CN103723800B - Method for protecting electric filter and removing electronegative colloids and particles in brine wastewater by electrodialysis - Google Patents
Method for protecting electric filter and removing electronegative colloids and particles in brine wastewater by electrodialysis Download PDFInfo
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- CN103723800B CN103723800B CN201310717320.4A CN201310717320A CN103723800B CN 103723800 B CN103723800 B CN 103723800B CN 201310717320 A CN201310717320 A CN 201310717320A CN 103723800 B CN103723800 B CN 103723800B
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Abstract
The invention relates to a method for protecting electric filter and removing electronegative colloids and particles in brine wastewater by electrodialysis. Anion-exchange membranes, partition meshes and anion-exchange membranes are sequentially and alternately arranged between the negative plate and positive plate to constitute an electric filter water channel, and are clamped by a clamping device to constitute an electric filter. When brine wastewater containing electronegative colloids and particles enter the electric filter, a direct current is applied between the positive and negative plates, so that the electronegative colloids and particles in the brine wastewater migrate to the anion-exchange membranes under the action of the electric field; and in the migration process, the electronegative colloids and particles are blocked by the anion-exchange membranes and adhere to the membrane surface or are embedded into the pores of the membranes, thereby removing the electronegative colloids and particles in the brine wastewater. The wastewater adsorbed by the electric filter enters subsequent electrodialysis equipment to perform desalting operation, thereby lowering the pollution level of the negative membranes of the electrodialysis equipment, ensuring the long-term stable operation of the electrodialysis equipment and prolonging the service life of the electrodialysis equipment.
Description
Technical field
The present invention relates to water treatment and brine waste concentration technique field, more specifically relating to a kind of removal in brine waste by electric field has the electronegativity colloid of serious harm, particulate and electronegativity macromolecular electrodialysis protection electrofilter and method to the steady running of electrodialytic desalting device.
Background technology
Along with the development of conventional electrodialysis technology, and society is to the requirement of water utilization rate, and electrodialytic technique is in field of industrial waste water treatment, and particularly high salt sewage disposal and sewage " zero release " aspect show its unique advantage.But in electrodialysis appts long-time running, due to complicated component in trade effluent, the pollution problem of electrodialytic membranes particularly cavity block becomes a bottleneck of restriction electrodialytic technique broader applications.
Electrodialyzer is made up of five parts such as anions and canons exchange membrane, dividing plate net, electrode, gripping unit and direct supplys.Under DC Electric Field, water intermediate ion displacement in the solution, utilizes the selective penetrated property of ion-exchange membrane, realizes concentrating, desalinate and purifying of solution.
After running for some time continuously for the electrodialysis unit of sewage disposal, there will be ion-exchange membrane surface and inner blocked, cause membrane resistance to increase, energy consumption rises, and runner pressure drop increases, and desalination declines, this phenomenon is called fouling membrane, and when pollution acquires a certain degree, device can not normally run.Thus studying the waste-load allocation of ion-exchange membrane, set up the measure of effectively alleviating and removing fouling membrane, is the key issue solving electrodialytic technique broader applications.
The principle of work of electrodialysis appts determines the pollution modes mainly fouling of electrodialyzer anode membrane, and the pollution of electrodialysis cavity block mainly in water electronegative colloid, particulate and some electronegativity macromole under the effect of electric field or be adsorbed in female die surface or be embedded in the cavity block dirt that cavity block internal gutter causes stifled, its phenomenon causes the decline of electrodialysis cavity block ratio of desalinization, resistance rising, energy consumption to strengthen, runner pressure drop raises, and causes electrodialytic desalting device to be paralysed time serious.Thus, effectively removing electronegative colloid, particulate and some electronegativity macromole in electrodialysis water inlet is one of important factor ensureing electrodialysis steady running.
At present, the measure of polluting about preventing electrodialytic membranes, mainly comprises following 5 aspects.
1, frequently pole-reversing;
2, direct current is replaced by pulsed electrical;
3, colloid or organic content in strict control water inlet;
4, strengthen compartment thickness, and import in compartment air play stirring and cleanup action;
5, medicament is added in the solution, with fouling tendency ionic interaction.
The above-mentioned measure overwhelming majority is for preventing electrodialysis anode membrane from polluting, and only has the 3rd article " in strict control water inlet colloid or organic content " to be for preventing electrodialysis cavity block from polluting, but does not provide concrete grammar.
Summary of the invention
The object of the present invention is to provide a kind of electrodialysis protection electrofilter and utilize this electrofilter to remove in brine waste and the electronegativity colloid of harm, particulate and the macromolecular low operating cost method of electronegativity are normally run to electrodialytic desalting device.
For reaching this object, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of electrodialysis protection electrofilter, and described electrofilter is made up of anion-exchange membrane, dividing plate net, electrode, gripping unit and direct supply;
Between negative plate and positive plate, be alternately arranged by anion-exchange membrane and dividing plate net and form electrofilter water stream channel, after gripping means grips, form electrofilter.
Gripping unit of the present invention can be known from prior art by those skilled in the art, in the specific implementation, can design with reference to the gripping unit in electrodialyzer.
Described electrodialysis protection electrofilter can be used for the object realizing removing electronegative macromole, colloid and particulate in brine waste, avoids the cavity block of follow-up electrodialysis appts to pollute.
Described dividing plate net adopts high resistivity thermoplastic material, is selected from polypropylene, polycarbonate or polycarbonate and ethylene vinyl acetate.
Described dividing plate net adopts rectangular configuration, and both sides are sealed edge, and meshed straight general formula inlet conduit is established in bottom, are connected with the water inlet cloth tank bottom electrofilter; Meshed straight general formula outlet passage is established at top, is connected with the water outlet collecting tray at electrofilter top.Described dividing plate netting gear has high-efficiency mixed flow effective structure, has good sealing function simultaneously.
Described anion-exchange membrane is selected from the one in out-phase anion-exchange membrane, half homogeneous-phase anion exchange film or homogeneous-phase anion exchange film.
Described anion-exchange membrane adopts the old film of replacing in electrodialytic desalting device, to realize the recycling of electrodialytic membranes, reduces the pollution to environment.
Two of object of the present invention is to provide a kind of method utilizing electrofilter as above to remove electronegativity colloid, particulate in brine waste,
After the brine waste containing electronegativity colloid, particulate enters electrofilter, direct current is added at positive/negative plate, electronegativity colloid in brine waste, particulate move to anion-exchange membrane under electric field action, in transition process, be subject to anion-exchange membrane intercept, be attached to film surface or embed in film inner duct, thus removing electronegativity colloid, the particulate in brine waste.
Described brine waste is for through falling the pretreated low-hardness waters such as hard, turbidity removal.
After electrofilter absorption is saturated, electrode is switched and is passed into after aqueous sodium hydroxide solution carries out backwash and regeneration to electrofilter, continues to use.
The volumetric molar concentration of described sodium hydroxide solution is 0.1 ~ 1mol/L.
Three of object of the present invention is that providing a kind of utilizes described electrofilter to carry out pre-treatment to water, thus ensure the method that electrodialysis long-term stability is run, brine waste is first after electrostatic filter adsorption treatment, remove electronegativity colloid, particulate and electronegativity macromole wherein, then enter follow-up electrodialysis appts and carry out de-salting operation.
Waste water after electrostatic filter adsorption treatment enters follow-up electrodialysis appts and carries out de-salting operation, can reduce the pollution level of electrodialysis appts cavity block, ensures that electrodialysis appts long-term stability is run.
Compared with prior art scheme, the present invention has following beneficial effect:
1) the present invention is according to the pollution mechanism of electrodialysis cavity block, under electric field action, utilizes anion-exchange membrane to carry out active adsorption, removal to endangering electronegativity colloid, particulate and the macromole that electrodialysis normally runs in water inlet;
2) electrofilter of the present invention is removed electronegativity colloid, particulate and macromole nearly all can pollute electrodialysis cavity block, and the material can not removed by electrofilter causes electrodialysis cavity block to pollute hardly, has very high selectivity and adsorption rate;
3) the present invention can utilize in electrodialytic desalting device the old film of replacing, and realizes the second stage employ of old film, is conducive to environment protection;
4) brine waste of process of the present invention comprises petrochemical industry sewer, Coal Chemical Industry coking chemical waste water and oily(waste)water etc.
Accompanying drawing explanation
Fig. 1 is the structural representation of electrodialysis protection electrofilter of the present invention.
Wherein: 1-anion-exchange membrane; 2-dividing plate net; 3-negative plate; 4-positive plate; 5-brine waste; 6-produces water.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
As shown in Figure 1, a kind of electrodialysis protection electrofilter, described electrofilter is made up of anion-exchange membrane 1, dividing plate net 2, electrode, gripping unit and direct supply;
Between negative plate 3 and positive plate 4, be alternately arranged by anion-exchange membrane and dividing plate net and form electrofilter water stream channel, after gripping means grips, form electrofilter.
Described dividing plate net adopts high resistivity thermoplastic material, is selected from polypropylene, polycarbonate or polycarbonate and ethylene vinyl acetate.
Described dividing plate net adopts rectangular configuration, and both sides are sealed edge, and meshed straight general formula inlet conduit is established in bottom, are connected with the water inlet cloth tank bottom electrofilter; Meshed straight general formula outlet passage is established at top, is connected with the water outlet collecting tray at electrofilter top.
Described anion-exchange membrane is selected from the one in out-phase anion-exchange membrane, half homogeneous-phase anion exchange film or homogeneous-phase anion exchange film.
The old film that described anion-exchange membrane can adopt electrodialytic desalting device to replace.
A kind of method utilizing above-mentioned electrofilter to remove electronegativity colloid, particulate in brine waste, after the brine waste 5 containing electronegativity colloid, particulate enters electrofilter, direct current is added at positive/negative plate, electronegativity colloid in brine waste 5, particulate move to anion-exchange membrane under electric field action, in transition process, be subject to anion-exchange membrane intercept, be attached to film surface or embed in film inner duct, thus removing electronegativity colloid, the particulate in brine waste 5, obtaining and produce water 6.
Described brine waste 5 is for through falling the pretreated low-hardness waters such as hard, turbidity removal.
After electrofilter absorption is saturated, electrode is switched and is passed into aqueous sodium hydroxide solution and carries out backwash and regeneration to electrofilter.
The volumetric molar concentration of described sodium hydroxide solution is 0.1 ~ 1mol/L.
Utilize above-mentioned electrofilter to carry out an electrodialytic method, brine waste, first after electrostatic filter adsorption treatment, is removed electronegativity colloid, particulate and electronegativity macromole wherein, is then entered follow-up electrodialysis appts and carry out de-salting operation.
Specific embodiment 1
Wastewater Form Circulating Cooling Water in petrochemical industry, through except water outlet after the pre-treatment such as hard, turbidity removal, promotes through pump and enters electrofilter of the present invention, run continuously.Flow velocity is regulated by under meter, and by regulating voltage and current control COD removal effect.The flooding velocity of electrofilter is 1m
3/ h, applying voltage is 30V, and display electric current is 8A, detects every sampling in 1 hour.Before and after process, water-quality guideline is shown in Table 1.From the results shown in Table 1, after this electrofilter process, in water, COD content obviously reduces, and average removal rate is 26%, reaches as high as 51.0%.
COD situation after the process of table 1 electrostatic filter
Specific embodiment 2
The Wastewater Form Circulating Cooling Water of Coal Chemical Industry coal chemical enterprise, through except water outlet after the pre-treatment such as hard, turbidity removal, promotes through topping-up pump and enters electrofilter of the present invention, run continuously.Flow velocity is regulated by under meter, and by regulating voltage and current control COD removal effect.The flooding velocity of electrofilter is 1m
3/ h, applying voltage is 35V, and display electric current is 10A, detects every sampling in 1 hour.Before and after process, water-quality guideline is shown in Table 2.From the results shown in Table 2, after this electrofilter process, in water, COD content obviously reduces, and average removal rate is 35.4%, reaches as high as 38.5%.
COD situation after the process of table 2 electrostatic filter
Comparative example 3
To adopt in petrochemical industry through turbidity removal, except the pretreated Wastewater Form Circulating Cooling Water such as hard is as former water, two same model electrodialyzers A, B are adopted to form two cover systems, a set of is electrofilter of the present invention+electrodialyzer A, another set of is electrodialyzer B, judging electrodialysis cavity block pollution level by measuring membrane stack Pressure Drop in operational process, comparing test.
Two electrodialyzer initial differential pressure measure: former water point two-way after pump promotes enters electrodialyzer A and B, keeps flooding velocity to be stabilized in 1m
3/ h, then adds constant voltage 30V, records electrodialyzer A, B import and export two ends pressure drop and is respectively 3.35kpa and 3.57kpa.
Electrodialyzer A, B share a D.C. regulated power supply, adopt constant voltage operation, and adopt dense water acid adding mode, regulate dense water pH value between 4 ~ 6, the fouling of prevention electrodialyzer anode membrane.Former water point two-way after pump promotes enters above-mentioned experimental installation, keeps flooding velocity to be stabilized in 1m
3/ h, it is 30V that electrofilter applies voltage, and display electric current is 8A, keeps voltage stabilization added by electrofilter, runs continuously.Then by detecting A, B two electrodialyzer Inlet and outlet water pressure reduction respectively, the large person of Inlet and outlet water pressure reduction, illustrate that the dirt of electrodialyzer runner is stifled serious, thus judge electrodialyzer runner and the stifled degree of cavity block dirt.
Table 3 different operating time electrodialyzer inlet outlet pressure differential
Comparative example 4
Adopt the sugary stoste in biochemical sugaring process, two cover systems are formed with two same model electrodialyzers A, B, a set of is electrofilter of the present invention+electrodialyzer A, another set of is electrodialyzer B, judging electrodialysis cavity block pollution level by measuring membrane stack Pressure Drop in operational process, comparing test.
Two electrodialyzer initial differential pressure measure: former water point two-way after pump promotes enters electrodialyzer A and B, keeps feed liquor stability of flow at 0.6m
3/ h, then adds constant voltage 30V, records electrodialyzer A, B import and export two ends pressure drop and is respectively 6.55kpa and 6.69kpa.
Electrodialyzer A, B share a D.C. regulated power supply, adopt constant voltage operation.Stoste point two-way after pump promotes enters above-mentioned experimental installation, keeps flooding velocity to be stabilized in 0.6m
3/ h, it is 30V that electrofilter applies voltage, and display electric current is 7.2A, keeps voltage stabilization added by electrofilter, runs continuously.Then by detecting A, B two electrodialyzer Inlet and outlet water pressure reduction respectively, the large person of Inlet and outlet water pressure reduction, illustrate that the dirt of electrodialyzer runner is stifled serious, thus judge electrodialyzer runner and the stifled degree of cavity block dirt.
Table 4 different operating time electrodialyzer inlet outlet pressure differential
Applicant states, the present invention illustrates detailed construction feature of the present invention and method by above-described embodiment, but the present invention is not limited to above-mentioned detailed construction feature and method, namely do not mean that the present invention must rely on above-mentioned detailed construction feature and method could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the increase of accessory, the concrete way choice etc. of parts selected by the present invention, all drops within protection scope of the present invention and open scope.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. an electrodialysis protection electrofilter, is characterized in that, described electrofilter is made up of anion-exchange membrane (1), dividing plate net (2), electrode, gripping unit and direct supply;
Between negative plate (3) and positive plate (4), be alternately arranged by anion-exchange membrane and dividing plate net and form electrofilter water stream channel, after gripping means grips, form electrofilter;
Described dividing plate net adopts rectangular configuration, and both sides are sealed edge, and meshed straight general formula inlet conduit is established in bottom, are connected with the water inlet cloth tank bottom electrofilter; Meshed straight general formula outlet passage is established at top, is connected with the water outlet collecting tray at electrofilter top.
2. electrofilter as claimed in claim 1, is characterized in that, described dividing plate net adopts high resistivity thermoplastic material.
3. electrofilter as claimed in claim 2, it is characterized in that, described high resistivity thermoplastic material is selected from polycarbonate and ethylene vinyl acetate, polypropylene or polycarbonate.
4. electrofilter as claimed in claim 1 or 2, it is characterized in that, described anion-exchange membrane is selected from the one in out-phase anion-exchange membrane, half homogeneous-phase anion exchange film or homogeneous-phase anion exchange film.
5. the electrofilter as described in one of claim 1-3, is characterized in that, the old film that described anion-exchange membrane adopts electrodialytic desalting device to replace.
6. utilize the electrofilter as described in one of claim 1-5 to remove a method for electronegativity colloid in brine waste, it is characterized in that,
After the brine waste containing electronegativity colloid enters electrofilter, direct current is added at positive/negative plate, electronegativity colloid in brine waste moves to anion-exchange membrane under electric field action, in transition process, be subject to anion-exchange membrane intercept, be attached to film surface or embed in film inner duct, thus removing the electronegativity colloid in brine waste.
7. method as claimed in claim 6, is characterized in that, described brine waste is through falling hard, the pretreated low-hardness water of turbidity removal.
8. method as claimed in claims 6 or 7, is characterized in that, after described electrofilter absorption is saturated, is switched and passes into aqueous sodium hydroxide solution carry out backwash and regeneration to electrofilter by electrode.
9. method as claimed in claim 8, it is characterized in that, the volumetric molar concentration of described sodium hydroxide solution is 0.1 ~ 1mol/L.
10. the application method of the electrofilter as described in one of claim 1-5, it is characterized in that, brine waste, first after electrostatic filter adsorption treatment, is removed electronegativity colloid wherein and electronegativity macromole, is then entered follow-up electrodialysis appts and carry out de-salting operation.
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