CN104016529A - Multi-stage countercurrent electrodialyzer reversal-based method for treating saline wastewater in coal chemical industry - Google Patents
Multi-stage countercurrent electrodialyzer reversal-based method for treating saline wastewater in coal chemical industry Download PDFInfo
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Abstract
The invention relates to the field of industrial wastewater treatment processes and provides a multi-stage countercurrent electrodialyzer reversal-based method for treating saline wastewater in the coal chemical industry. The method comprises the following steps: 1) carrying out catalytic ozonation treatment on the saline wastewater in the coal chemical industry; 2) carrying out multi-media filtration and membrane filtration treatment on the wastewater subjected to catalytic ozonation in the step 1) in sequence; and 3) treating the effluent obtained after membrane filtration in the step 2) with a multi-stage countercurrent electrodialyzer reversal, thus achieving deep treatment, desalting and recycling of the saline wastewater in the coal chemical industry, wherein the multi-stage countercurrent electrodialyzer reversal comprises an electrodialysis membrane stack unit, a frequency reversal control unit and an online monitoring and process control unit. The method has the advantages of high fresh water recovery rate, low concentrated water discharge, low operating cost, stability in system operation and the like and can avoid the problems of low fresh water recovery rate, low concentration multiple, high treatment cost, serious membrane pollution, instability in system operation and the like in the routine techniques.
Description
Technical field
The present invention relates to technique for treating industrial wastewater field, particularly, the present invention relates to the Coal Chemical Industry salt-containing waste water treatment method based on multi-stage countercurrent pole-reversing electroosmosis device.
Background technology
Coal Chemical Industry brine waste is mainly derived from gas washing wastewater in production process, circulating water system draining, chemical water station draining etc., sometimes also comprise the organic waste water after biochemical treatment, be characterized in that saltiness is high, pollutent is taking total salinity as main, also contains the organism of difficult degradation in part waste water.This class waste water TDS is conventionally in 5000mg/L left and right, even higher, cannot direct reuse.At present, although this class trade effluent COD, ammonia nitrogen etc. reach the outer row's standard of environmental protection, NaCl, Na are contained in water the inside
2sO
4, CaCl
2, MgSO
4, MgCl
2deng salt, direct reuse can cause equipment scaling, corrosion and ooze deposition etc., need carry out desalting treatment.Although can be used for coal ash humidification and rinse road surface or flush the toilet, consumption is also very limited.Therefore, need to carry out advanced treatment and desalination reuse to Coal Chemical Industry brine waste, realize cycling utilization of wastewater and reduce outer row.
Although at present more about the report of coal chemical industrial waste water processing, be to study how to realize coal chemical industrial waste water qualified discharge mostly.As having reported A/O method, Wang Fengjun (little nitrogenous fertilizer, 2010,38 (1): 1-4) processes the application of coal chemical industrial waste water; Wang Wenbiaos etc. (Guangdong chemical industry, 2010,37 (6): 186-188) have been reported employing chlor-alkali oxidation/coagulation air-float/HBF-N process integration processing Anhui coal chemical industry enterprises comprehensive wastewater, and water outlet can reach first discharge standard; Tang Xiuhua (Chinese water supply and drainage, 2011,27 (16): 85-87) enhanced biological decarburization denitrogenation and reuse technology processing coal chemical industrial waste water have been reported, and adopt ozone BAC Technology as advanced treatment unit, although effluent quality reaches " urban sewage reutilization industry water standard " standard, but still cannot recycle as industrial circulating water.Relevant coal chemical industrial waste water is processed and the patent of invention of applying in recent years, as " biochemical processing method of coal chemical industrial waste water " (CN201310198071), the method for extracting and dephenolizing of phenol ammonia coal chemical industrial waste water " a kind of high density containing " (CN103496757), " coal chemical industrial waste water outer circulation moving-burden bed reactor and BAF coupling short-cut denitrification system and method " (CN103351078), " coal gasification waste water advanced treatment system " (CN201310475332) etc., to propose to utilize biological process mostly, ozone oxidation, methods such as extraction or combine use, object is to make coal chemical industrial waste water realize qualified discharge.
Although Coal Chemical Industry brine waste can reach country and local wastewater discharge standard (COD<100mg/L, SS<60mg/L, pH6～9), but still there is part hardly degraded organic substance, microorganism, colloid, particle suspensions, Ca in this class trade effluent
2+and Mg
2+and other high valence ions, inorganic salt etc.At present, conventionally adopt the impurity in membrane sepn or hot concentration technology enrichment waste water, clear water is back to circulating water system, and dense water is arranged outward.As Xie Xiao and Ling Yimin (water treatment information reports, 2010,6:15-20) inquire into coal chemical industry wastewater zero emission strategy, pointed out that the measure of disposing high slat-containing wastewater and wastewater zero discharge abroad has: the spontaneous evaporation pool, deep well injection, burning, steam-powered multiple-effect evaporation, mechanically compress circulating and evaporating technology (MVC) etc.; And domestic employing water saving art improves water use efficiency, and by membrane technique as technical finesses such as reverse osmosis membrane (RO), electrodialysis (ED), micro-filtration (MF), ultrafiltration (UF) and membrane bioreactor (MBR) techniques, reduce to greatest extent high slat-containing wastewater amount.Guo Sen etc. (Coal Chemical Industry, 2011,1:27-30) have inquired into the treatment process of Coal Chemical Industry brine waste, think that reverse osmosis membrane technology and hot concentration technology can be used for the processing of Coal Chemical Industry brine waste.In recent years about the patent of invention of high saliferous Industrial Wastewater Treatment and zero release, as " utilizing circulating water afterheat to process the device and method of high slat-containing wastewater " (CN103553166), " utilizing waste heat flue gas to process the method for high slat-containing wastewater " (CN103553170), " the high dense brine waste treatment process of a kind of agricultureization " (CN103601331), be to utilize hot concentration technology to realize high slat-containing wastewater to reduce discharging mostly.
Coal Chemical Industry brine waste is mainly to adopt heat to concentrate and membrane technique processing at present, but the problem that hot concentration technology ubiquity equipment is huge, energy consumption is high, and the corrosion of chlorion to equipment and the fouling of calcium ions and magnesium ions in the hot concentration process of waste water, can cause maintenance cost high, and add investment and the operation risk of large enterprises.Adopt the two embrane methods of ultrafiltration-reverse osmosis to process coal chemical industrial waste water, only have the fresh water reuse of 60%-70%, the dense water of residue 30%-40% also needs outer row.Because organic concentration in waste water is higher, easily form film and pollute, need to often carry out matting, cause film shortening in work-ing life, mould material loss is large, and system cannot steady in a long-term be moved, and investment running cost is high.And salinity is large in efflux wastewater, outer row is easy to cause soil compaction, when serious, can make salting of soil.Although electrodialytic technique obtains application in brackish water desalination, the concentrated salt manufacturing of seawater etc., owing to being subject to the impact of reverse osmosis technology, this technology is in stagnating and atrophing state at present.Adopt conventional electrodialytic technique to process Coal Chemical Industry brine waste, because the foreign matter content in Coal Chemical Industry brine waste is high, also contain a small amount of hardly degraded organic substance, will inevitably cause the problems such as electrodialysis process desalting efficiency is low, film is seriously polluted, system is difficult for long-term stable operation, maintenance cost height.In a word, existing desalting technology is for the processing of Coal Chemical Industry brine waste, and its facility investment and running cost are all higher, uneconomical economically.Need further research efficiently, wastewater processing technology cheaply, improve the recovery utilization rate of this class waste water.
Summary of the invention
For the water quality characteristics of Coal Chemical Industry brine waste, the present invention proposes a kind of novel method that adopts multi-stage countercurrent pole-reversing electroosmosis to process Coal Chemical Industry brine waste, the method, technology couplings such as pole-reversing electroosmosis and catalytic ozonation, multi-medium filtering, membrane filtrations, realizes advanced treatment and the desalination reuse of Coal Chemical Industry brine waste.Adopt this technical finesse Coal Chemical Industry brine waste, have that fresh water productive rate is high, concentrated water drainage is high-volume little, reduce electrodialytic membranes and pollute and improve the features such as system run all right, wherein fresh water productive rate exceedes 85%, and dense water is concentrated more than 10 times.The method exists can avoid conventional ultrafiltration-reverse osmosis technology to process Coal Chemical Industry brine waste time that fresh-water recovery rate is low, cycles of concentration is low, running cost is high, film is seriously polluted and the problem such as system fluctuation of service, can promote the through engineering approaches of the industry brine waste advanced treatment such as Coal Chemical Industry and desalination reuse to apply.
Particularly, the Coal Chemical Industry salt-containing waste water treatment method based on multi-stage countercurrent pole-reversing electroosmosis device of the present invention, comprises the following steps:
1) Coal Chemical Industry brine waste is used to catalytic ozonation processing;
2) by step 1) waste water after catalytic ozonation is successively through multi-medium filtering, secondary filter and membrane filtration processing;
3) by step 2) film filtration effluent is through the processing of multi-stage countercurrent pole-reversing electroosmosis device, realizes advanced treatment and the desalination reuse of Coal Chemical Industry brine waste;
Wherein, described multi-stage countercurrent pole-reversing electroosmosis device comprises: electrodialysis membrane stack unit, frequently pole-reversing control unit and on-line monitoring and process control unit;
Described electrodialysis cell comprises: electrodialysis membrane stack 3, infusion pump, under meter, tensimeter, pipeline, container for storing liquid 4, assembling frame and rectifier 5; Described electrodialysis membrane stack 3 comprises: the antipollution ion-exchange membrane of some alternative arrangements, dividing plate, the battery lead plate of membrane stack both sides, gripping unit, form utmost point chamber, desalting chamber and the concentration compartments of electrodialysis membrane stack 3 jointly; Form one group by two the above membrane stacks, same group of membrane stack is by rectifier 5 parallel operations; Membrane stack 3 more than two is connected; Described container for storing liquid 4 comprises utmost point water pot, dense water pot, fresh water tank; The series connection of pipeline between the different compartments of described different membrane stack 3, the flow direction of controlling its dense water/fresh water is contrary, forms thus multistage/counter current system, to reduce in membrane stack 3 concentration diffusion between adjacent compartments, improves waste water ratio of desalinization and cycles of concentration.
The described control unit of falling the utmost point comprises: PLC unit 6, automatically controlled valve and rectifier 5, and for completing, electrodialysis membrane stack 3 process of falling utmost point automatically controlled valves open or cut out, rectifier 5 positive and negative electrode commutation signal outputs, and electrodialysis process control; Carry out delay time and the manually setting of automatic mode of the timed interval of falling the utmost point, power-off or the unlatching of membrane stack 3 by touch-screen.
Described parameter online and process control unit comprise: conductivity sensor 1, temperature sensor 2, recording instrument without paper, PLC unit 6, automatically controlled valve; Described multiple conductivity sensor 1 is arranged on the rising pipe of fresh water in membrane stack and/or dense water, for one group of membrane stack of on-line monitoring, 3 fresh water ratio of desalinization and dense water cycles of concentration; By PLC unit 6, the data transmission of conductivity sensor 1 is preserved to recording instrument without paper, and compare with preset value, open or close by the corresponding automatically controlled valve of PLC unit 6 output signal controls, realize that different compartments's solution circulates in membrane stack 3 or part circulation, make fresh water in pipeline/dense water return to another group membrane stack 3 and process or directly discharge; Described temperature sensor 2, is used for monitoring the temperature of membrane stack utmost point chamber solution.
Coal Chemical Industry brine waste of the present invention, include but not limited to derive from gas washing wastewater in Coal Chemical Industry industry production process, circulating water system draining, chemical water station draining etc., sometimes also comprise the organic waste water after biochemical treatment, be characterized in saltiness high (TDS is conventionally even higher in 5000mg/L left and right), also contain part hardly degraded organic substance, this class waste water needs further advanced treatment and electrodialytic desalting could realize reuse.In Coal Chemical Industry brine waste, contain part hardly degraded organic substance, and bacterium, colloid, particle suspensions, Ca
2+and Mg
2+and other high valence ions, other soluble inorganic salts etc., although reached outer row's standard, can cause a large amount of water resource waste, realize this trade effluent resource utilization and recycle, essentially further remove remaining organism and the inorganic salt etc. in waste water.The present invention proposes a kind of method that adopts multi-stage countercurrent pole-reversing electroosmosis to process Coal Chemical Industry brine waste, it is characterized in that the Coal Chemical Industry brine waste through conventional processing qualified discharge, first adopt the technical finesses such as catalytic ozonation, multi-medium filtering, membrane filtration, and adopt the desalination of multi-stage countercurrent pole-reversing electroosmosis, realize advanced treatment and the desalination reuse of Coal Chemical Industry brine waste.Its objective is coupling and the synergy of utilizing the technology such as multi-stage countercurrent pole-reversing electroosmosis and catalytic ozonation, multi-medium filtering and membrane filtration, performance different technologies advantage and the limitation that overcomes monotechnics.The novel method of electrodialysis process Coal Chemical Industry brine waste that the present invention proposes, exists can avoid conventional ultrafiltration-reverse osmosis technology to process Coal Chemical Industry brine waste time that fresh-water recovery rate is low, cycles of concentration is low, processing cost is high, film is seriously polluted and the problem such as system fluctuation of service.The method has former water strong adaptability, high, the dense water cycles of concentration of fresh-water recovery rate high, increase substantially the fresh-water recovery rate of Coal Chemical Industry brine waste and reduce concentrated water drainage high-volume, this technology is also applicable to advanced treatment and the desalination reuse of the industry brine wastes such as chemical industry, oil field, weaving, papermaking.
Described multi-stage countercurrent pole-reversing electroosmosis is processed the method for Coal Chemical Industry brine waste, be characterized in, described multi-stage countercurrent pole-reversing electroosmosis desalination unit, adopt Special electric dialyzer and the combination of electrodialytic membranes heap optimization of the processing of Coal Chemical Industry brine waste, can significantly improve fresh-water recovery rate, reduce concentrated water drainage high-volume, reduce film and pollute and improve system run all right.
The described multi-stage countercurrent pole-reversing electroosmosis unit for the processing of Coal Chemical Industry brine waste, is characterized in, described Special electric dialyzer is made up of jointly electrodialysis membrane stack unit, the control unit of falling the utmost point, on-line monitoring and process control unit etc.Electrodialysis system, by multiple electrodialysis membrane stack serial or parallel connections, is realized multistage desalination or the concentration of Coal Chemical Industry brine waste; Pipeline by different compartments between membrane stack connects with solution stream to control, and the fresh water that makes every group of electrodialysis membrane stack to contrary, reduces concentration diffusion between adjacent fresh water and dense water compartment, raising fresh water ratio of desalinization and dense water cycles of concentration with concentrated stream; By PLC Controlling System, rectifier and automatically controlled valve (as motorized valve, pneumavalve or magnetic valve) etc., jointly realize the electrodialytic desalting unit automatic pouring utmost point, and fall and can regulate according to Coal Chemical Industry brine waste water quality and processing target polar period, the concentration polarization and the film that reduce electrodialysis process pollute.Adopt described multi-stage countercurrent pole-reversing electroosmosis cell processing Coal Chemical Industry brine waste, can realize fresh water productive rate and be greater than 85%, dense water is concentrated more than 10 times.
Described multi-stage countercurrent pole-reversing electroosmosis unit, refer to the series connection of more than at least 2 or 2 electrodialysis membrane stack and combination thereof, improve fresh water ratio of desalinization and dense water cycles of concentration, can realize Coal Chemical Industry brine waste ratio of desalinization is 80%-95%, meet service water reuse standard, and ratio of desalinization can regulate according to processing target.
Antipollution ion-exchange membrane of the present invention is the thin film layer at ionic membrane surface coverage and body membrane oppositely charged, utilizes electrostatic interaction and reduces film surfaceness, and contaminant restraining is in the absorption deposition on film surface.
Multi-stage countercurrent pole-reversing electroosmosis of the present invention is processed the method for Coal Chemical Industry brine waste, utilize multi-medium filtering, secondary filter and membrane filtration etc. further to process the water outlet after catalytic ozonation, remove a small amount of colloid remaining in waste water, suspended substance, thalline, larger molecular organics etc.Wherein, described multi-medium filtering uses quartz sand, gac and flyash as filtration medium; Described membrane filtration adopts one or more in micro-filtration, ultrafiltration and Nanofiltration-membrane technique.By preferred film assembly and combination thereof, improve film filtration effluent water quality, the film that reduces follow-up pole-reversing electroosmosis demineralising process pollutes.
Described catalytic ozonation unit, adopts effective catalyst to improve ozone oxidation efficiency, can promote the oxidation removal of hardly degraded organic substance, significantly reduces hardly degraded organic substance remaining in Coal Chemical Industry brine waste.Particularly, described catalytic ozonation carries out in ozone catalytic tower, wherein fills carbon back composite efficient catalyzer (as KL-CO3), and catalyzer work-ing life is 1-3.Described catalytic ozonation technology, have catalyzed oxidation efficiency high, do not bring other impurity into, to the advantages such as hardly degraded organic substance removal effect is good in high saliferous trade effluent.This catalytic ozonation unit can make up electrodialytic desalting unit can not remove organic deficiency, improves electric osmose division water water quality and reduces electrodialytic membranes and pollute.The present invention proposes to adopt catalytic ozonation to process Coal Chemical Industry brine waste, have catalyzed oxidation efficiency high, do not bring other impurity into, to advantages such as hardly degraded organic substance removal effect in waste water are good.Do not get rid of other high-level oxidation technologies as the use of (electricity) Fenton, wet oxidation process, ultraviolet catalytic oxidation etc., its target is to remove organism, sulfide and Fe remaining in Coal Chemical Industry brine waste simultaneously
2+deng, make hardly degraded organic substance generation open loop and oxidative degradation and kill bacteria etc.
The monotechnics couplings such as described multi-stage countercurrent pole-reversing electroosmosis and catalytic ozonation, multi-medium filtering, membrane filtration, can remove bacterium, particle suspensions, colloid, larger molecular organics, Ca in Coal Chemical Industry brine waste in advance
2+and Mg
2+and high valence ion etc., reducing follow-up electrodialytic membranes pollutes, and the film cleaning interval extends 3-6 month.Can reduce water treatment running cost and improve system run all right simultaneously.
The present invention proposes a kind of method that adopts multi-stage countercurrent pole-reversing electroosmosis to process Coal Chemical Industry brine waste, and with the coupling of the technology such as catalytic ozonation, multi-medium filtering, membrane filtration and synergy, realize advanced treatment and the desalination reuse of Coal Chemical Industry brine waste.Have that fresh-water recovery rate is high, the high-volume advantage such as low, running cost is low, system run all right of concentrated water drainage, can avoid conventional ultrafiltration-reverse osmosis technology to process Coal Chemical Industry brine waste time, have that fresh-water recovery rate is low, cycles of concentration is low, processing cost is high, film is seriously polluted and the problem such as system fluctuation of service.Wherein produce fresh water and can be used as production technique water, recirculated cooling water or feedwater etc.; A small amount of dense water can further evaporate or for coal washing, flushing cinder etc., can be to environment.
The present invention's advantage is compared with prior art:
(1) the present invention adopts multi-stage countercurrent pole-reversing electroosmosis for the processing of Coal Chemical Industry brine waste, with the coupling of the technology such as catalytic ozonation, multi-medium filtering, membrane filtration and synergy, realize advanced treatment and the desalination reuse of Coal Chemical Industry brine waste,, system run all right strong to former water wide accommodation, shock resistance.
(2) the present invention proposes Coal Chemical Industry brine waste advanced treatment and desalination reuse treatment process, have the features such as high, the dense water cycles of concentration of fresh-water recovery rate is high, running cost is low.System producing water ratio is greater than 85%, is less than 15% and arrange the dense water yield outward.
(3) the present invention proposes Coal Chemical Industry brine waste advanced treatment and desalination reuse treatment process, adopt efficient ozone oxide catalyst, can improve the clearance of hardly degraded organic substance in waste water, significantly reduce the film pollution of subsequent processes and put forward high yield water water quality.
Brief description of the drawings
Fig. 1 is Coal Chemical Industry salt-containing waste water treatment method schema of the present invention.
Fig. 2 is the electrodialysis cell schematic diagram of multi-stage countercurrent pole-reversing electroosmosis device of the present invention.
Reference numeral
1, conductivity sensor 2, temperature sensor
3, electrodialysis membrane stack 4, container for storing liquid (containing utmost point water pot, fresh water tank, dense water pot)
5, electrical control cubicles (containing rectifier) 6, PLC unit
Embodiment
Narration especially openly in this specification sheets to obtain arbitrary feature, unless all can be replaced by other equivalences or the alternative features with similar object.Unless narration especially, each feature is an example in a series of equivalences or similar characteristics.Described being only used to helps to understand the present invention, should not be considered as concrete restriction of the present invention.
As shown in Figure 1, the present invention proposes to adopt multi-stage countercurrent pole-reversing electroosmosis to process Coal Chemical Industry brine waste, and utilizes the technology couplings and synergy such as catalytic ozonation, multi-medium filtering, membrane filtration, realizes advanced treatment and the desalination reuse of Coal Chemical Industry containing waste water.Be that Coal Chemical Industry brine waste is first processed and removed most of hardly degraded organic substance (COD) through catalytic ozonation, its clear liquid enters membrane filter unit after multi-medium filtering and secondary filter, remove bacterium, particle suspensions, larger molecular organics and high valence ion etc. through membrane filtration, membrane filtration produces water further through the desalination of multi-stage countercurrent pole-reversing electroosmosis.Whole treatment system producing water ratio is greater than 85%, and the dense water of outer row is less than 15%.It produces water and can be used for production technique water, recirculated cooling water moisturizing and boiler feed water.Coal Chemical Industry brine waste advanced treatment and desalination reuse method that the present invention proposes, also can be used for advanced treatment and the desalination reuse of the industry brine wastes such as chemical industry, metallurgy, weaving, oil field, papermaking.
As shown in Figure 2, the described Special electric dialyzer for the processing of Coal Chemical Industry brine waste comprises: electrodialysis membrane stack unit, frequently pole-reversing control unit, on-line monitoring and process control unit; Described electrodialysis cell comprises: multiple electrodialysis membrane stacks 3, infusion pump, under meter, tensimeter, pipeline, container for storing liquid 4, assembling frame and rectifier 5; Described electrodialysis membrane stack 3 comprises: the antipollution ion-exchange membrane of some alternative arrangements, dividing plate, the battery lead plate of membrane stack both sides, gripping unit, form utmost point chamber, desalting chamber and the concentration compartments of electrodialysis membrane stack 3 jointly; Described membrane stack is 1 group by more than 2 or 2 membrane stack, and same group of membrane stack 3 be by rectifier 5 parallel operations, and according to membrane stack ratio of desalinization size, and 2 groups or 2 groups of above membrane stacks 3 are connected; Described container for storing liquid 4 comprises utmost point water pot, dense water pot, fresh water tank; Described electrodialysis membrane stack unit, pipeline series connection between different membrane stack 3 different compartments, the flow direction of controlling its dense water/fresh water is contrary, be that fresh water is by the 1st grade of water inlet of first group, last 1 grade of water outlet of last group, dense water is from last 1 grade of water inlet of last group, the 1st grade of water outlet of first group, form thus multistage/counter current system, to reduce in membrane stack 3 concentration diffusion between adjacent compartments, improve waste water ratio of desalinization and cycles of concentration.The described control unit of falling the utmost point comprises: PLC unit 6, automatically controlled valve, rectifier 5, for completing signal output and the electrodialysis process controls such as electrodialysis membrane stack 3 process of falling utmost point automatically controlled valve On/Off, rectifier 5 positive and negative electrode commutations; Can conveniently carry out the setting of 3 timed intervals of falling the utmost point of membrane stack, power-off/open time delay time, manual/auto pattern by touch-screen.Described parameter online and process control unit comprise: conductivity sensor 1, temperature sensor 2, recording instrument without paper, PLC unit 6, automatically controlled valve; Described multiple conductivity sensor 1 is arranged on the rising pipe of fresh water in membrane stack/dense water, for one group of membrane stack of on-line monitoring, 3 fresh water ratio of desalinization and dense water cycles of concentration; By PLC unit 6, the data transmission of conductivity sensor 1 is preserved to recording instrument without paper, and compare with preset value, by the corresponding automatically controlled valve On/Off of PLC unit 6 output signal controls, realize that different compartments's solution circulates in membrane stack 3 or part circulation, make fresh water in pipeline/dense water return to another group membrane stack 3 and further process or directly discharge; Described temperature sensor 2, is used for monitoring the temperature of membrane stack utmost point chamber solution; In the time that monitor temperature is greater than systemic presupposition value, by PLC unit 6 output signal Controlling System power-off/stoppage protections, output alarm signal.
Embodiment 1 simulates the electrodialytic desalting of Coal Chemical Industry brine waste
Adopt electrodialytic technique treatment of simulated Coal Chemical Industry brine waste, the impact on ratio of desalinization, energy consumption and membrane stack voltage etc. while investigating dense water, the different initial Cl-ion of fresh water.Research shows, when Cl-starting point concentration in fresh water is 600mg/L, and dense water starting point concentration is respectively 1200,5000 and when 8000mg/L, under constant-pressure conditions, reduces its resistance to increase with fresh water saltiness, can cause current density to decline.In the time of 150min, in fresh water, Cl-ionic concn can drop to below 250mg/L, and in the time that in dense water, Cl-ionic concn is higher, its Cl-ion removes speed and slows down, and it is that in dense water, Cl-ion counter diffusion causes that its reason is inferred; The dense water current efficiency of different starting point concentrations all presents front desalination early stage higher (more than 85%), along with desalination is carried out its current efficiency and dropped to gradually below 60%.When fresh water starting point concentration is 1200mg/L, control the initial Cl-ionic concn of dense water and be 1200,5000,8000 and 12000mg/L, under constant potential, operate equally, in fresh water, Cl-ion remaval rate increases and reduces with Cl-ionic concn in dense water, means that Cl-ion in fresh water is removed to prescribed concentration needs the longer time.Result shows, in the time that in fresh water, Cl-ionic concn is higher, in its unit time, the absolute migration amount of ion is greater than the brine waste that starting point concentration is lower; Secondly, the concentration of dense water, fresh water differs and more also can cause the aggravation of ion counter diffusion, thereby reduces its current efficiency; Although its current efficiency presents similar variation tendency in the time that fresh water concentration is higher, slow when its fall is lower than fresh water starting point concentration.
The electrodialytic desalting of the actual Coal Chemical Industry brine waste of embodiment 2
Taking the outer draining of Coal Chemical Industry BAF as example, although reached the outer row's standard of trade effluent, owing to limiting its recycle containing the inorganic salt such as Cl-ion, a small amount of hardly degraded organic substance, particle suspensions and bacterium etc., need further to remove mineral ion and other pollutents such as Cl-.Adopt electrodialytic technique to carry out desalting treatment, after adopting constant potential operation, dense water and fresh water all to adopt the cotton filtration of 5 μ m PP, directly intake as electrodialysis system, find through 10 batches of continuous desalination experiments, carry out with electrodialytic, similar to simulated wastewater, under identical desalination condition, in fresh water, Cl-ion drops to and is less than 250mg/L and reaches reuse standard.But current density is all carried out all on a declining curvely with demineralising process in every batch of experiment, and different batches downtrending is comparatively similar, and under constant potential, the initial current density of different batches slightly declines, infer that with electrodialytic desalting process, film may occur pollutes.Further tearing membrane stack open finds, all can obviously observe tawny pollutent tectum on anion-exchange membrane two sides, but obvious film contamination phenomenon is not observed on cationic exchange membrane surface, analyze reason and be anion-exchange membrane due to positively charged, and in Coal Chemical Industry brine waste, electronegative organism is adsorbed onto film surface by electrostatic interaction and forms.The film pollution that anion-exchange membrane surface forms causes Coal Chemical Industry brine waste electrodialysis process to be difficult to continual and steady operation, needs further to inquire into its film and pollutes formation mechanism and prevent and treat method.
Except measuring the COD variation in dense water and fresh water, further by investigating organic migration in fresh water in electrodialysis process.If dense water is with not containing organic Coal Chemical Industry simulated wastewater, fresh water with front identical, electrodialysis experiment finds that negatively charged ion and light chamber coal chemical industrial waste water contact surface can be observed obvious film and pollute, pollute and do not observe film with simulated wastewater contact surface, show that the light organic pollutants overwhelming majority is trapped in fresh water by cavity block and can not be concentrated by electrodialysis process.In this system, not observing equally anode membrane surface pollutes.Because the film pollution level of female die surface reduces, in 10 batches of electrodialytic desalting experiments, do not observe degradation phenomenon under obvious current density, ratio of desalinization, current efficiency.But along with the carrying out of electrodialytic desalting process, its film pollutes inevitable aggravation gradually, also will inevitably affect the stability of electrodialysis operation.
Embodiment 3 multi-stage countercurrent pole-reversing electroosmosis are processed actual Coal Chemical Industry brine waste
For the outer draining of domestic large-scale iron and steel enterprise Coal Chemical Industry BAF (being called for short Coal Chemical Industry brine waste), although reached outer row's standard, in waste water, also contain a small amount of hardly degraded organic substance, soluble inorganic salt, Ca
2+and Mg
2+ion, suspended substance, colloid, colourity and other impurity etc., after sand filter, directly adopt the processing of multi-stage countercurrent pole-reversing electroosmosis, after continuous 5 days of system, find to decline gradually applying equally current density under voltage, cause electrodialytic desalting speed sharply to decline, unit waste water ratio of desalinization also significantly reduces, and membrane resistance significantly raises, and causes electrodialytic desalting system to be difficult to continuous service.Tear electrodialysis membrane stack open and find, ion-exchange membrane surface contamination is serious, the especially visible one deck tawny colloidal adsorption layer in anion-exchange membrane surface, and also by matting, ion-exchange membrane performance recovery effect is undesirable.Result shows, Coal Chemical Industry brine waste need carry out pre-treatment, adopts the further desalination of electrodialytic technique after reducing the component that causes film to pollute again.
Thus, the present invention a kind of method that adopts multi-stage countercurrent pole-reversing electroosmosis to process Coal Chemical Industry brine waste proposed, and with the technology coupling and synergy such as catalytic ozonation, multi-medium filtering, membrane filtration.Be that Coal Chemical Industry brine waste is after the pre-treatment such as catalytic ozonation, multi-medium filtering, membrane filtration, can remove most of hardly degraded organic substance, hardness, colourity and particle suspensions etc., wherein in waste water, COD drops to and is less than 20mg/L from 100mg/L left and right, waste water is become colorless transparent by light tan, can significantly reduce follow-up electrodialytic membranes and pollute.Again through multi-stage countercurrent electrodialytic desalting desalting treatment, its ratio of desalinization can be stablized and reaches more than 90%, and wherein Cl-ionic concn is less than 250mg/L, meets industrial effluent reusing standard.Result shows, the operation continuously in 3-6 month of electrodialysis system process, and anion-exchange membrane, cationic exchange membrane all do not occur that obvious film pollutes, all kept stables in system operational process such as its ratio of desalinization, current efficiency, unit consumption of energy.Prove thus, Coal Chemical Industry brine waste advanced treatment and desalination reuse method that the present invention proposes, to Coal Chemical Industry brine waste, processing has better adaptability, the good and applicable large-scale promotion application of application prospect.
Non-elaborated part of the present invention belongs to techniques well known.
Certainly; the present invention can also have various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art can openly make various corresponding changes and distortion according to of the present invention, but these corresponding changes and distortion all should belong to the protection domain of claim of the present invention.
Claims (6)
1. the Coal Chemical Industry salt-containing waste water treatment method based on multi-stage countercurrent pole-reversing electroosmosis device, comprises the following steps:
1) Coal Chemical Industry brine waste is used to catalytic ozonation processing;
2) by step 1) waste water after catalytic ozonation is successively through multi-medium filtering and membrane filtration processing;
3) by step 2) film filtration effluent is through the processing of multi-stage countercurrent pole-reversing electroosmosis device, realizes advanced treatment and the desalination reuse of Coal Chemical Industry brine waste;
Wherein, described multi-stage countercurrent pole-reversing electroosmosis device comprises: electrodialysis membrane stack unit, frequently pole-reversing control unit and on-line monitoring and process control unit;
Described electrodialysis cell comprises: electrodialysis membrane stack (3), infusion pump, under meter, tensimeter, pipeline, container for storing liquid (4) and assembling frame and rectifier (5); Described electrodialysis membrane stack (3) comprising: the antipollution ion-exchange membrane of some alternative arrangements, dividing plate, the battery lead plate of membrane stack both sides, gripping unit, form utmost point chamber, desalting chamber and the concentration compartments of electrodialysis membrane stack (3) jointly; Form one group by two the above membrane stacks, same group of membrane stack is by a rectifier (5) parallel operation; Membrane stack (3) more than two is connected; Described container for storing liquid (4) comprises utmost point water pot, dense water pot, fresh water tank; Pipeline series connection between the different compartments of described different membrane stack (3), the flow direction of controlling its dense water/fresh water is contrary, form thus multistage/counter current system, to reduce in membrane stack (3) concentration diffusion between adjacent compartments, improve waste water ratio of desalinization and cycles of concentration.
2. Coal Chemical Industry salt-containing waste water treatment method according to claim 1, is characterized in that, described multi-medium filtering uses quartz sand, gac and flyash as filtration medium.
3. Coal Chemical Industry salt-containing waste water treatment method according to claim 1, is characterized in that, described membrane filtration adopts one or more in micro-filtration, ultrafiltration and Nanofiltration-membrane technique.
4. Coal Chemical Industry salt-containing waste water treatment method according to claim 1, it is characterized in that, the described control unit of falling the utmost point comprises: PLC unit (6), automatically controlled valve and rectifier (5), be used for that electrodialysis membrane stack (3) process of falling utmost point automatically controlled valve opens or cuts out, rectifier (5) positive and negative electrode commutation signal output, and electrodialysis process control; Carry out delay time and the manually setting of automatic mode of the timed interval of falling the utmost point, power-off or the unlatching of membrane stack (3) by touch-screen.
5. Coal Chemical Industry salt-containing waste water treatment method according to claim 1, it is characterized in that, described parameter online and process control unit comprise: conductivity sensor (1), temperature sensor (2), recording instrument without paper, PLC unit (6) and automatically controlled valve; Described multiple conductivity sensor (1) is arranged on the rising pipe of fresh water in membrane stack and/or dense water, for one group of membrane stack of on-line monitoring (3) fresh water ratio of desalinization and dense water cycles of concentration; By PLC unit (6), the data transmission of conductivity sensor (1) is preserved to recording instrument without paper, and compare with preset value, open or close by the corresponding automatically controlled valve of PLC unit (6) output signal control, realize that different compartments's solution circulates in membrane stack (3) or part circulation, make fresh water in pipeline/dense water return to that another group membrane stack (3) is processed or directly discharge; Described temperature sensor (2), is used for monitoring the temperature of membrane stack utmost point chamber solution.
6. according to the Coal Chemical Industry salt-containing waste water treatment method described in claim 1,4 or 5, it is characterized in that, described antipollution ion-exchange membrane is the thin film layer at ionic membrane surface coverage and body membrane oppositely charged, utilize electrostatic interaction and reduce film surfaceness, contaminant restraining is in the absorption deposition on film surface.
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