CN102826686A - Double-membrane treatment method of iron and steel industrial wastewater - Google Patents

Double-membrane treatment method of iron and steel industrial wastewater Download PDF

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CN102826686A
CN102826686A CN2012103438273A CN201210343827A CN102826686A CN 102826686 A CN102826686 A CN 102826686A CN 2012103438273 A CN2012103438273 A CN 2012103438273A CN 201210343827 A CN201210343827 A CN 201210343827A CN 102826686 A CN102826686 A CN 102826686A
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wastewater
waste water
water
reverse osmosis
treatment
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CN2012103438273A
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CN102826686B (en
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贺占超
赵瑞峰
王瑞红
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山西太钢不锈钢股份有限公司
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Abstract

The invention provides a double-membrane treatment method of iron and steel industrial wastewater. The method comprises the following steps that the pH value of the wastewater is regulated to be greater than 7, and then, oxygen gas is introduced into the wastewater until the total iron content in the wastewater is reduced to a value smaller than 0.5mg/l; the pH value of the wastewater is regulated to 8.0 to 8.5, flocculating agents and coagulant aids are added into the wastewater under the stirring condition, and then, the static settlement is carried out; the wastewater subjected to preliminary treatment is subjected to filtering treatment in a filter so that the water outlet turbidity of the wastewater is smaller than 2NTU; the wastewater subjected to filtering treatment is subjected to full flow filtering treatment; the wastewater subjected to pretreatment is subjected to two-stage reverse osmosis treatment; and the wastewater subjected to the two-stage reverse osmosis treatment is subjected to fine treatment through a mixing bed. The double-membrane treatment method has the advantages that the treated wastewater reaches the demineralized water standard, the cyclic utilization rate of water resources is improved, the consumption of new water is saved, and the outward discharge water of a ton of steel is reduced.

Description

The Wastewater Of Steel Industry double membrane processing method
Technical field
The present invention relates to a kind of Wastewater Of Steel Industry treatment process, especially a kind of Wastewater Of Steel Industry double membrane processing method that adopts ultra-filtration membrane and reverse osmosis membrane to carry out.
Background technology
Over nearly 30 years; The development of ultra-filtration technique is very rapid, not only original effect is being arranged aspect the separation of singular solution, and the application aspect the industrial sewage reuse is also more and more; The Chang Zuowei pre-processing device is guaranteed the long-term safety steady running of follow-up equipments such as r-o-.
Ultrafiltration is a kind of membrane separation technique, and its film is the porousness unsymmetrical structure.Filtration procedure is to be motivating force with the both sides differential pressure of membrane, and with a kind of solution separating process that the mechanical grading principle is the basis, applying pressure is generally 0.03 ~ 0.6MPa, and the screening aperture is from 0.005 ~ 0.1 μ m, and molecular weight cut-off is about 1000 ~ 500,000 dalton.One of its topmost form is a hollow-fibre membrane, is capillary, forms through spray silk spinning system.Its internal surface or outside surface are tight zone, or claim active coating, and inside is the porous supporting mass.
The principle of reverse osmosis desalination is: in water salty (Ru Yuanshui); Impose than naturally osmotic and press bigger pressure, infiltration is carried out round about, be pressed onto the water molecules in the former water the other side of film; Become clean water (de-mineralized water), thereby reach the purpose of removing the middle salinity that anhydrates.Separation method with other is compared, and r-o-has significant advantage: do not undergo phase transition, do not produce secondary pollution, need not heat, equipment is simple, efficient is high, take up an area of less, energy consumption is low, simple to operate, flexible etc.In higher salt concentration scope, r-o-has lower energy consumption than desalting process such as IX and electrodialysis, and also constantly mechanize, robotization of masking technique.
Reverse osmosis technology just began one's study in the fifties; Process reverse osmosis membrane with commercial value to the end of the sixties; Began to have the industrialness reverse osmosis unit to put into operation in 1971, adopt reverse osmosis method to carry out water treatment now and spread all over countries such as the U.S., Japan, France, Italy in power plant.China begins to introduce the water treatment of reverse osmosis unit in the power station the end of the seventies; The nineties, the development of reverse osmosis membrane became focus, and reverse osmosis technology is mainly used in wastewater treatments such as sea water desaltination, pure water and ultrapure water preparation, city water processing, municipal sewage treatment and application, industrial electro waste electroplating and pulp and paper industry wastewater treatment, chemical wastewater treatment, foodstuffs industry, medicine industry now.This has proved that fully reverse osmosis technology is in reusing sewage Treatment Technology mature and reliable.
Owing to the complicacy and the unstable of steel wastewater, sophisticated Technology does not appear in the also not popularization and application in steel wastewater reuse field of embrane method technology at present.
Summary of the invention
Technical problem to be solved by this invention is: overcome the defective that existing steel wastewater treatment process can not reach the de-mineralized water standard; Providing a kind of adopts two embrane method water technologies to handle the method that reclaims Iron and Steel Production waste water; Waste water after the processing reaches the de-mineralized water standard; Improve the water resources cyclic utilization rate, practiced thrift new water consumption, reduced the outer draining of ton steel.
The present invention is directed to steel rolling, smelting wastewater water quality characteristics; Reasonable, efficient, the energy-conservation pre-treatment and the pretreatment technology flow process that adopt; Be operations such as aeration, Youxiaolin sterilization, coagulating sedimentation, multi-medium filtering, ultrafiltration, waste water has reached the influent quality standard of reverse osmosis unit requirement after treatment.In addition, optimization of the present invention adds the auxiliary agent kind, adds the auxiliary agent point, adds assistant concentration, and process efficiency is further improved, and has guaranteed reverse osmosis system steady running.
In order to solve the problems of the technologies described above, first technical scheme provided by the invention is, a kind of Wastewater Of Steel Industry double membrane processing method, and this method comprises:
B. pre-treatment
A1) aeration oxide treatment: waste water ph is adjusted to greater than 7, aerating oxygen in waste water then, total iron content drops to<0.5mg/l in waste water;
A2) automatic reaction, precipitation process: waste water ph is adjusted to 8.0-8.5, under agitation condition, in waste water, adds flocculation agent and coagulant aids, staticly settle then, make the wastewater effluent turbidity reach below the 5NTU;
B. pre-treatment
B1) filtration treatment: the waste water after the pre-treatment is carried out filtration treatment in strainer, so that the wastewater effluent turbidity is less than 2NTU;
B2) uf processing: the waste water after the filtration treatment is carried out grossflow filtration handle, feasible pollution index≤3 through the waste water after the uf processing;
C. the twin-stage reverse-osmosis treated is carried out two steps ro with pretreated waste water and is handled;
D. precision processing adopts mixed bed to carry out precision processing the waste water after the twin-stage reverse-osmosis treated.
Aforesaid Wastewater Of Steel Industry double membrane processing method is at step a2) in, said flocculation agent is a Poly aluminum Chloride (PAC), polyaluminium sulfate, polymer phosphate aluminium, bodied ferric sulfate, poly-ferric chloride or polymer phosphate iron; Said coagulant aids is a SEPIGEL 305, polydimethyl dipropenyl ammonium chloride, gelatine or sodium-alginate; Preferably, flocculation agent is a Poly aluminum Chloride (PAC), is 20-30mg/l in the wastewater volume flocculant addition; Coagulant aids is a SEPIGEL 305, is 0.1-0.2mg/l in wastewater volume coagulant aids add-on.
Aforesaid Wastewater Of Steel Industry double membrane processing method; At step a2) taking a step forward comprises degerming algae treatment step: add in the waste water after the aeration oxide treatment that chlorine residue is 1.2-1.5mg/l in the water outlet of chloro sterilizing agent control settling tank, said chloro sterilizing agent is Youxiaolin, liquid chlorine or dioxide peroxide.
Aforesaid Wastewater Of Steel Industry double membrane processing method is at step b1) in, said strainer is a more medium filter, the waste water flow velocity is 6-10m/h.
Aforesaid Wastewater Of Steel Industry double membrane processing method is at step b2) in, the membrane pore size of said ultrafiltration apparatus is 0.03-0.1 μ m, filtering molecular weight is more than 20,000.
Aforesaid Wastewater Of Steel Industry double membrane processing method, pretreated waste water are regulated waste water ph to 6.5-7.5 before carrying out the first-stage reverse osmosis processing.
Aforesaid Wastewater Of Steel Industry double membrane processing method, pretreated waste water adds the Scale inhibitors organic phosphonate before carrying out the first-stage reverse osmosis processing, be 3.5-5mg/l in wastewater volume Scale inhibitors add-on.
Aforesaid Wastewater Of Steel Industry double membrane processing method, pretreated waste water is before carrying out the first-stage reverse osmosis processing, and adding reductive agent to waste water is 200mv ± 10mv in redox potential (ORP); Said reductive agent is inferior sodium pyrosulfate, potassium aluminium sulfate, S-WAT or sodium sulfite anhy 96.
Aforesaid Wastewater Of Steel Industry double membrane processing method, the waste water after first-stage reverse osmosis is handled are regulated waste water ph to 7-8 before carrying out the two-pass reverse osmosis processing.
Aforesaid Wastewater Of Steel Industry double membrane processing method, the intersegmental pressure reduction of first-stage reverse osmosis is controlled at below the 0.3MPa, and the intersegmental pressure reduction of two-pass reverse osmosis is controlled at below the 0.2MPa.
Aforesaid Wastewater Of Steel Industry double membrane processing method adopts each auxiliary agent of computer control to add volume pump and corresponding technical process pump interlocking start and stop.
Aforesaid Wastewater Of Steel Industry double membrane processing method; Pretreated waste water is before carrying out the twin-stage reverse-osmosis treated; Adopt security personnel's strainer to carry out filtration treatment, and two-stage hoisting pump frequency conversion and ultrafiltration to produce the jellyfish pipe pressure chain, guarantee that waste water reaches the pressure requirement of the strainer of ensuring public security.
Aforesaid Wastewater Of Steel Industry double membrane processing method; Periodically in pretreated waste water, add non-oxidizable sterilant; Wherein said non-oxidizable sterilant is dichlorophen, dioxy cyanic acid methane, RH-893, dodecylbenzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide or 2,2-dibrominated-3-nitrilo propionic acid amide.
Adopt the two embrane method water technologies of the present invention to handle and reclaim high pollution Iron and Steel Production waste water, processing reaches the de-mineralized water standard, has improved the water resources cyclic utilization rate, has reduced new water consumption, has reduced the outer draining of ton steel.
Description of drawings
Fig. 1 is said to be process flow sheet of the present invention.
Embodiment
For fully understanding the present invention's purpose, characteristic and effect,, the present invention is elaborated by following concrete embodiment.
The steel rolling that the present invention handles, smelt and produce the waste water that produces, its pollutant component is complicated, and electricity is led in the waste water, hardness, bacterium, mikrobe, organic content is high and fluctuation is big, and water quality is quite abominable, and it handles quite difficulty.
The present invention is directed to steel rolling, smelting wastewater water quality characteristics; Reasonable, efficient, the energy-conservation pre-treatment and the pretreatment technology flow process that adopt; Be operations such as aeration, sterilization, coagulating sedimentation, multi-medium filtering, ultrafiltration; Waste water has reached the influent quality standard of reverse osmosis unit requirement after treatment, and system is stable, and is reliable.In addition, optimization of the present invention adds the auxiliary agent kind, adds the auxiliary agent point, adds assistant concentration, and process efficiency is further improved, and has guaranteed reverse osmosis system steady running.
In the two membrane process crafts of the present invention; Do not set up intermediate water tank between ultrafiltration and the r-o-, it is chain to produce the jellyfish pipe pressure through two-stage hoisting pump frequency conversion and ultrafiltration, guarantees the pressure of 0.21MPa; Reduce the investment of a water tank and lift pump, practiced thrift the operation energy consumption cost simultaneously.
The present invention is directed to organic content height in the steel wastewater water quality characteristics water, bacterium, content of microorganisms height are bred fast characteristics; Behind reductive agent dispensing point; Increased non-oxidizable sterilant dosing system again, regularly sterilization has been carried out in r-o-, avoided microbial contamination stifled the dirt of film.
Cross flow filter was all adopted in ultrafiltration in reusing sewage in the past, in the WWT and the ultrafiltration producer suggestion hyperfiltration reverse-rinsing cycle between 20-40min, flux is 45L/m 2About h.And full filtration filter has been adopted in ultrafiltration among the present invention, designs long 72min of hyperfiltration reverse-rinsing cycle, has effectively promoted the recovery of ultrafiltration; Simultaneously, big flux design 56.8L/m is adopted in ultrafiltration 2H.
The handled waste water of the present invention is that Iron and Steel Production is rolled the mixing water of distinguishing and smelting two kinds of waste water.Rolling effluent comprises: in the hot-rolled process, need use the water cooling roll through pricking when roller is rolled into various steel (steel plate, rod iron, rail etc.) with steel ingot, flushing iron scale and the waste water that produces; The diluted acid water that rolling system produces, nitration mixture, alkali oil waste water etc. are to neutralization station and the waste water that produces of back; Pipeline transports the waste water that powdered iron ore produces; All waste water of rolling system such as continuous casting system is clean, turbid circulating water sewer.Smelting wastewater comprises: circulation water of blast furnace draining, Coal-gas Washing Water Using, blast furnace water-break, grain slag, sintering, smelting system waste water such as coking.
Through macrocyclic statistical study,,,, formed technology of the present invention through continuous process modification through bench-scale testing repeatedly in conjunction with existing water technology to the steel wastewater water quality data.First-stage reverse osmosis ability of the present invention is 1400m 3/ h, whole process system is divided into: pre-treatment, pre-treatment, twin-stage r-o-and precision processing four parts.The present invention is core with the reverse osmosis desalination, and pre-treatment comprises aeration oxide treatment and automatic reaction deposition, and pre-treatment comprises that more medium filter filters and ultrafiltration, and precision processing comprises that mixing bed handles.The present invention guarantees that process system produces the requirement that water meets BW.
Specify steel wastewater treatment process of the present invention and related equipment below in conjunction with Fig. 1.
1. pre-treatment
The main purpose of pre-treatment steel wastewater is most of iron, manganese, suspended substance, colloid and the partial organic substances of removing in the waste water, alleviates its product water water quality of burden and raising of pretreatment system.Pretreating device mainly comprises aeration oxidation pond, automatic reaction settling tank and the inclined-plate clarifying basin that connects successively.This pretreating device further comprises: mechanical grille, Youxiaolin medicine machine, flocculation agent medicine machine and coagulant aids medicine machine.Before mechanical grille was arranged on the aeration oxidation pond, the Youxiaolin medicine machine was connected with the aeration oxidation pond, and the flocculation agent medicine machine is connected with the automatic reaction settling tank with the coagulant aids medicine machine.
1.1 aeration oxide treatment
Waste water ph is adjusted to greater than 7, aerating oxygen in waste water then, total iron content drops to<0.5mg/l in waste water.
Concrete, this aeration oxidation operation mainly carries out in the aeration oxidation pond.Iron is with Fe in the waste water 2+Form exist, can not be removed, the present invention adds alkali in waste water, mineral alkali commonly used such as sodium hydroxide, Pottasium Hydroxide for example is adjusted to waste water ph>7.Then, oxygen is passed in the waste water, (CO simultaneously leaves preferably to adopt conventional air aeration method 2), airborne oxygen is with the Fe in the waste water 2+Be oxidized to Fe 3+, and form Fe (OH) 3Colloid.This Fe (OH) 3Colloid can be removed in post precipitation is handled.The time of aerating oxygen drops to<0.5mg/l for total iron content in waste water in waste water, and this residence time is about 20 minutes usually.
The steel wastewater iron-holder is 1-15mg/l, with the coagulating sedimentation+more medium filter of operation sewage employing forward, can only remove a few part iron.The present invention adopts the aeration oxide treatment, can total iron content be dropped to<0.5mg/l.
1.2 automatic reaction, precipitation process
Waste water ph is adjusted to 8.0-8.5 (preferred 8.2), under agitation condition, in waste water, adds flocculation agent and coagulant aids, staticly settle then.
The automatic reaction precipitation process is in order to remove iron, manganese, the calcium ion in the waste water.Concrete, after the aeration oxide treatment, waste water is delivered in the automatic reaction pond, preferably adopt the one-level lift pump that waste water is delivered to the automatic reaction pond.Before waste water gets into the automatic reaction pond, add alkali, for example mineral alkali commonly used such as sodium hydroxide, Pottasium Hydroxide is adjusted to 8.0-8.5 (preferred 8.2) with waste water ph.
In the automatic reaction pond, adopt stirrer, make medicament (flocculation agent and coagulant aids) and the abundant mixing of waste water.Preferably, in the automatic reaction pond, adopt many group stirrers, and the stirring velocity of these stirrers reduces gradually from fast to slow to discharge port from mechanical reaction tank opening for feed, make medicament (flocculation agent and coagulant aids) and the abundant mixing of waste water.For example, the automatic reaction pond is made up of three groups of stirrers (4 every group), and rotating speed reduces to discharge port from mechanical reaction tank opening for feed from fast to slow gradually, and the impeller middle line speed of three groups of stirrers is respectively 0.54m/s, 0.35m/s, 0.15m/s.
In the automatic reaction pond waste water with add flocculation agent and coagulant aids and mix afterwards oneself and flow into settling tank and leave standstill, most suspended substances is removed in settling tank, delivery turbidity reaches below the 5NTU.The present invention preferably adopts conventional radial-flow inclined-plate clarifying basin, and the present invention does not have particular requirement to the quantity and the size of radial-flow inclined-plate clarifying basin, the decision of the wastewater flow rate that can handle as required, and for example adopting 2 diameters is 29 meters radial-flow inclined-plate clarifying basin.
The flocculation agent that the present invention preferably uses is an inorganic polymer flocculant; For example Poly aluminum Chloride (PAC) (PAC) polyaluminium sulfate (PAS), polymer phosphate aluminium (PAP), bodied ferric sulfate (PFS), poly-ferric chloride (PFC), polymer phosphate iron (PFP); More preferably adopt Poly aluminum Chloride (PAC) as flocculation agent, particularly contain 30wt%Al 2O 3Solid polyaluminium chloride as flocculation agent, in wastewater volume, the concentration that adds of Poly aluminum Chloride (PAC) is 20-30mg/l.The coagulant aids that the present invention preferably uses is the organic polymer coagulant aids, SEPIGEL 305 for example, and the polydimethyl dipropenyl ammonium chloride, gelatine, sodium-alginate, more preferably SEPIGEL 305 is as coagulant aids, and the concentration that adds of SEPIGEL 305 is 0.1-0.2mg/l.
Preferably, pre-treatment of the present invention further comprises the steps:
1.3 water intaking is handled
Before waste water gets into the aeration oxide treatment, with big swimmer in the grid interception waste water.For example, during from water reservoir water intaking (rolling effluent and smelting wastewater), grid is set, big swimmer in the interception waste water at intake.
1.4 the degerming algae is handled
Before automatic reaction, precipitation process, add the chloro sterilizing agent in the waste water after the aeration oxide treatment, control settling tank water outlet chlorine residue 1.2-1.5mg/l.Said chloro sterilizing agent is Youxiaolin, liquid chlorine or dioxide peroxide.
Because organic content is 40-80mg/l in the waste water, and ammonia nitrogen is up to 18mg/l, and wastewater temperature is between 15-28 ℃.Under such condition, be fit to the growth of bacterium algae, especially summer, the microbial contamination of waste water is serious.Get into the post-order process step and form the biological clay pollution for fear of the bacterium algae; And for fear of the safe and stable operation that influences ultrafiltration, reverse osmosis membrane; Add the chloro sterilizing agent in the waste water after the aeration oxide treatment; For example effective chlorine density is the Youxiaolin of 10-15mg/l, and control settling tank water outlet chlorine residue 1.2-1.5mg/l, and follow-up ultrafiltration water outlet chlorine residue is between 0.5-0.8mg/l.
2. pre-treatment
The main purpose of pre-treatment steel wastewater is further to remove the impurity that suspended substance in the waste water, colloid, colourity, turbidity, organism etc. hinder follow-up reverse-osmosis treated.Pretreatment unit mainly comprises more medium filter and the ultrafiltration apparatus that connects successively.Pretreatment unit further comprises filter backwash pump, filter backwash water tank, roots blower, hyperfiltration reverse-rinsing pump, hyperfiltration reverse-rinsing water pot, ultrafiltration cleaning system and Youxiaolin medicine system.The filter backwash water tank is connected with the filter backwash pump successively, and is connected with more medium filter, and roots blower is connected with more medium filter.The hyperfiltration reverse-rinsing water pot is connected with the hyperfiltration reverse-rinsing pump successively, and is connected with ultrafiltration apparatus, and the Youxiaolin medicine system is connected with the hyperfiltration reverse-rinsing water pot.The ultrafiltration cleaning system is connected with ultrafiltration apparatus.
2.1 filtration treatment
Waste water after the pre-treatment advances two-stage hoisting pump water tank from settling tank, and the waste water after adopting secondary deduction pump with pre-treatment then adds and is sent in the strainer.Waste water after the pre-treatment is carried out filtration treatment in strainer, so that the wastewater effluent turbidity is less than 2NTU.
Preferably, adopt conventional more medium filter to carry out filtration treatment, the waste water flow velocity is 6-10m/h (preferred 9m/h), and pressure is greater than 0.2Mpa.More medium filter is mainly held back through filtering layer and is removed most suspended substances and colloid in the water.Preferably, the filler of more medium filter adopts hard coal, silica sand and pebbles, for example following filling-material structure: (1) hard coal (upper strata): particle diameter: 0.8-1.2mm, thickness: 400mm; (2) silica sand (lower floor): particle diameter: 0.5-0.8mm, thickness: 700mm; (3) silica sand (bed course): particle diameter: 3.0-4.0mm, thickness: 100mm; (4) silica sand (bed course): particle diameter: 4.0-8.0mm, thickness: 100mm; (5) pebbles (bed course): particle diameter: 6.0-12.0mm, thickness: 100mm; (6) pebbles (bed course): particle diameter: 12.0-18.0mm, thickness: 100mm; (7) pebbles (bed course): particle diameter: 18.0-25.0mm, thickness: 100mm.
The backwash cycle of strainer confirms that according to Inlet and outlet water pressure reduction or accumulated running time for example specification φ 5000, handles flow 194m 3/ h, the strainer of flow velocity 9.0m/h carries out backwash after 24 hours working times.Backwash water adopts strainer to produce water, and the strainer in the filter backwash water tank produces water under the filter backwash pumping action, according to backwash intensity 8-12L/m 2.s (preferred 10L/m 2.s) strainer is carried out backwash.Water enters the steel wastewater pond after the backwash, gets into pre-treatment once more.Adopt roots blower to carry out gas and clean, and gas scouring intensity is 8-12L/m 2.s (preferred 10L/m 2.s).
2.2 uf processing
Waste water after the filtration treatment is carried out grossflow filtration (full dose filtration) to be handled.Big flux design is adopted in ultrafiltration of the present invention, and the product water flux is 56.8L/m 2H is greater than the product water flux 45L/m of common WWT design 2H.
The effect of uf processing (UF) waste water is to remove impurity such as particle in the waste water, suspended substance, colloid, organism, guarantees to produce water pollution index (SDI)≤3, satisfies the requirement of reverse osmosis unit.Uf processing waste water reclamation rate of the present invention is >=90%.
Ultrafiltration apparatus preferred film aperture is the film of 0.03-0.1 μ m (preferred 0.03 μ m), and its material can be the conventional ultrafiltration membrane material, for example pvdf (PVDF).Preferred its film silk inside/outside of ultra-filtration membrane directly is 0.6-0.8/1.2-1.4mm (preferred 0.7/1.3mm), filtration cycle >=72min.According to wastewater flow, ultrafiltration apparatus can be selected many cover membrane modules for use, for example selects 12 cover ultrafiltration apparatuss for use, and every cover comprises 64 membrane modules, and every covering device designing treatment amount is 189m 3/ h.
Ultrafiltration apparatus operation for some time, need carry out backwash and handle.The backwash water water source adopts ultrafiltration to produce water, adds the Youxiaolin sterilization in the backwash water, and the concentration of Youxiaolin is 30-40mg/l in the backwash water.Backwash pressure reduction is increased to maximum operating pressure differential, and backwash intensity is 100-150L/m 2H.The Youxiaolin medicine system is produced the ultrafiltration that Youxiaolin joins in the hyperfiltration reverse-rinsing water pot in the water, and the ultrafiltration under the hyperfiltration reverse-rinsing pumping action in the hyperfiltration reverse-rinsing water pot is produced water entering ultrafiltration apparatus and carried out backwash.The mode of gas-water associating is adopted in the backwash of ultra-filtration equipment (SFR), and every operation backwash in 72 minutes once.
Water production rate is little or when reaching 2 months working time, need carry out matting to ultrafiltration apparatus.In the hyperfiltration membrane assembly long-time running process, the film surface can be covered by the various detrimental impurity that it is held back and form cake layer, even fenestra also can increase the film pressure of passing through of waste water by more tiny impurity obstruction.The quality of useless pretreatment quality can only solve the speed problem of the contaminated speed of film, and contaminated solution problem fundamentally needs regularly carry out matting to ultrafiltration apparatus for this reason.The cleaning interval of ultrafiltration apparatus receives the influence of itself material capability parameter, operational conditions (like temperature, pressure etc.).
When cleaning organic matter and microbial contamination, the chemical formulation of the cleaning ultrafiltration apparatus that the present invention adopts is NaOH and the 0.15-0.25wt%NaClO of the aqueous solution that comprises following material: 0.03-0.07wt%, preferred 0.05wt%NaOH+0.2wt%NaClO.In this cleaning process through adding PH that alkali guarantees matting water at 11-12.
Cleaning iron pollution, carbonate crystallization dirt are blocked up when reaching the part colloid; The chemical formulation of the cleaning ultrafiltration apparatus that the present invention adopts is oxalic acid solution or the hydrochloric acid of concentration 0.3-0.5wt% or the citric acid solution of concentration 1.5-2.5wt%, the hydrochloric acid of the oxalic acid solution of preferred concentration 2wt% or concentration 0.4wt% or the citric acid solution of concentration 2wt% of concentration 1.5-2.5wt%.In this cleaning process through adding PH that acid guarantees matting water at 1.5-2.0.
3. twin-stage reverse-osmosis treated
Adopt the one-level HPP to deliver to the twin-stage reverse osmosis unit pretreated waste water and carry out the two steps ro processing.Wherein the intersegmental pressure reduction of first-stage reverse osmosis is controlled at below the 0.3MPa, and the intersegmental pressure reduction of two-pass reverse osmosis is controlled at below the 0.2MPa.One-level infiltration of the present invention and secondary infiltration are formed by multistage.Intersegmental pressure reduction is meant: the pressure reduction between the dense water of certain section water inlet and this section.The waste water reclamation rate of twin-stage reverse-osmosis treated of the present invention is 75%, and this lower waste water reclamation rate is easy to prevent that fouling and film from polluting.
Twin-stage reverse osmosis unit of the present invention mainly comprises one-level HPP, first-stage reverse osmosis device, secondary HPP, two-pass reverse osmosis device, first-stage reverse osmosis water tank and two-pass reverse osmosis water tank.The effect of pretreated waste water process one-level HPP is sent in the first-stage reverse osmosis device; A first-stage reverse osmosis device water outlet part gets into the associating pumping plant; Outer confession de-mineralized water user; It is personal that a part gets into the first-stage reverse osmosis water tank, and a part gets in the two-pass reverse osmosis device via the effect of secondary HPP, gets into the two-pass reverse osmosis water tank then.Specify the waste water of handling through two-pass reverse osmosis below.
The main purpose of reverse-osmosis treated is to remove dissolved salts in the waste water, removes small-particle that some macromole and last stage do not remove etc. simultaneously.According to the difference of wastewater flow, can select the quantity of reverse osmosis unit.Preferably, select for use low pressure pollution resistant composite film (BW30-365FR and BW30-400FR) as reverse osmosis membrane of the present invention, single film ratio of desalinization reaches more than 99.5%.
Preferably, the first-stage reverse osmosis device comprises 7 covers, and it is 32:16 that 1#-4# unit pressurized vessel is arranged; Every cover adopts 336 membrane elements, and it is 36:18 that 5#-6# unit pressurized vessel is arranged, and every cover adopts 324 membrane elements; It is 30:15 that 0# unit pressurized vessel is arranged, and adopts 315 membrane elements.When the reverse osmosis equipment temperature was 20 ℃, the every cover of first-stage reverse osmosis device was exerted oneself and is 235m 3/ h, the recovery is 75%, and ratio of desalinization is not less than 97%.
The two-pass reverse osmosis device further removes first-stage reverse osmosis and produces the salt in the water, prolongs the regeneration period of mixing bed.Preferably, the two-pass reverse osmosis device comprises 3 covers, and it is 11:4 that the unit pressurized vessel is arranged, and every cover adopts 90 membrane elements.
First-stage reverse osmosis device water production rate is 1400m 3/ h, two-pass reverse osmosis device water production rate is 300m 3/ h.One-level HPP and secondary HPP provide enough pressure to reverse osmosis unit; Situation according to actual reverse osmosis unit and waste water; Can adjust the force value that one-level HPP and secondary HPP provide, for example one-level HPP and secondary HPP provide the pressure of 1MPa in an embodiment.Waste water under the effect of one-level HPP after the ultrafiltration gets into the first-stage reverse osmosis device, and under the effect of secondary HPP, the waste water after the first-stage reverse osmosis apparatus processes gets into the two-pass reverse osmosis device.
Reverse osmosis unit must not be stopped transport for a long time, and move 2 hours every day at least.If prepare to shut down more than 72 hours, use chemical cleaning system in assembly, to dash the sodium sulfite solution of dress concentration, to implement protection as 1wt%.The each start of reverse osmosis unit (RO) all should intake pressure less than the 0.5MPa condition under flushing 5-10 minute.Stifled for the dirt of effectively eliminating, alleviate film, reverse osmosis unit film unit was carried out big yield wash once in per 24 hours.
Reverse osmosis unit is normally in service; Membrane element can receive the flushing of wet water; So only descend 10% or more in theory, pressure drop increase more than 15%, ratio of desalinization obviously descend under the degradation situation, just need carry out matting to reverse osmosis unit at reverse osmosis unit (RO) aquifer yield.But in order to guarantee the long safe operation of reverse osmosis unit, common 1 month matting reverse osmosis unit once.Need segmentation to clean during cleaning, it is identical with the direction of operation to clean direction, does not allow reverse cleaning, to avoid film and rolls up and stretch out and damage membrane element.
During matting, working pressure is controlled to be: under the prerequisite that satisfies water production rate and water quality, get low force value as far as possible; Quantity discharged control: because the variation of factors such as water temperature, working pressure makes the water production rate of device that corresponding variation also take place, at this moment tackle quantity discharged adjustment, ratio is 1:3 between control quantity discharged and the water production rate.
Be in operation, the RO film possibly polluted or obstruction by inorganics dirt, colloid, mikrobe, MOX etc.These electrodeposition substances will cause that RO film transit dose descends and ratio of desalinization reduces on the film surface.Therefore, for transit dose and the desalting performance that recovers the RO film, need carry out matting termly to RO.
Alkali cleaning is applicable to organism and microbial contamination; The chemical cleaning solution of the alkali cleaning reverse osmosis unit that the present invention adopts is the solution that comprises following composition: 1.5-2.5wt% (preferred 2wt%) YD 30 (EDTA); 1.5-2.5wt% (preferred 2wt%) tripoly phosphate sodium STPP, 0.120-0.130wt% (preferred 0.125wt%) dodecyl.Guarantee that through adding alkali (for example conventional alkali such as sodium hydroxide, Pottasium Hydroxide) PH is at 11-12 in the cleaning process.
Pickling is applicable to iron pollution, the dirty stifled and part colloid of carbonate crystallization; The chemical cleaning solution of the pickling reverse osmosis unit that the present invention adopts is: the citric acid solution of the hydrochloric acid of concentration 0.3-0.5wt% or concentration 1.5-2.5wt%, the citric acid solution of the hydrochloric acid of preferred concentration 0.4wt% or concentration 2wt%.In this cleaning process through adding PH that acid guarantees matting water at 1.5-2.0.
The present invention generally adopts pickling after the first alkali cleaning, according to pollution cause also can first pickling after alkali cleaning.Cause the two-pass reverse osmosis device to pollute for the pollutent that prevents the first-stage reverse osmosis device gets into the two-pass reverse osmosis device, clean at first pass and want partition running, clean the two-pass reverse osmosis device earlier and clean the first-stage reverse osmosis device again.Must wash reverse osmosis system 10 ~ 30 minutes with the r-o-water outlet before cleaning.When cleaning the two-pass reverse osmosis device, adjustment matting scavenging solution flow to 70 ~ 100m 3/ h must guarantee PH in the 1.5-2.0 scope in the whole cleaning process, temperature≤38 ℃, pressure reduction≤0.25Mpa.When the cleaning flow of every pressurized vessel can reach 9m 3/ h explains that two-pass reverse osmosis device cleaning performance is good, can clean the first-stage reverse osmosis device.
Cleaning first-stage reverse osmosis device adjustment matting scavenging solution flow is 100-150m3/h, notes guaranteeing in the whole cleaning process PH in the 11-12 scope, temperature≤38 ℃, △ P≤0.25Mpa.When the cleaning flow of every pressurized vessel can reach 9m 3/ h explains that first-stage reverse osmosis device cleaning performance is good, can finish to clean.
The each cleaning all will be used r-o-water outlet flushing reverse osmosis unit after finishing, till the dense water PH of reverse osmosis unit is during near the pH value of reverse osmosis unit water inlet waste water.
Preferably, adopt the non-oxidiser sterilization that circulates.Per hour measure the pH value of a scavenging solution in the whole cleaning process, observe the color of scavenging solution and the pH value of timely adjustment scavenging solution and arrive specialized range.When scavenging solution darkens, should change scavenging solution, per hour write down temperature one time, inlet and outlet pressure and pressure reduction, flow, pH value etc.
Twin-stage reverse osmosis unit of the present invention comprises that further sour adding equipment, Scale inhibitors add equipment, reductive agent adds equipment, security personnel's strainer and non-oxidizable sterilant equipment.Before acid adding equipment, Scale inhibitors adding equipment, reductive agent adding equipment and security personnel's strainer are arranged on the one-level HPP.
Preferably, pretreated waste water is before getting into the first-stage reverse osmosis device, and (conventional mineral acid all can be applicable to the present invention to add acid by acid adding equipment; Hydrochloric acid for example, sulfuric acid, phosphoric acid); In order to regulate waste water ph to 6.5-7.5, to reduce the trend of dense water side carbonate fouling.
Preferably; Pretreated waste water is before getting into the first-stage reverse osmosis device; Add equipment by Scale inhibitors and in feed water by reverse osmosis, add Scale inhibitors; The used Scale inhibitors of the present invention is an organic phosphonate, and for example ATMP (ATMP), ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS), ethylene diamine tetra methylene phosphonic acid (EDTMPA) etc. preferably can use the Flocon135 in commercially available U.S. big lake.Dosage in wastewater volume Scale inhibitors of the present invention is 3.5-5mg/l; Can prevent that difficulty (slightly soluble) salt such as lime carbonate, magnesiumcarbonate, calcium sulfate, permanent white, Strontium Sulphate, Calcium Fluoride (Fluorspan) are separated out fouling after concentrating in the reverse osmosis concentrated water side; Stop up reverse osmosis membrane, thereby damage the application characteristic of membrane element.
Preferably; For protecting follow-up reverse osmosis membrane, pretreated waste water adds conventional water treatment by reductive agent adding equipment and uses reductive agent before getting into the first-stage reverse osmosis device; For example inferior sodium pyrosulfate, potassium aluminium sulfate, S-WAT, sodium sulfite anhy 96; With the chlorine residue in the reducing waste water, it is about 200mv that add-on is controlled to be the redox potential that adopts online ORP (redox potential) table to detect in the water, and 10mv fluctuates.The preferred reductive agent of the present invention is a sodium sulfite anhy 96.
Preferably, before waste water is sent out osmotic treated, carry out secondary filter.Concrete, adopting security personnel's strainer, this security personnel's strainer is arranged on before the RO, and purpose is that the macrobead thing in the anti-sealing gets into reverse osmosis membrane, damages reverse osmosis membrane, to guarantee the normal operation of RO.The principle of work of security personnel's strainer is: utilize the hole of filter core 5 μ m to carry out mechanical filter, remaining trace suspension particle, colloid, mikrobe etc. are trapped or are adsorbed in cartridge surface and the hole in the waste water.The present invention adopts PLC CONTROL PROCESS flow process, and it is chain to produce the jellyfish pipe pressure through two-stage hoisting pump frequency conversion and ultrafiltration, guarantees that waste water pressure reaches the requirement of security personnel's strainer pressure, the for example pressure of 0.21MPa.
Along with the growth of treatment time of water, security personnel's filter element is because of the pollution of trapped substance, and its running resistance rises gradually, when moving to when importing and exporting differential water pressures and reaching 0.1MPa, and renew cartridge more.Preferably, security personnel's strainer is vertical column equipment, adorns 101 long 40 inches filter cores in security personnel's strainer, and filtering accuracy is 5 μ m.
Preferably, behind reductive agent adding equipment, on the HPP back with water inlet line, increase non-oxidizable sterilant adding equipment, regularly reverse osmosis membrane has been carried out germicidal treatment, stifled to avoid microbial contamination to the dirt of film.Spring and autumn is during season alternation, for the situation of severe contamination, whenever adds non-oxidizable sterilant once at a distance from 2-3 days, and each 2 hours, concentration was 200mg/l.For slight pollution or be used for the maintenance of reverse osmosis membrane, whenever added non-oxidizable sterilant once at a distance from 3 days, each 2 hours, concentration was 100mg/l.Wherein said non-oxidizable sterilant is dichlorophen, dioxy cyanic acid methane, RH-893, dodecylbenzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide or 2,2-dibrominated-3-nitrilo propionic acid amide.
4. precision processing
Adopt mixed bed to carry out precision processing the waste water after the twin-stage reverse-osmosis treated.
Mix the bed precision processing and can further remove yin, yang ion, CO in the waste water 2And SiO 2, guarantee that effluent quality reaches product water water quality requirement.The positive and negative ion that various inorganic salt ionization generate in the waste water; Through resinbed the time; Replaced by hydrogen ion in the resin cation(R.C.) and the hydroxide ion in the resin anion(R.A) respectively; The hydrogen ion and the hydroxide ion that get in the water combine to generate water molecules, thereby obtain the effect of removing inorganic salts in the waste water.Preferably, waste water filtering speed is 30-45m/h.The present invention can select to mix the quantity and the specification of bed according to the flow of waste water, for example adopts 3 to mix bed, specification Every nominal output 150m 3/ h.The used mixed bed of the present invention is the conventional commercially available mixed bed in this area, and wherein resin anion(R.A) and resin cation(R.C.) are all the conventional bed sewage water filtration that mixes and use material, and for example resin anion(R.A) adopts 201 * 7 (to have quaternary ammonium group (N (CH on vinylbenzene-divinylbenzene copolymerization matrix 3) 3OH); Resin cation(R.C.) adopts 001 * 1 styrene type cation exchange resin; 001 * 2 styrene type cation exchange resin, 001 * 4 styrene type cation exchange resin, 001 * 7 styrene type cation exchange resin (has sulfonic group (SO on vinylbenzene-divinylbenzene copolymerization matrix 3H)), 002 * 7 styrene type cation exchange resin, 003 * 7 styrene type cation exchange resin, 004 * 7 styrene type cation exchange resin.
After using for some time; Mixed bed needs regeneration; The sun regeneration of resin the good regenerator of dilution from bottom to top reverse flow through resin layer; With the resin of the different attitudes of regenerating according to this from top to bottom, the regeneration of negative resin is the good regenerator of the dilution resin layer of forward flowing through from top to bottom, with the resin of the different attitudes of regenerating according to this from top to bottom.Mix in the bed strongly acidic cationic exchange resin and strongly basic anion exchange resin are housed, the filling ratio of Zeo-karb and anionite-exchange resin is 1:2, as numerous placed in-line multiple bed unit.Through the H in the water of hybrid ionic exchange back +And OH -Generate the very low water molecules of degree of ionization immediately, the gegenion in the time of seldom possibly forming positively charged ion or anionresin can make permutoid reaction carry out very thoroughly.
Reclaim equiment comprises sour high-order storage tank, the high-order storage tank of alkali, sour low level batch meter, alkali low level batch meter, injector and neutralization tank.
The material that the high-order storage tank of acid, the high-order storage tank of alkali adopt is respectively steel lining glue (acid) and steel is coated with epoxy resin (alkali), adopts the ejector applications vacuum method to carry regenerator.
Acid low level batch meter, alkali low level batch meter adopt steel lining to mould container.Volume can satisfy regeneration acid, alkali number once respectively.Usually, specification Nominal output 150m 3The mixed bed of/h, acid solution (31%) primary recycling amount is 800L, alkali lye (40%) primary recycling amount is 700L.Acid, alkali are disposed to neutralization tank and carry out neutralizing treatment.
Mix the bed start-stop and move automatically, also can manually control according to mixing bed water outlet high water tank.Mixing the regeneration of bed can manually carry out also can carrying out automatically.
Technology and apparatus features according to the present invention preferably adopt PLC that each operation is realized control automatically.Simultaneously, through the signal that data collecting card is gathered, concentrate on each processing parameter of demonstration on the upper computer.Whole PLC system possesses the function of centralized supervisory control, warning, interlock protection, procedure operation.
The PLC system can be carried out man-machine dialogue.Whole waste water treatment process is monitored all printable record of all operating parameters, guard signal through upper computer picture and mouse.
Specify the principle of PLC system below.
The PLC system adopts Siemens S7 series of PLC through the newly-built ultrafiltration of Ethernet (ICP/IP protocol), reverse osmosis system dispatch control system.PLC is the FPGA unit, it according to the program of establishment and adopt data message carry out logical operation, and operation result is outputed to the operation that topworks comes control system equipment through signal.
The condition of technology of the present invention and equipment operation is:
(1) satisfy condition: each auxiliary agent adds the liquid level>low liquid level of equipment
(2) operation form: operation automatically.
(3) system alarm: Interlock Status.
(4) interlocking of liquid level: the variation to high water tank mainly realizes with warning being main, judges by operator whether liquid level signal is true.
Specify PLC system adds equipment to each auxiliary agent control below.
The auxiliary agent that the present invention adds comprises the flocculation agent (for example Poly aluminum Chloride (PAC) (PAC)) that reduces turbidity; Quicken the flco aggegation settled coagulant aids (for example SEPIGEL 305 (PAM)) of uniting; Degrade former water bacteria, organic oxygenant (for example Youxiaolin); Prevent the Scale inhibitors of the dense water end (W.E.) fouling of reverse osmosis membrane; Prevent the reductive agent (for example sodium sulfite anhy 96) of reverse osmosis membrane oxidation; Regulate acid (for example hydrochloric acid), the alkali (for example sodium hydroxide) of one-level, two-pass reverse osmosis device (RO) water inlet PH.
The add-on of each auxiliary agent is controlled through volume pump, each volume pump and corresponding technical process pump interlocking start and stop.
Concrete, the Youxiaolin volume pump of pretreatment procedure, flocculation agent volume pump, coagulant aids volume pump, alkali (preferred sodium hydroxide) volume pump and with the start and stop of pretreated waste water amount interlocking.
The Youxiaolin add-on is adjusted the volume pump frequency automatically according to settling tank water outlet chlorine residue; Control settling tank water outlet chlorine residue 1.2-1.5mg/l; Coagulant aids add-on, flocculant addition are according to the automatic regulating frequency of wastewater flow rate, and it is 20-30mg/l that the control flocculation agent adds concentration, and it is 0.1-0.2mg/l that coagulant aids adds concentration; Alkali (preferred sodium hydroxide) adding concentration pumps water ph value according to two-stage hoisting and adjusts frequency automatically, and control PH is about 8.0-8.5.
In addition, hyperfiltration reverse-rinsing Youxiaolin volume pump also with the start and stop of hyperfiltration reverse-rinsing interlocking.
Reductant metering pump and the chain start and stop of one-level HPP, the reductive agent add-on is adjusted the volume pump frequency automatically according to first-stage reverse osmosis device water-in, and control first-stage reverse osmosis device water-in fluctuates 10 at redox potential (ORP) 200mv.Preferably, operation 1-2 cover reverse osmosis unit then starts 1 volume pump automatically, and operation 3-4 cover reverse osmosis unit then starts 2 volume pumps automatically, and operation 5-6 cover reverse osmosis unit then starts 3 volume pumps automatically.
Scale inhibitors volume pump, sour volume pump and the chain start and stop of one-level HPP.The Scale inhibitors add-on is according to the proportional automatic adjusting metering pump frequency of one-level HPP general import wastewater flow, control Scale inhibitors dosage 3.5-5mg/l.Preferably, operation 1-2 cover reverse osmosis unit then starts 1 volume pump automatically, and operation 3-4 cover reverse osmosis unit then starts 2 volume pumps automatically, and operation 5-6 cover reverse osmosis unit then starts 3 volume pumps automatically.The acid add-on is adjusted the volume pump frequency automatically according to ultrafiltration water outlet PH, and the about 5-10mg/l of sour add-on is preferred, and operation 1-4 cover reverse osmosis unit then starts 1 volume pump automatically, and operation 5-6 cover reverse osmosis unit then starts 2 volume pumps automatically.
Alkali volume pump and the chain start and stop of secondary HPP, add-on is adjusted the volume pump frequency automatically according to the secondary HPP PH of always intaking, and PH is at 7-8 for the water inlet of control secondary HPP, and alkali is gone into the about 5mg/l of dose, preferably, 2 volume pump the using and the reserved.
The two-stage hoisting pumping capacity realizes control automatically according to ultrafiltration rising pipe upward pressure, guarantees pressure-stabilisation.
Specify the control of more medium filter below.
The control of more medium filter is opening/stopping and realizing operation, backwash, operating process automatically such as subsequent use through ON/OFF, the pump of control Pneumatic butterfly valve.The cycle of backwash mainly is to confirm according to the accumulated running time of equipment and integrated flow.In addition, be provided with tensimeter,, flow signal sent into microcomputer show, write down, control at the inlet flow rate meter of each strainer at the inlet pipe of strainer and each outlet.
Specify the control of ultra-filtration equipment below.
The startup of ultra-filtration equipment, operation, backwash, air bump rinse operation, just wash, shut down process such as subsequent use and all can realize control automatically by PLC.Simultaneously, ultrafiltration system also is provided with a local panel and a local operation dish, the readable relevant processing parameter that goes out ultrafiltration on local panel, and can on the local operation dish, operate relevant water pump and automatic valve.Important parameter such as pressure, flow etc. to ultra-filtration equipment are equipped with the on-line detector table, and are set with the overload alarm function.
The backwash of ultrafiltration system is according to the backwash condition of working time as ultrafiltration system, and general every separated 72min backwash once; The mode that comes into operation of ultrafiltration system: specified operation time, use after the time out of servicely automatically, change operation after the backwash automatically over to.The matting of ultrafiltration system can automatically also can be manual.
Specify the control of HPP below.
The HPP of RO device is imported and exported low pressure and high voltage protective switch is housed.Be lower than a certain set(ting)value (being generally 0.05MPa) when the service discharge deficiency makes the hydraulic pressure of HPP inlet, can send signal automatically and stop the HPP operation, the protection HPP is not worked under the idle running situation.Reason or mishandle when system because of other, when making the top hole pressure of HPP surpass certain set(ting)value (being generally 2.0MPa), the protection of HPP top hole pressure can automatic cut off high pump power supply, the corresponding RO device of stopping transport simultaneously, securing system equipment is without prejudice.
Specify the control of reverse osmosis unit (RO) below.
Processes such as the startup of RO device, operation, flushing, shutdown are subsequent use all can realize control automatically by PLC.Simultaneously, the RO system also is provided with a local panel and a local operation dish, on local panel, can read the relevant processing parameter of RO, like specific conductivity, flow, pressure etc.; And can on the local operation dish, reach relevant automatic valve by start and stop RO water inlet HPP.
After RO stops using or move 12-24 hour, to reverse osmosis membrane assembly automatically about flushing 10 ~ 30min, influence the performance of film in the surface deposition fouling of RO film to avoid high concentration salts in the dense water with product water.Regularly low-pressure washing also contaminant reducing to the pollution tendencies of reverse osmosis membrane.First-stage reverse osmosis (RO) device of operation washes according to the big yield flushing cycle of setting automatically, and length can not surpass 24 hours, the first-stage reverse osmosis of stoppage in transit (RO) device and two-pass reverse osmosis device by the operations staff according to the working specification periodic flushing.
Set forth the present invention through concrete embodiment below, one skilled in the art will appreciate that this should not be understood that the restriction to claim scope of the present invention.
Embodiment
Embodiment 1
The waste water of using among the embodiment rolls the district for Taiyuan Iron And Steel Plant and smelts the mixing water of two kinds of waste water, and concrete parameter is seen table 1.
Table 1
(above-mentioned being up to is meant that index value can occur at short notice)
The performance index of each auxiliary agent of using among the embodiment and interpolation situation are seen table 2
Table 2
Adopt PLC that each operation of present embodiment is realized control automatically.
1. pre-treatment
Waste water pump in the water reservoir is sent into the aeration oxidation pond.Intake at water reservoir is provided with grid, big swimmer in the interception waste water.In the aeration oxidation pond, in waste water, add the sodium hydroxide solution of concentration 30wt%, waste water ph is adjusted to greater than 7.Then, adopt conventional air aeration method, aerating oxygen is 20 minutes in waste water, sampling and measuring, and total iron content drops to<0.5mg/l in the waste water.Add Youxiaolin in the waste water after the aeration oxide treatment, through PLC, the Youxiaolin add-on is adjusted Youxiaolin volume pump frequency automatically according to post precipitation pond water outlet chlorine residue 1.2-1.5mg/l, and effective chlorine density is 10-15mg/l in the waste water.
Adopt the one-level lift pump that waste water is delivered to the automatic reaction pond, before waste water gets into the automatic reaction pond, add the sodium hydroxide solution of concentration 30wt%, waste water ph is adjusted to about 8.2.
Present embodiment automatic reaction pond is made up of three groups of stirrers (4 every group), and rotating speed reduces to discharge port from mechanical reaction tank opening for feed from fast to slow gradually, and the impeller middle line speed of three groups of stirrers is respectively 0.54m/s, 0.35m/s, 0.15m/s.Coagulant aids SEPIGEL 305 (PAM) add-on, flocculant poly aluminum chloride PAC (aluminium sesquioxide is more than or equal to 29%) add-on are regulated the metering pump frequency automatically according to wastewater flow rate; It is 20-30mg/l that the control flocculation agent adds concentration, and it is 0.1-0.2mg/l that coagulant aids adds concentration.
Waste water is with after flocculation agent and coagulant aids mix in the automatic reaction pond, and the radial-flow inclined-plate clarifying basin that flows into 2 diameters certainly and be 29 meters leaves standstill, sampling and measuring, and delivery turbidity is below the 5NTU.
2. pre-treatment
The settling tank water outlet gets into two-stage hoisting pump water tank, through the two-stage hoisting pump more medium filter is sent in the waste water pressurization again.The more medium filter main technical details is following:
Quantity: 13; Specification: φ 5000;
Bulk material: carbon steel; Inner anticorrosion: line with rubber
Pressure: 0.6MPa; WP: greater than 0.2Mpa
Working time: backwash in 24 hours is (by actual adjustment) once, also can come backwash according to flow accumulation
The backwash time: 90min/ time; Turbidity: water outlet < 5mg/>L
Backwash intensity: 10L/m 2.s gas is cleaned intensity: 10L/m2.s
Operation flow velocity: 9.0m/h; Equipment is exerted oneself: normal 194m 3/ h
Filtrate is loaded grating:
(1) hard coal (upper strata): particle diameter: 0.8-1.2mm, thickness: 400mm; (2) silica sand (lower floor): particle diameter: 0.5-0.8mm, thickness: 700mm; (3) silica sand (bed course): particle diameter: 3.0-4.0mm, thickness: 100mm; (4) silica sand (bed course): particle diameter: 4.0-8.0mm, thickness: 100mm; (5) pebbles (bed course): particle diameter: 6.0-12.0mm, thickness: 100mm; (6) pebbles (bed course): particle diameter: 12.0-18.0mm, thickness: 100mm; (7) pebbles (bed course): particle diameter: 18.0-25.0mm, thickness: 100mm.
Backwash water adopts strainer to produce water, adopts roots blower to carry out gas and cleans.
Waste water after the more medium filter processing is sent into ultrafiltration apparatus.The main technical details of ultrafiltration apparatus is following:
Device quantity: 12 covers; Device is exerted oneself: Q=189m 3/ h/ cover;
Membrane module model: SFP2860; Membrane module quantity: 64/cover;
System recoveries rate: >=90%; Membrane pore size: 0.03 μ m;
Film silk inside/outside footpath: 0.7/1.3mm; Transmitance: 56.8L/m 2h
Filtration area: 52m 2/; Filter molecular weight: 20,000
Membrane material: PVDF (pvdf)
MWP: 0.6MPa; Maximum operating pressure differential: 0.21Mpa
PH scope: 2~12 (during cleanings 1 ~ 12)
Maximum continuously water inlet chlorine residue: 200mg/l (cleaning maximum tolerance chlorine content 5000mg/l)
Working forms: grossflow filtration
Filtration cycle: >=72min
Water backwash intensity: 100-150L/m 2h
3. twin-stage reverse-osmosis treated
Add equipment by acid and in waste water, add concentration 30wt% hydrochloric acid soln, sour add-on is adjusted acid automatically according to ultrafiltration water outlet PH and is added the volume pump frequency, and the about 5-10mg/l of sour add-on regulates waste water ph to 6.5-7.5.
Add equipment by Scale inhibitors and in waste water, add Scale inhibitors Flocon135, dosage 3.5-5mg/l.The Scale inhibitors add-on adds the volume pump frequency according to the proportional automatic adjusting Scale inhibitors of one-level HPP general import wastewater flow.
Add equipment by reductive agent and in waste water, add sodium sulfite anhy 96; The reductive agent add-on is adjusted reductive agent automatically according to first-stage reverse osmosis device water-in wastewater flow and is added the volume pump frequency, control first-stage reverse osmosis device water-in in redox potential (ORP) at 200mv ± 10mv.
It is chain that the jellyfish pipe pressure is produced in two-stage hoisting pump frequency conversion and ultrafiltration, guarantees waste water pressure 0.21MPa, and waste water is sent into security personnel's strainer.The main technical details of security personnel's strainer is following:
Quantity: 13; Specification: φ 1000 vertical cylinder;
Cylindrical shell material: stainless steel; Filter core material: Vestolen PP 7052 (PP);
Filtering accuracy: 5 μ m; Flow: 200m 3/ h;
WP: 0.4MPa; Front and back operting differential pressure: < 0.3MPa
Water inlet condition: SDI < 3; Turbidity < 0.5mg/>l
Waste water after security personnel's filter process is delivered to the first-stage reverse osmosis device with the one-level HPP with the pressure pump of 1MPa carry out filtration treatment.The first-stage reverse osmosis device comprises 7 covers, and it is 32:16 that 1#-4# unit pressurized vessel is arranged, and every cover adopts 336 membrane elements; It is 36:18 that 5#-6# unit pressurized vessel is arranged; Every cover adopts 324 membrane elements, and it is 30:15 that 0# unit pressurized vessel is arranged, and adopts 315 membrane elements.The intersegmental pressure reduction of first-stage reverse osmosis is controlled at below the 0.3MPa.Select for use BW30-365FR and BW30-400FR composite package as the reverse-osmosis treated film.When the reverse osmosis equipment temperature was 20 ℃, the every cover of first-stage reverse osmosis device was exerted oneself and is 235m 3/ h.A first-stage reverse osmosis device water outlet part gets into the associating pumping plant, supplies the de-mineralized water user outward, and it is personal that a part gets into the first-stage reverse osmosis water tank, and a part is delivered in the two-pass reverse osmosis device with the pressure pump of 1MPa via the secondary HPP.Alkali volume pump and the chain start and stop of secondary HPP, alkali (concentration 30wt% sodium hydroxide solution) add-on is adjusted alkali volume pump frequency automatically according to the secondary HPP PH of always intaking, and PH is in the 7-8 scope for the water inlet of control secondary HPP.
The two-pass reverse osmosis device comprises 3 covers, and it is 11:4 that the unit pressurized vessel is arranged, and every cover adopts 90 membrane elements.First-stage reverse osmosis device water production rate is 1400m 3/ h, two-pass reverse osmosis device water production rate is 300m 3/ h.The intersegmental pressure reduction of two-pass reverse osmosis is controlled at below the 0.2MPa.
4. precision processing
Waste water after the two-pass reverse osmosis apparatus processes gets into two-pass reverse osmosis and produces water tank, under the effect of mixed bed lift pump, gets into then and mixes bed, and waste water filtering speed is 40m/h.Mixed bed adopts 3, specification altogether Every nominal output 150m 3/ h.Mixing bed employing resin anion(R.A) is 201 * 7, and resin cation(R.C.) is 001 * 7.The water outlet that mixes after bed is handled gets into mixed bed product water tank, supplies the outer use that supplies.
The water outlet parameter that each operation stage records is as shown in table 3:
Table 3
Adopt of the present invention pair of embrane method treatment technology, have following beneficial effect at least:
1. first-stage reverse osmosis output (de-mineralized water) 1400m among the embodiment 3/ h, 2.5 yuan/ton of costs, 5.5 tons of de-mineralized water prices, year increase benefit:
1400m 3Unit/the m of/h * (5.5-2.5) 3* 24h * 365 day=3679.2 ten thousand yuan.
Practice thrift outer draining benefit: 1400m 3/ h * 0.5 yuan/ton * 24h * 365 day=613.2 ten thousand yuan.Amount to ten thousand yuan of year create beneficial result: 3679.2+613.2=4292.4.
2. the present invention has reclaimed trade effluent, has reduced effluxing, and has reduced the water at low temperature rate of water make-up, has opened up a new water source for Iron And Steel Industry, has solved stainless steel system reform water shortage problem.The present invention meets national energy-saving and emission-reduction; The strategy of sustainable development; Alleviated the situation of existing water resources critical shortage and water pollution, water pollution and environment protection have been produced positive effect, and the experience of worth reference is provided for China's iron and steel metallurgy industry water technology innovation.

Claims (13)

1. Wastewater Of Steel Industry double membrane processing method, this method comprises:
A. pre-treatment
A1) aeration oxide treatment: waste water ph is adjusted to greater than 7, aerating oxygen in waste water then, total iron content drops to<0.5mg/l in waste water;
A2) automatic reaction, precipitation process: waste water ph is adjusted to 8.0-8.5, under agitation condition, in waste water, adds flocculation agent and coagulant aids, staticly settle then, make the wastewater effluent turbidity reach below the 5NTU;
B. pre-treatment
B1) filtration treatment: the waste water after the pre-treatment is carried out filtration treatment in strainer, so that the wastewater effluent turbidity is less than 2NTU;
B2) uf processing: the waste water after the filtration treatment is carried out grossflow filtration handle, feasible pollution index≤3 through the waste water after the uf processing;
C. twin-stage reverse-osmosis treated
Pretreated waste water is carried out two steps ro to be handled;
D. precision processing
Adopt mixed bed to carry out precision processing the waste water after the twin-stage reverse-osmosis treated.
2. Wastewater Of Steel Industry double membrane processing method according to claim 1 is characterized in that, at step a2) in, said flocculation agent is a Poly aluminum Chloride (PAC), polyaluminium sulfate, polymer phosphate aluminium, bodied ferric sulfate, poly-ferric chloride or polymer phosphate iron; Said coagulant aids is a SEPIGEL 305, polydimethyl dipropenyl ammonium chloride, gelatine or sodium-alginate; Preferably, flocculation agent is a Poly aluminum Chloride (PAC), is 20-30mg/l in the wastewater volume flocculant addition; Coagulant aids is a SEPIGEL 305, is 0.1-0.2mg/l in wastewater volume coagulant aids add-on.
3. Wastewater Of Steel Industry double membrane processing method according to claim 1 and 2; It is characterized in that; At step a2) taking a step forward comprises degerming algae treatment step: add in the waste water after the aeration oxide treatment that chlorine residue is 1.2-1.5mg/l in the water outlet of chloro sterilizing agent control settling tank; Wherein, said chloro sterilizing agent is Youxiaolin, liquid chlorine or dioxide peroxide.
4. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-3, it is characterized in that, at step b1) in, said strainer is a more medium filter, the waste water flow velocity is 6-10m/h.
5. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-4, it is characterized in that, at step b2) in, said ultra-filtration filters is handled the membrane pore size of using and is 0.03-0.1 μ m, and filtering molecular weight is more than 20,000.
6. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-5, it is characterized in that pretreated waste water is regulated waste water ph to 6.5-7.5 before carrying out the first-stage reverse osmosis processing.
7. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-6; It is characterized in that; Pretreated waste water adds the Scale inhibitors organic phosphonate before carrying out the first-stage reverse osmosis processing, be 3.5-5mg/l in wastewater volume Scale inhibitors add-on.
8. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-7, it is characterized in that pretreated waste water is before carrying out the first-stage reverse osmosis processing, adding reductive agent to waste water is 200mv ± 10mv in redox potential (ORP); Said reductive agent is inferior sodium pyrosulfate, potassium aluminium sulfate, S-WAT or sodium sulfite anhy 96.
9. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-8, it is characterized in that the waste water after first-stage reverse osmosis is handled is regulated waste water ph to 7-8 before carrying out the two-pass reverse osmosis processing.
10. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-8, it is characterized in that the intersegmental pressure reduction of first-stage reverse osmosis is controlled at below the 0.3MPa, the intersegmental pressure reduction of two-pass reverse osmosis is controlled at below the 0.2MPa.
11. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-10, it is characterized in that, adopt each auxiliary agent of computer control to add volume pump and corresponding technical process pump interlocking start and stop.
12. according to each described Wastewater Of Steel Industry double membrane processing method of claim 11; It is characterized in that; Pretreated waste water is before carrying out the twin-stage reverse-osmosis treated; Adopt security personnel's strainer to carry out filtration treatment, and it is chain to adopt two-stage hoisting pump frequency conversion and ultrafiltration to produce the jellyfish pipe pressure, guarantees that waste water reaches the pressure requirement of security personnel's strainer.
13. according to each described Wastewater Of Steel Industry double membrane processing method of claim 1-12; It is characterized in that; Periodically in pretreated waste water, add non-oxidizable sterilant; Wherein said non-oxidizable sterilant is dichlorophen, dioxy cyanic acid methane, RH-893, dodecylbenzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide or 2,2-dibrominated-3-nitrilo propionic acid amide.
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