aluminium polychlorid and calcium chloride, the addition of flocculant can remove 10%-17% through Fenton oxidation The precipitation that small organic molecule is formed, is connected with described reaction precipitation tank by the described first online pH detection device, with really Protect the water quality in described reaction precipitation tank reaching pH is 9-10;
Step 6, in described second regulating reservoir, the time of staying of waste water is 20-26h, and adds nutrient substance, to water sample Further regulated, be suitable for the water environment of growth of microorganism, by the described second online pH detection device and described the Two regulating reservoirs are connected, with guarantee the water quality in described second regulating reservoir reach pH as 6-8 about;
Step 7, when carrying out pickling waste waters biochemical treatment, regulates described second elevator pump, and control flow is 1-5m3/h;
Step 8, at described A2In/O biochemical treatment apparatus, the total residence time of waste water is 20-24h, at described hypoxia response The time of staying in device is 2-6h, and the time of staying in described anaerobic reactor is 3-9h, in described aerobic reactor The time of staying be 9-15h, in described aerobic reactor during aeration, by aerator adjust aeration air mass flow be 0.5-1.8m3/min;
Step 9, in described sedimentation tank, the time of staying of waste water is 1-8h, and function is mud-water separation, and a mud part is returned Flowing to described anaerobic reactor, supernatant flows into described intermediate water tank by outlet pipe, in described sedimentation tank as processing water Excess sludge entered in described storage basin by sludge pipe;
Step 10, regulates described force (forcing) pump, adjusts flow and does not exceeds 2.4m3/ h, is filtering dress through described activated carbon Put process;
Device containing incretion interferent pickling waste waters include the first regulating reservoir, foam separator, Fenton oxidation retort, Reaction precipitation tank, the second regulating reservoir, A2/ O biochemical treatment apparatus, sedimentation tank, intermediate water tank, CMF device, activated carbon mistake Filter tank and product water tank, wherein:
Described first regulating reservoir is connected with described foam separator, and described first regulating reservoir is connected with wastewater outlet, described First regulating reservoir is connected with described CMF device and described active carbon filtering device;
Described foam separator is connected with demister, and described foam separator is connected with described Fenton oxidation tank;
Ferrous sulfate grug feeding jar is connected with described Fenton oxidation tank, and hydrogen peroxide grug feeding jar is connected with described Fenton oxidation tank, institute State Fenton oxidation tank to be connected with described reaction precipitation tank;
Calcium chloride grug feeding jar is connected with described reaction precipitation tank, and PAC grug feeding jar is connected with described reaction precipitation tank, PAM dosing Tank is connected with described reaction precipitation tank, and described reaction precipitation tank is connected with storage basin, described reaction precipitation tank and described second Regulating reservoir is connected, and arranges the first online pH and detect device in described reaction precipitation tank;
Described A2/ O biochemical treatment apparatus includes anaerobic reactor, anoxic reacter and aerobic reactor;Described anaerobic reaction Device is connected with described anoxic reacter, and described anoxic reacter is connected with described aerobic reactor, described aerobic reactor with Described sedimentation tank is connected;
Described second regulating reservoir is connected with nutrient substance grug feeding jar, described second regulating reservoir and described A2/ O biochemical treatment apparatus Described in anaerobic reactor be connected, arrange in described second regulating reservoir second online pH detection device;
Described sedimentation tank and described A2Anaerobic reactor described in/O biochemical treatment apparatus is connected, described sedimentation tank and storage basin Being connected, described storage basin is connected with filter press, and described sedimentation tank is connected with described intermediate water tank;
Described intermediate water tank is connected with described CMF device, and described CMF device is connected with described active carbon filtering device, institute Stating active carbon filtering device to be connected with described product water tank, described product water tank is connected with chlorine tablets grug feeding jar;
Described pickling waste waters is passed directly into the first regulating reservoir by entering waste pipe, enters to arrange intake pump on waste pipe described;
It is connected with described foam separator top by the first outlet pipe bottom described first regulating reservoir, goes out described first First elevator pump is set on water pipe;
By the 5th outlet pipe and described A bottom described second regulating reservoir2Anaerobic reactor top described in/O biochemical treatment apparatus Portion is connected, and arranges the second elevator pump on described 5th outlet pipe;
By reflux sludge tube and described A bottom described sedimentation tank2Anaerobic reactor top phase described in/O biochemical treatment apparatus Even, described reflux sludge tube arranges sludge pump;
It is connected with described filter press by sludge discharging pipe bottom described storage basin, described sludge discharging pipe arranges screw rod Pump;
It is connected with described CMF bottom of device, on described 8th outlet pipe by the 8th outlet pipe bottom described intermediate water tank Arranging force (forcing) pump and self-cleaning filter, described force (forcing) pump is connected with described self-cleaning filter;
Described active carbon filtering device is connected with described product water tank by the tenth outlet pipe, described tenth outlet pipe is arranged anti- Wash water pump;
Select pipeline as the connection unit of each ingredient.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: described Arranging agitating device in storage basin, described agitating device is QJB diving mixer.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: described A2Described in/O biochemical treatment apparatus, aerobic reaction pond is connected with aerator, and described aerator is Roots blower.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: described First elevator pump, described second elevator pump, described sludge pump, described screw pump, described force (forcing) pump and described backwash water The quantity of pump is two.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: described Processing means is fixed in moveable device.
Processing method containing incretion interferent pickling waste waters the most according to claim 5, it is characterised in that: described Movably device is mobile container.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: described The flow of intake pump is 3m3/ h, the flow of described second elevator pump is 2-3m3/ h, the air mass flow of described aerator aeration For 1.0-1.3m3/ min, the flow of described force (forcing) pump is 1.5-2.2m3/h。
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: in institute Stating residence time in regulating reservoir is 48h, and in described foam separator, residence time is 20-30min, described In Fenton oxidation device, the time of staying of waste water is 6-8h, and in described reaction precipitation tank, the time of staying of waste water is 3-7h, In described second regulating reservoir, the time of staying of waste water is 24h, and in described sedimentation tank, the time of staying of waste water is 2-6h.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: in institute State in step 6, Fe2+It is 3:1, FeSO with hydrogen peroxide ratio4·7H2The mass percent of O is 5wt%-15wt%, peroxidating The mass percent of hydrogen is 30-35wt%.
Processing method containing incretion interferent pickling waste waters the most according to claim 1, it is characterised in that: in institute State in step 8, at described A2In/O biochemical treatment apparatus, the total residence time of waste water is 23h, at described anoxic reacter The interior time of staying is 4-5h, and the time of staying in described anaerobic reactor is 6-8h, in described aerobic reactor The time of staying is 10-13h.
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