CN103496766B - A kind of high-level efficiency less energy-consumption type waste water reclamation utilizes device and application thereof - Google Patents
A kind of high-level efficiency less energy-consumption type waste water reclamation utilizes device and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-level efficiency less energy-consumption type waste water reclamation and utilize device and application thereof, it is characterized in that: comprise former water storage tank, under meter group, concentrated type electrodialyzer group, anode water gas-liquid separator and negative electrode aqueous vapor liquid/gas separator; Under meter group is connected with negative electrode hydroecium with the freshwater room of first step concentrated type electrodialyzer, dense hydroecium, anode hydroecium respectively by pipeline; The anode hydroecium of final stage concentrated type electrodialyzer is connected with former water storage tank through anode water gas-liquid separator by pipeline, negative electrode hydroecium is connected with former water storage tank through negative electrode aqueous vapor liquid/gas separator by pipeline, dense hydroecium is exported through product concentrated stream gauge through dense water output pump by pipeline, and freshwater room is directly exported by pipeline.The present invention by conservative control obtain high enrichment, the dense water of useful resources containing recovery value and reclaim Freshwater resources, finally realize trade effluent " zero release ".The present invention has dependable performance, saves the advantages such as energy consumption.
Description
Technical field
The present invention relates to trade effluent and reclaim field, specifically a kind of high-level efficiency less energy-consumption type waste water reclamation utilizes device and application thereof.
Background technology
Waste water reclaiming is other useful chemical resource in recycle-water resource and waste water, realizes wastewater zero discharge, the important technology of preserving the ecological environment.The critical equipment of zero discharge of industrial waste water is electrodialysis thickener.
1, the object that waste water reclamation utilizes has two: one to be reclaim the water resources in waste water, and in waste water, water resources accounts for more than 90%, removes salt wherein, reaches the requirement of production technique water, is back in production.Namely avoid contaminated wastewater environment water, avoid again consuming nature and excessively developed, very short Freshwater resources; Two is the resources reclaiming in waste water other, various metallic salts in waste water, be source of pollution, it is again recuperable resource, and be exactly often raw material or the product of production technique, if can by it recovery, then production cost must decline, also reduce effluent charge simultaneously, make enterprise therefrom obtain dual economic benefit.
2, waste water reclamation utilizes conventional means to have two kinds: one to be method of evaporation.So-called evaporation, is exactly by the liquid water in waste water, is vaporizated into water vapour, obtains fresh water after condensation.Typical example application is exactly multistage flash evaporation type sea water desalinating plant.What method of evaporation was conventional has (multistage) vacuum-evaporation and thermo-compression evaporation two kinds of techniques, and its object is all the consumption in order to steam saving, reduces cost for wastewater treatment.We know, the energy (vaporization/latent heat) that the water of evaporation 1m3 consumes is it is heated to energy required for 100 DEG C (intensification/sensible heat) from 0 DEG C 5 times, so evaporation is the technological process of a high energy consumption.It is more worthwhile that the industrial occasion having surplus heat uses.The dense water that evaporation concentration obtains, generally directly or can obtain the saline crystallization of solid through overcooling (freezing), then through whizzer, it is separated with mother liquor, washs, drying can obtain finished product; Certainly, if production technique allows, also can by dense water direct reuse in production; Two is electroosmose processs.The industrial application history of electroosmose process has had more than 40 year, and it only needs consuming electric power, and utilization rate of electrical also reaches more than 90%, and the work-ing life of device also can reach more than 5 years, is a kind of very practical technical equipment.Electroosmose process is used for wastewater treatment, not only can obtain fresh water easily but also can by Waste water concentrating to tens times of even hundreds of times, through (freezing or evaporation) crystallization, separation, washing, the dry solid crystal that just can obtain useful chemical resource.Electroosmose process is when meeting the task of same waste water reclaiming, and the consumption of energy is only the 1/5-1/10 of method of evaporation, and only needs consuming electric power, do not need Industrial Boiler and supporting auxiliary facility thereof, so treatment system composition is simple, long service life, cost for wastewater treatment is low.In order to make electroosmose process better for waste water reclaiming, special by the mechanical seal of the core of this law-concentrated type electrodialyzer and structure, technical process, supply of electric power three main aspects, redesign.The practical result of industry shows, in the current electroosmose process waste water reclaiming engineering all redesigned, reaches design requirements.
Therefore the electrodialyzer of concentrated type is the important thickener of waste water reclaiming.Its energy consumption is only the 1/5-1/10 of evaporation concentration.And can combine with evaporation easily, be applied to the resource utilization of some special waste water.Here waste water reclaiming refers to: one is water resources will be reclaimed, and in the method for recovery, very the important point removes wherein each kind of salt with concentrated type electrodialyzer exactly, makes it the standard reaching industrial process waters, again gets back in industrial manufacture process and go; Two is metal-salt useful in trade effluent or other useful resources will be reclaimed, in the method reclaimed, very the important point is exactly concentrate metallic salt wherein with concentrated type electrodialyzer, can freezing and crystallizing be passed through afterwards, or obtain solid-state metallic compound through evaporation again.Different from common desalination type electrodialyzer, concentrated type electrodialyzer must be have high water yield, otherwise does not just reach cycles of concentration or be called the requirement of concentration rate, and the steam output after increase, also just adds the consumption of the energy.
Generally speaking, use concentrated type electrodialyzer to concentrate waste water, obtain the technique recovery water that saltiness is equivalent to tap water level, simultaneously, also obtain high enrichment, the dense water of useful chemical resource containing recovery value, then through freezing and crystallizing or evaporate a little, just can obtain crystalline solid.Because the at this moment volume of mother liquor, be percentum of original wastewater quality, so even if use the way of evaporation, making its energy consumed of all vaporizing, is also acceptable.The above is exactly the waste water zero emission that it has often been said.Reach the object of zero release, concentrated type electrodialyzer is indispensable.Further, direct supply is the vital guarantee of concentrated type electrodialyzer throughput, constant current power supply is significant for concentrated type electrodialyzer.
Application concentrated type electrodialyzer carries out waste water resource and reclaims the same with application desalination type electrodialyzer, is also made up of three major portions, that is:
First is membrane stack body---comprise locking end plate, electrode vessel, membrane stack, the basic demand for them effectively to prevent the mutual seepage between pole water, dense water, fresh water.Especially electrode vessel, needs to redesign the electrode vessel different from desalination electrodialyzer, just can meet the demands.Will select in addition can resistant to pollution film.The process of film before cutting is more even more important than desalination type electrodialyzer;
Second waterway control system when being concentrated and technical process---can reach design cycles of concentration this be vital, the waterway control system of redesign and technical process, could meet the design requirements of cycles of concentration;
3rd is the power supply of concentrated type electrodialyzer---the working current of concentrated type electrodialyzer is all very large, as the energy resource supply of electrodialyzer process, concentrated type electrodialyzer for the requirement of power supply far above desalination type.The power supply of constant-current source type is necessary, and it is the guarantee of throughput.
This three part all must meet the requirement of concentrated type electrodialyzer simultaneously, just can complete the task that trade effluent is concentrated.
After electrodialysis develops into the advanced stage of " autofrequently changing pole electro dialysis (head word EDR) " before 30 years, due to self cleaning can be carried out by self-timing during non-stop run, ensure that electrodialyzer can work for a long time, continuously, stably.So the electrodialyzer major part in modern times adopts EDR type, the concentrated type electrodialyzer in the present invention is certainly no exception.
In prior art, concentrated type electrodialyzer as shown in Figure 1, lock end plate 1 ', offset plate pad I 2 ', electrode frame 3 ', gasket II 4 ', cuticula orifice plate 5 ' and pole film and membrane stack 6 ' by membrane stack to be fixedly connected sequentially and to form, electrode 8 ' is provided with in electrode frame 3 ', 7 ' be electrode water outlet in figure in addition, 9 ' be electrode water import, 10 ' is cuticula orifice plate perforate part.There is following defect in electrodialyzer of the prior art:
1, the thickness of electrode frame 3 ' of the prior art is generally 20mm ~ 25mm, and to meet the requirement of the pole water flow velocity>=10cm/s generally acknowledged both at home and abroad, pole water consumption is comparatively large, and the room, membrane stack each pole of 400 × 1600 at least needs 2.5m
3/ h.Offset plate pad I 2 due to electrode frame 3 ' both sides ' and gasket II 4 ' the middle portion usage of trade all hollows out, and spacer thickness 3mm, so in fact the thickness of electrode vessel is 26mm, pole water needs 3.3m
3/ h, could meet the requirement of pole water flow velocity>=10cm/s.This becomes brackish water desalination Waste water utilization rate and is difficult to one of main cause improved, so usually all use little pole water yield, the flow velocity of pole water is also just very little.The pole water that flow velocity is less is difficult to go out electrode vessel 3 ' fouling chip; especially the electrode water import 9 ' of Fig. 1 exports 7 ' all in side with electrode water; the distribution of electrode water in the hydroecium of pole is very uneven; bias current is serious, will cause the dirt bits accumulation in electrode vessel 3 ' come off during the operation of falling pole, make pole water flow not smooth further; the result of vicious cycle; cause increasing the weight of of electrode vessel fouling, have to shut down snaking, this is much in engineering.In addition because pole water flow velocity is little, pressure drop is little, also easily makes cuticula orifice plate perforate part 10 ' be pressed towards electrode frame internal strain, causes electrodialysis body to leak.Water that is dense, freshwater room also can be caused simultaneously to permeate to pole chamber pressure, electrodialytic water yield is declined.So-called electrodeless water power dialyzer, in fact utilizing dense, freshwater room to the infiltration of electrode vessel to obtain pole water, is not really do not have pole water.If really break pole water, electrode will be overheated, and electrode vessel will be caused further to damage;
2, electrode frame 3 ' is discrete with cuticula orifice plate 5 ' is two parts, has set up a gasket II 4 for this reason ', add the hidden danger that electrodialysis is leaked, too increase the trouble of membrane stack assembling;
What 3, cuticula orifice plate 5 ' designed is general thinner, and general employing thickness is the PVC board of 6 ~ 8mm, and when multistage electrodialysis is connected, because hydraulic pressure falls comparatively large, it is common occurrence that cuticula orifice plate is crushed out of shape, and causes electrodialysis to be leaked, and have to take membrane stack apart and change orifice plate.Because orifice plate is thinner, intensity and rigidity are all not enough, and percentage of open area can only accomplish 40%, thus cause room, pole resistance to increase.
The high water yield that waste water resource reclaims is the fundamental means of saving water resource.Due to the requirement of environment protection, wish that waste water obtains reuse as far as possible, so that reach zero release.Especially containing useful chemical resource in many waste water, if its discharge of leaving is by while causing severe contamination to environment, the resource of recovery value is wasted.So the Industrial Wastewater Treatment in modern times all takes much count of the concentrated of waste water, so that reclaim useful chemical resource wherein.Reverse osmosis (RO) technology is exactly conventional, but because the water yield of the restriction RO of technology and equipment condition only has 75%, that is the cycles of concentration of dense water only has 4 times, wants to reclaim the useful chemical resource in waste water, also needs to add the very large evaporation technology equipment of power consumption.
Conventional electrodialytic waterway control system and technical process, as shown in Figure 3 (time of falling pole switch water route pipeline do not express), in figure: 101 ' is raw water box, 102 ' is concentrated stream gauge, 103 ' is raw water flow meter, 104 ' is pole water ga(u)ge, and 105 ' is raw water pump, and 106 ' is third stage electrodialyzer, 107 ' is second stage electrodialyzer, 108 ' is first step electrodialyzer, and A is fresh water delivery conduit, and B is dense water delivery pipe road.For brackish water desalination project, adopt apparatus system as shown in Figure 3, water-yielding capacity 10m
3/ h.Each piping flow is as follows; Raw water flow is 14m
3/ h, fresh-water flow is 10m
3/ h, concentrated stream amount is 3.5m
3/ h, dense water uses former water, uses rear discharge; Pole discharge is 0.5m
3/ h, uses former water, with after return raw water box, water yield=10/(10+3.5) × 100%=74%.
To sum up analyze, be badly in need of a kind of concentrated type electrodialyzer of efficient energy-saving being provided and applying this electrodialyzer carrying out the system of trade effluent recovery to solve the deficiencies in the prior art.
Summary of the invention
According to the technical problem of above-mentioned proposition, and a kind of high-level efficiency less energy-consumption type waste water reclamation is provided to utilize device and application thereof.
The technique means that the present invention adopts is as follows:
A kind of high-level efficiency less energy-consumption type waste water reclamation utilizes device, it is characterized in that: comprise former water storage tank, by the under meter group that pipeline is connected with described former water storage tank through raw water pump, by the concentrated type electrodialyzer group that pipeline is connected with described under meter group, anode water gas-liquid separator and negative electrode aqueous vapor liquid/gas separator, wherein, described concentrated type electrodialyzer group comprises at least two-stage concentrated type electrodialyzer;
Described under meter group comprises raw water flow meter, concentrated stream gauge, anode water under meter and cathode water gauge, and above-mentioned under meter is connected with negative electrode hydroecium with the freshwater room of first step concentrated type electrodialyzer, dense hydroecium, anode hydroecium respectively by pipeline;
The anode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank through described anode water gas-liquid separator by pipeline; The negative electrode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank through described negative electrode aqueous vapor liquid/gas separator by pipeline;
The dense hydroecium of described final stage concentrated type electrodialyzer is exported through product concentrated stream gauge through dense water output pump by pipeline; The freshwater room of described final stage concentrated type electrodialyzer is directly exported by pipeline.
As preferably, described concentrated type electrodialyzer comprise be fixedly connected sequentially membrane stack locking end plate, gasket, integrated electrode room and pole film and membrane stack;
Described integrated electrode room comprises electrode cabin for hold electrodes and cuticula orifice plate; The upper/lower terminal of described membrane stack locking end plate is respectively equipped with electrode water outlet and electrode water import, and the upper/lower terminal of described gasket is respectively equipped with and exports with described electrode water and opening I that described electrode water import matches and opening II.
As preferably, the Thickness Ratio of described electrode cabin and described cuticula orifice plate is 1:3-4.
As preferably, the percentage of open area of described cuticula orifice plate is more than or equal to 60%.
As preferably, pole film before use, all need be soaked more than 48h with required yin, yang film by described pole film and membrane stack in the aqueous solution of the salt identical with the maximum concentration that concentrated solution can reach.
As preferably, described under meter group also comprises dense water makeup water stream gauge, and described dense water makeup water stream gauge is connected by the delivery conduit of pipeline with the dense hydroecium of final stage concentrated type electrodialyzer, and is connected with described concentrated stream gauge through dense water-circulating pump.
As preferably, the freshwater room of described first step concentrated type electrodialyzer, dense hydroecium ingress are provided with the trip switch valving I for the work of falling pole; The freshwater room of described final stage concentrated type electrodialyzer, dense hydroecium exit are provided with the trip switch valving II for the work of falling pole.
As preferably, when the progression of described concentrated type electrodialyzer is less than or equal to secondary, described concentrated type electrodialyzer adopts constant current power supply to power; When the progression of described concentrated type electrodialyzer is greater than secondary, first and second grade of concentrated type electrodialyzer adopts constant current power supply to power, and the concentrated type electrodialyzer more than third stage adopts constant voltage power supply to power.In addition, when the water quality of former water can not meet the requirement of pole water, independent pole water circulation system should be set up, receive infringement to prevent electrode.
The invention also discloses the application that above-mentioned high-level efficiency less energy-consumption type waste water reclamation utilizes device, it is characterized in that: comprise waste water reclamation and utilize device, freezing/evaporative crystallizer, separating centrifuge, moisture eliminator; Waste water utilizes after device process through waste water reclamation and is divided into two portions, and a part is the Freshwater resources reclaimed, and gets back in production technique; The solid crystal of the useful chemical resource that another part is recycled through freezing/evaporative crystallizer, separating centrifuge, moisture eliminator successively, wherein the isolated crystalline mother solution of separating centrifuge is got back to waste water reclamation and is utilized in device the concentration that circulates.Adopt this waste water reclamation to utilize device can obtain fresh water and have the crystalline solid of useful chemical resource of recovery value, reaching the zero release of waste water.Further, the concentrated type electrodialyzer proposed in the present invention is equally applicable to desalination type electrodialyzer, can increase substantially water use efficiency, improve energy-saving effect.
Comparatively prior art is compared, high-level efficiency less energy-consumption type waste water reclamation provided by the invention utilizes device to adopt the concentrated type electrodialysis system of modern crafts through redesigning, water yield is greatly improved, from original 65-85%, namely cycles of concentration 3-7 doubly brings up to 20 times, namely water yield reaches more than 95%, and this is close to the maximum value of cycles of concentration when only having an electrodialyzer system.
Wherein, concentrated type electrodialyzer tool provided by the invention has the following advantages:
1. integrated electrode room is in certain thickness PVC board, use milling machine, after milling out the electrode cabin of certain depth, the PVC board of residual thickness is holed, form cuticula orifice plate, ensureing that the Thickness Ratio of electrode cabin and cuticula orifice plate is 1:3-4, is 15mm as PVC board is thick, so the thickness in electrode cabin is 3mm, and cuticula orifice plate thickness is 12mm.Electrode cabin can use various wire form electrode and net formula electrode.Integrated electrode room provided by the invention is when pole water flow velocity reaches 10cm/s flow velocity, and the consumption of pole water is only 1/10 of Fig. 1.
The membrane stack of 400 × 1600 uses, and the calculated value of the consumption of pole water is each pole room 0.4 ~ 0.5m
3/ h.In fact, at this moment the duty ratio of electrode itself can not be ignored, and such as net formula electrode is close to the flat board that 1mm is thick, now, and the actual amount 0.3m of pole, room, each pole water
3/ h.Water-saving result is remarkable.Even if when processing severe brackish water, the pole water after using does not reclaim, and the impact for water yield is also only about 3%.
It is emphasized that the middle portion of the gasket in the present invention does not hollow out (as in Fig. 1, the middle portion of gasket I and gasket II is the state of hollowing out), in order to avoid affect the flow velocity of pole water.
Because pole water consumption is little, negative electrode water and anode water can supply respectively, decrease the electric leakage between two electrodes, improve current efficiency.Concentrated type electrodialyzer due to the saltiness of waste water of process all more, when using as pole water, by the confession of cathode and anode moisture, otherwise must will cause electric leakage increasing.
Also because pole water flow velocity is comparatively large, pressure and the pressure that is dense, freshwater room of room, pole are close, eliminate the possibility of oozing to pole hydroecium pressure, and this is also vital for raising water yield.
If bias current is relatively more serious when 2. pole water enters electrode vessel, can dead angle area be formed, cause the accumulation that alkaline scale consider, after the fouling of room, pole to such an extent as to electrodialyzer shutdown, time serious, have to cleaning be taken apart.And electrode vessel of the present invention adopts from locking end plate supply pole water, two entery and delivery ports can be arranged easily, avoid pole water bias current;
3. in order to increase the mobility of water in hole to reduce the volts lost of room, pole, the percentage of open area of cuticula orifice plate is increased to and is more than or equal to 60%, and the volts lost of polar region is minimized, because the rigidity of the electrode vessel of integration and intensity are all better, just make percentage of open area be improved; Thicker support and the reinforcement having again electrode frame of cuticula orifice plate, may almost not having of distortion, the hidden danger that electrodialyzer runs is eliminated.
4. save the materials cost of electrode vessel, decrease the trouble of membrane stack in assembling.
Before assembling concentrated type electrodialyzer of the present invention, pre-treatment need be carried out to cutting cephacoria, namely need more than the aqueous solution soaking 48h of the salt identical with the concentrated solution of process, could assemble for membrane stack after cutting.Membrane stack is in the process of assembling, the clean of pole film, negative and positive film and baffle surface must be noted, whether the position at the interval in the middle of each 8 dense, fresh water runner holes at dividing plate two ends there are foreign material, such as, the silk head of the silk screen that dividing plate net is used, because be the place the most easily causing dense, fresh water to ooze mutually here.Certainly, the foreign material of other position also need careful removing.
Waste water reclamation provided by the invention utilize device comparatively prior art there is following difference:
First, the pole water in this device have employed former water, and electrode vessel adopts integrated form.Assuming that each electrode vessel water consumption is 0.4m
3during/h, pole water flow velocity can reach 13cm/s, and the pressure of pole chamber pressure and dense hydroecium and freshwater room balances.Prevent dense, freshwater room to the infiltration of pole hydroecium, to guarantee that desalination rate and water yield reach design requirements; In order to prevent interpenetrating of dense hydroecium and freshwater room, being provided with dense water-circulating pump, making the concentrated stream amount in electrodialysis body equal with raw water flow, also just ensure that the pressure of dense hydroecium and freshwater room is balance mutually.Because dense water will make desalination rate can not be up to standard to freshwater room infiltration; And fresh water will dilute dense water to the infiltration of dense hydroecium, it will be made not reach the dense water concentration of requirement.Because the working current of concentrated type electrodialyzer is comparatively large, the aerogenesis Cl of anode
2and O
2, and the aerogenesis H of negative electrode
2growing amount all many, must drain into outdoor respectively by after gas delivery, the water after separation returns raw water box.In a word, guarantee to only have by dense water refill flow meter unobstructed to dense this road of water moisturizing of circulation, other all leakage approach can not have without exception, and accomplishes that the core of this point is that the pressure of each hydroecium is equal.For certain waste water reclamation project, adopt device as shown in Figure 4, apply its water route and control and technical process, water-yielding capacity 10m
3/ h.Each piping flow is as follows; Former (giving up) discharge is 11.5m
3/ h, fresh-water flow is 10m
3/ h, dense water make up water flow is 0.5m
3/ h, pole discharge is (0.5 × 2=1) m
3/ h, uses former water, with after return raw water box, dense water cycle discharge is 9.5m
3/ h, water yield=10/(10+0.5) × 100%=95.2%.That is: dense water multiple=0.5/0.5=21(doubly).In order to obtain denseer dense water, the dense water of such as 20%-50% mass concentration, then increase a concentrated type electrodialyzer.When former water is due to the problem of water quality, and be not suitable as pole water use.Following way can be adopted: (1) carrys out antiscale by the method that former water adds hydrochloric acid.At this moment the pole water increased by the saltiness crossed regularly is discharged in former water by pole water alone cycle; (2) with the fresh water that tap water or concentrated type electrodialyzer self produce, pole water is prepared with corresponding salt, and alone cycle.Also want regularly the pole water increased by the saltiness crossed to be discharged in former water.
Secondly, through research and practice for many years, concentrated type electrodialyzer is the load of a kind of concentration difference store battery in essence, and access direct supply can charge (shown in the first width figure in Fig. 6, A is to work, and the 4th width figure is that B is to work); Depart from power supply and can be discharged (shown in the second width figure in Fig. 6) by such as lighting.In actual use, when pole starts, direct current supply stops, the voltage at this moment voltmeter demonstrated, and is exactly the electromotive force of concentration difference store battery.
Often the two sides accumulated concentrations of sheet film is poor at work for concentrated type electrodialyzer, and namely the concentration of dense room is higher than light room, forms film concentration difference electricity (position) kinetic potential, is equivalent to charging of accumulators.After departing from power supply, under the driving of concentration difference electromotive force, the ion permeable film of dense room spreads to light room, namely defines the electric current in second class conductor (i.e. ionogen, film is solid state electrolyte).Depart from after power supply and just can measure volts DS on the electrode at concentrated type electrodialyzer two ends, connect a miniature bulb, can continue to light, the discharge process of Here it is concentration difference store battery.Concentrated type electrodialyzer is made up of several dense rooms, light room, that is has several monomer concentration difference electricity (position) kinetic potentials to superpose.Here it is our said concentration difference store battery.
As seen from Figure 6, concentrated type electrodialyzer is a store battery load with a large resistance R for power supply, the same with all store batteries, all wishes that R is the smaller the better, thus can improve the utilization ratio for electric energy.The R that concentrated type electrodialyzer is connected, the content comprised is a lot: 1. the physical structure parameter of electrodialysis body: film logarithm-film logarithm is more, and the resistance that film and dividing plate net are formed is larger; The form of dividing plate and thickness thereof-have loop and loop-free dividing plate, the dividing plate that 0.5-2mm is thick, its resistance value is different; The resistance value of the structure-3mm thin electrodes room of electrode vessel is less than 20mm thick electrode room; Percentage of open area-its resistance value of percentage of open area height person of electrode vessel orifice plate is also little.2. the concentration of dense water, fresh water, pole water: concentration its resistance value higher of each water is also less.3. the temperature of dense water, fresh water, pole water: temperature its resistance value higher of each water is also less.The occasion had surplus heat uses as far as possible.4. the velocity of flow of dense water, fresh water, pole water: the flow velocity of water is high, and the destruction for laminar flow is more severe, concentration difference that is dense, freshwater room is less, and ion exhausts that layer is thinner, and resistance value is less.But general flow velocity 3 ~ 10cm/s enough, higher, increases the power consumption of water pump in vain.When concentration that is dense, fresh water is all higher, such as more than 10g/L, then flow velocity is little also can not cause concentration polarization to 0.5mm/s, and resistance value does not increase.Pole water is owing to only having a Room, and resistance is very little, in order to dense, freshwater room pressure equilibrium, wish that flow velocity is higher, such as 10 ~ 20cm/s, for electrode reaction, cooling of electrode, go out dirt bits all favourable.But it is little for dynamic consumable impact.5. the concentration difference value at dense, water outlet place: in desalination type electrodialyzer, when concentration difference value is little, can not consider.Concentrated type electrodialyzer due to water yield high especially, so dense water out mass concentration may reach hundreds of times of water outlet mass concentration, now the electromotive force of concentration difference store battery also needs other impressed voltage to balance, and this is also equivalent to a kind of additional resistance.The difference that dense water out mass concentration may reach water outlet mass concentration is larger, and additional resistance is also larger.
Store battery must use constant current source charging when charging.Fig. 7 is the charging and discharging curve of lithium ion (storing) battery.Final voltage during electric discharge is 3.2v, and final voltage during charging is 4.2v, is that constant current is carried out during charging.The voltage of charging is also high than 3.7v, and the same with all store batteries, lithium ion battery also has internal resistance.Exceed how many as charging voltage, then will see condition at that time, such as temperature is at that time how many, and temperature height then electrolytical resistance is little, and the voltage that charger exports will be smaller.Internal resistance is also vicissitudinous in fact.Certainly, voltage, as the impellent of process of charging, must reserve sufficient leeway.The charger of the lithium ion battery of single-unit has the voltage of 5v to export.
Also be the process of a charging of accumulators during work of concentrated type electrodialyzer, shown in Fig. 8, the charging and discharging curve of itself and ion (storing) battery is basically identical as seen.During the work of concentrated type electrodialyzer, in fact be exactly in accumulative " concentration difference ", make fresh water more and more lighter, dense water is more and more denseer, once remove direct supply, concentration difference accumulative in concentrated type electrodialyzer, the electrode at concentrated type electrodialyzer two ends just can obtain voltage, connect miniature bulb, concentrated type electrodialyzer is just under concentration diffusion natural force promotes, concentrated type electrodialyzer inner ion is moved to light room by dense room, the electrochemical reaction of the electrode of the electrode vessel through concentrated type electrodialyzer two ends, by the ionic conduction of the two class conductor aqueous solution, be converted to the electronic conduction of a class conductor metal, miniature bulb will be light.
In order to ensure the work capacity of concentrated type electrodialyzer, certain voltage U must be had
workpromote the carrying out of concentration process, voltage can fluctuate along with the concentration of water and temperature fluctuation, but can't change owing to have employed constant current source working current, the salt amount that is concentrated type electrodialyzer is transferred within the unit time is constant.The mass concentration that such concentrated type electrodialyzer produces water is exactly constant.If the mass concentration of former water reduces, and working current is invariable, and concentrated type electrodialyzer will be caused to be in polarized state, makes U
workbe increased to U
polarization, amount of scale buildup will roll up, and why multistage last, the two-stage of Here it is concentrated type electrodialyzer adopt constant current source then what reason of constant pressure source-strengthen of adaptive faculty adopt to(for) influent density change.
Have again, the electrodialysis of the operation of falling pole is called as the electrodialysis of automatic frequent pole, utilize dexterously while switching polarity of electrode and switch physical location that is dense in concentrated type electrodialyzer, freshwater room, by the nucleus of the crystallization that original cathode compartment and former dense hydroecium have just generated, again through desalination after again dissolving.The yin, yang transposition of electrode vessel also can eliminate the alkaline scale of original cathode compartment.The present invention adopts trip switch valve group to realize the operation of falling pole.In the time of falling pole, also causes current/voltage to change accordingly, if in the time of falling pole, is etc. not dense, freshwater room is replaced, just first switch polarity of electrode, be called " directly pole " (as shown in Fig. 6 the 3rd width figure), at this moment desalination type electrodialyzer just there will be 3-5 doubly to the surge impact electric current I of working current
short circuit, and last for several minutes, cause very major injury to power supply, pilot circuit, electrodialyzer body, in fact this situation is equivalent to power supply and the mutual short circuit of concentrated type electrodialyzer, just due to the restriction I of large valued resistor R
short circuitjust be unlikely to be in divergent state.Even if take segmentation to switch water route, classification partly presses electricity, at different levels each section all partly press electricity after, after continuing for half pressure power supply for some time again, total head is powered again, surge current can be limited to the working current of 1.2 times, but it is all underproof for falling the water of output between crisis, the throughput for electrodialyzer causes larger impact.In addition, the surge impact electric current of the generation of falling pole has outclassed limiting current, can increase the amount of scale buildup of electrodialyzer.Just for the result of the further investigation of the load characteristic of electrodialyzer, just had the design success of concentrated type electrodialyzer, this is the process of a theoretical direction practice, the development and application of such as constant current power supply.
As the above analysis, concentrated type electrodialyzer due to working current more much bigger than desalination type electrodialyzer, the impact of the above-mentioned process of falling pole will be very serious, therefore must use constant-current type power supply.The process of constant current source pole is fairly simple, and after dense, the freshwater room of every section of electrodialyzer have been replaced, total current is powered immediately, and owing to adopting constant current source, so do not have surge impact electric current to occur, the fastest speed of use completes the process of falling pole.Ensure that and produce water water quality, protect the safety of power supply and pilot circuit, electrodialyzer membrane stack.
When comprising multistage electrodialysis device in concentration systems, then can adopt constant current source in first and second level, and what adopts constant pressure source, makes it the fluctuation for raw water quality and water temperature, has certain adaptability, reduces the fluctuation of producing water water quality below.Because what electric current rear is all smaller, after adopting the displacement of dense, freshwater room, total head powers on, excessive surge impact electric current can not be caused, and little surge current is owing to having left sufficient surplus in Power Management Design, so no matter can afford for power supply, pilot circuit or membrane stack, be unlikely to cause earlier period damage.
Employing constant current operation is a much progress of concentrated type electrodialyzer, be in particular in: the mass concentration of dense water has had practical guarantee, because desalting process strictly follows Faraday's law of electrolysis, so the salt amount shifted in electrodialyzer work is directly related with constant working current, thus the mass concentration of dense water has also just had practical guarantee; Can the pH value of strict water production control, to produce water pH meta-acid be because ultralimit current work causes the result that polarizes, and now, dense water alkalescence often, the probability making dense hydroecium tie alkali dirt greatly increases.In order to put forward high yield water efficiency, working current is close to 90% of limiting current, and the normal fluctuation of various condition is inevitable, and when using constant pressure source, working current can easily exceed limiting current, causes electrodialyzer fouling to increase the weight of.Use limiting current value that constant current source draws according to robot calculator process calculation program to set up working current, then, then after slightly biased little directional trim, general fluctuation can not affect constant current value.It is controlled that scale problems that is dense, freshwater room also just becomes; Because constant current operation has fundamentally stopped surge current, so the reserved capacity of power supply can reduce, power supply manufacturing cost is lowered.Stop the surge of electrodialyzer body, electrode and power supply, reduce manufacturing cost and daily loss; Electrodialytic water production rate can be improved, experiment proves, even if direct pole, the surge current of constant pressure source is the 300%-500% of working current, and the constant current value of constant current source only changes 1-3%, that is electric current is now that limiting current 90% is increased to 91%-93%, does not have the possibility of the generation of surge current at all.After replacing each hydroecium, partly need not press electricity and go to reduce surge current, but can directly total current power, which reduces the ineffective time of the transient process of falling pole, improve water production rate.
To sum up, had just be suitable for Waste water concentrating the concentrated type electrodialyzer with integrated electrode room, water preparation process flow process and Controlling System and constant current power supply and this three of the pulse power organic assembling, just had can reclaim Freshwater resources and other useful chemical resource, dependable performance, saving energy consumption simultaneously, realize wastewater zero discharge, can for a long time, the high-level efficiency less energy-consumption type waste water reclamation of the present invention of steady running utilizes device.The present invention extensively can promote in fields such as waste water resource recovery for the foregoing reasons.In addition, the present invention also can be applied to desalination type electrodialyzer, and its working efficiency and energy-saving effect can be made equally to increase substantially.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is the structural representation of concentrated type electrodialyzer in prior art.
Fig. 2 is the structural representation of concentrated type electrodialyzer of the present invention.
Fig. 3 is the process flow diagram reclaiming waste water plant in prior art.
Fig. 4 is the process flow diagram that waste water reclamation of the present invention utilizes device.
Fig. 5 is the schematic diagram of trip switch valving I of the present invention and trip switch valving II.
Fig. 6 is the load characteristic explanatory view of concentrated type electrodialyzer.
Fig. 7 is the charging and discharging curve of lithium ion (storing) battery.
Fig. 8 is the principle analysis figure that concentrated type electrodialyzer of the present invention employing constant current power supply is powered.
Fig. 9 is the process flow sheet of the present invention when being applied to waste water reclamation.
Embodiment
A kind of high-level efficiency less energy-consumption type waste water reclamation utilizes device (as shown in Figure 4), comprise former water storage tank 101, by the under meter group that pipeline is connected with described former water storage tank 101 through raw water pump 105, by the concentrated type electrodialyzer group that pipeline is connected with described under meter group, anode water gas-liquid separator 114 and negative electrode aqueous vapor liquid/gas separator 115, wherein, described concentrated type electrodialyzer group comprises at least two-stage concentrated type electrodialyzer;
Described under meter group comprises raw water flow meter 109, concentrated stream gauge 110, anode water under meter 103 and cathode water gauge 104, and above-mentioned under meter is connected with negative electrode hydroecium with the freshwater room of first step concentrated type electrodialyzer, dense hydroecium, anode hydroecium respectively by pipeline;
The anode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank 101 through described anode water gas-liquid separator 114 by pipeline; The negative electrode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank 101 through described negative electrode aqueous vapor liquid/gas separator 115 by pipeline;
The dense hydroecium of described final stage concentrated type electrodialyzer is exported through product concentrated stream gauge 112 through dense water output pump 113 by pipeline; The freshwater room of described final stage concentrated type electrodialyzer is directly exported by pipeline.
Described under meter group also comprises dense water makeup water stream gauge 102, and described dense water makeup water stream gauge 102 is connected by the delivery conduit of pipeline with the dense hydroecium of final stage concentrated type electrodialyzer, and is connected with described concentrated stream gauge 110 through dense water-circulating pump 111.
The freshwater room of described first step concentrated type electrodialyzer, dense hydroecium ingress are provided with the trip switch valving I for the work of falling pole; The freshwater room of described final stage concentrated type electrodialyzer, dense hydroecium exit be provided with for the work of falling pole trip switch valving II (as shown in Figure 6, C is trip switch valving I, D is trip switch valving II), by the open and close controlling water (flow) direction to automatic valve V1-V8, switching of water route when realizing the operation of falling pole.
Wherein, as shown in Figure 2, described concentrated type electrodialyzer comprise be fixedly connected sequentially membrane stack locking end plate 1, gasket 2, integrated electrode room 3 and pole film and membrane stack 4; Described integrated electrode room 3 comprises electrode cabin 6 for hold electrodes and cuticula orifice plate 8; The upper/lower terminal of described membrane stack locking end plate 1 is respectively equipped with electrode water outlet 5 and electrode water import 7, and the upper/lower terminal of described gasket 2 is respectively equipped with and exports 5 and the opening I that matches of described electrode water import 7 and opening II with described electrode water.The Thickness Ratio of described electrode cabin 6 and described cuticula orifice plate 8 is 1:3-4.The percentage of open area of described cuticula orifice plate 8 is more than or equal to 60%.Pole film before use, all need be soaked more than 48h with required yin, yang film by described pole film and membrane stack 4 in the aqueous solution of the salt identical with the maximum concentration that concentrated solution can reach.
As shown in Figure 9, be a concrete application example of the present invention, comprise waste water reclamation and utilize device I, freezing/evaporative crystallizer II, separating centrifuge III, moisture eliminator IV; Waste water is divided into two portions after waste water reclamation utilizes device I to process, and a part is the Freshwater resources reclaimed, and gets back in production technique; The solid crystal of the useful chemical resource that another part is recycled through freezing/evaporative crystallizer II, separating centrifuge III, moisture eliminator IV successively, wherein the isolated crystalline mother solution of separating centrifuge III is got back to waste water reclamation and is utilized in device I concentration that circulates.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (8)
1. a high-level efficiency less energy-consumption type waste water reclamation utilizes device, it is characterized in that: comprise former water storage tank (101), by the under meter group that pipeline is connected with described former water storage tank (101) through raw water pump (105), by the concentrated type electrodialyzer group that pipeline is connected with described under meter group, anode water gas-liquid separator (114) and negative electrode aqueous vapor liquid/gas separator (115), wherein, described concentrated type electrodialyzer group comprises at least two-stage concentrated type electrodialyzer;
Described concentrated type electrodialyzer comprises the membrane stack be fixedly connected sequentially and locks end plate (1), gasket (2), integrated electrode room (3) and pole film and membrane stack (4);
Described integrated electrode room (3) comprises electrode cabin (6) for hold electrodes and cuticula orifice plate (8); The upper/lower terminal of described membrane stack locking end plate (1) is respectively equipped with electrode water outlet (5) and electrode water import (7), and the upper/lower terminal of described gasket (2) is respectively equipped with and exports the opening I and opening II that (5) and described electrode water import (7) match with described electrode water;
Described under meter group comprises raw water flow meter (109), concentrated stream gauge (110), anode water under meter (103) and cathode water gauge (104), and above-mentioned under meter is connected with negative electrode hydroecium with the freshwater room of first step concentrated type electrodialyzer, dense hydroecium, anode hydroecium respectively by pipeline;
The anode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank (101) through described anode water gas-liquid separator (114) by pipeline; The negative electrode hydroecium of final stage concentrated type electrodialyzer is connected with described former water storage tank (101) through described negative electrode aqueous vapor liquid/gas separator (115) by pipeline;
The dense hydroecium of described final stage concentrated type electrodialyzer is exported through product concentrated stream gauge (112) through dense water output pump (113) by pipeline; The freshwater room of described final stage concentrated type electrodialyzer is directly exported by pipeline.
2. high-level efficiency less energy-consumption type waste water reclamation according to claim 1 utilizes device, it is characterized in that: the Thickness Ratio of described electrode cabin (6) and described cuticula orifice plate (8) is 1:3-4.
3. high-level efficiency less energy-consumption type waste water reclamation according to claim 1 utilizes device, it is characterized in that: the percentage of open area of described cuticula orifice plate (8) is more than or equal to 60%.
4. high-level efficiency less energy-consumption type waste water reclamation according to claim 1 utilizes device, it is characterized in that: pole film before use, all need be soaked more than 48h with required yin, yang film by described pole film and membrane stack (4) in the aqueous solution of the salt identical with the maximum concentration that concentrated solution can reach.
5. the high-level efficiency less energy-consumption type waste water reclamation according to any one of Claims 1-4 utilizes device, it is characterized in that: described under meter group also comprises dense water makeup water stream gauge (102), described dense water makeup water stream gauge (102) is connected by the delivery conduit of pipeline with the dense hydroecium of final stage concentrated type electrodialyzer, and is connected with described concentrated stream gauge (110) through dense water-circulating pump (111).
6. high-level efficiency less energy-consumption type waste water reclamation according to claim 5 utilizes device, it is characterized in that: the freshwater room of described first step concentrated type electrodialyzer, dense hydroecium ingress are provided with the trip switch valving I for the work of falling pole; The freshwater room of described final stage concentrated type electrodialyzer, dense hydroecium exit are provided with the trip switch valving II for the work of falling pole.
7. high-level efficiency less energy-consumption type waste water reclamation according to claim 6 utilizes device, it is characterized in that: when the progression of described concentrated type electrodialyzer is less than or equal to secondary, and described concentrated type electrodialyzer adopts constant current power supply to power; When the progression of described concentrated type electrodialyzer is greater than secondary, first and second grade of concentrated type electrodialyzer adopts constant current power supply to power, and the concentrated type electrodialyzer more than third stage adopts constant voltage power supply to power.
8. high-level efficiency less energy-consumption type waste water reclamation according to claim 1 utilizes an application for device, it is characterized in that: comprise waste water reclamation and utilize device (I), freezing/evaporative crystallizer (II), separating centrifuge (III), moisture eliminator (IV); Waste water is divided into two portions after waste water reclamation utilizes device (I) to process, and a part is the Freshwater resources reclaimed, and gets back in production technique; The solid crystal of the useful chemical resource that another part is recycled through freezing/evaporative crystallizer (II), separating centrifuge (III), moisture eliminator (IV) successively, wherein separating centrifuge (III) isolated crystalline mother solution is got back to waste water reclamation and is utilized circulation concentration in device (I).
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