CN1590322A - Membrane separation method of zero discharge of electroplating waste water treatment - Google Patents
Membrane separation method of zero discharge of electroplating waste water treatment Download PDFInfo
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- CN1590322A CN1590322A CN 03157655 CN03157655A CN1590322A CN 1590322 A CN1590322 A CN 1590322A CN 03157655 CN03157655 CN 03157655 CN 03157655 A CN03157655 A CN 03157655A CN 1590322 A CN1590322 A CN 1590322A
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Abstract
A membrane separation method for reclaiming the electroplating sewage includes liqui material treating, lifting, pressurizing and delivering. It features the 3-class membrane separation to remove impurities, organic substances, fine suspended substances, Na ions, heavy metal ions, inorganic ions, etc. the regulation of pH value to prevent deposition of hydroxide, periodical automatic flushing and reuse of treated water.
Description
Technical field
The invention belongs to electroplating wastewater processing and water reuse and heavy metal resources reclaims.Specifically adopt membrane integrating technique to handle electroplating wastewater, reclaim heavy metal and water resources in the waste water respectively: heavy metal telegram in reply coating bath or make heavy metallic salt, water is got back to and is done rinsing usefulness in the production technique, realizes that resource reclaims and the electroplating wastewater processing zero release comprehensively.
Background technology
Electroplating wastewater is because plating is different with electroplating technology, and treatment process has tens kinds.According to " electroplating and finish " 22 (2) (2000) 6, publish the article " review that China's electroplating wastewater is administered over 50 years ", author Dong Ruiguang; " Shanghai plating ", 2 (1998) 11, publish the article " electroplating industry water saving approach is all ", author Zheng Ruiting; Reach " electroplating and environmental protection " 20 (2) (2000) 3 according to this, " the Shanghai electroplating industry is general situation of development and prospect in recent years " literary composition publication, author Shen Pinhua has quoted from the method for electroplating wastewater treatment present situation, directly under the jurisdiction of a municipal government and suburbs and counties under the jurisdiction of a large city's 226 tame Electroplate Factory point sampling investigation statisticses with regard to Shanghai, in the common method, account for 72.0% with ramps Precipitation method in the chemistry of chemical method, the air supporting method accounts for 8.1% (adding up to 80.1%), and ion exchange method accounts for 12.0%, electrolytic process accounts for 2.3%, and additive method accounts for 5.5%.
Report of survey shows: electroplating wastewater adopts chemical Treatment to account for the overwhelming majority, and the electroplating wastewater of qualified discharge after the chemical Treatment, even qualified discharge, wherein still have micro heavy to exist, be present in the water body with the heavy metal compound state, be transferred to organism easily by animalcule or plant absorbing, accumulation, and in the food chain mode, involve human body; And discharge water can not recycle, can not be multiplexing after the advanced treatment; Moreover it is big that chemical Treatment produces the sludge quantity that contains heavy metal, is difficult for handling, and causes secondary pollution.
Electrolytic process is handled electroplating wastewater, though the treatment process comparative maturity, stable and reliable operation, simple to operate, management and maintenance convenience, this method current consumption is big.As when handling chromium plating wastewater, current consumption is big, and sludge quantity is also many.During Treatment of Cyanide-containing Wastewater, its current consumption is bigger 10 times than alkaline chlorination process, and processing costs is high 1 times.During electrolytic process is handled in many cases, except that power consumption is big, also to produce and distribute toxic gas.
Need to regenerate or transition after the absorption of ion exchange method processing intermediate ion exchange resin is saturated with acid, alkali, need consume a large amount of acid, bases chemical raw material during regeneration, processing cost height, processing requirement complexity, resin is in use easily broken, and its application is affected.The accumulation problem that also has salt in the water in the ion exchange method after the plastic resin treatment, brackish water are done the rinse water reuse has disadvantageous effect to the quality of plating piece, contains purity and the concentration that Na+ will influence bath solution because of resin elution liquid when cooking the electroplate liquid reuse.
In a word, though the treatment process of existing main flow is widely used, problems still exist.
Summary of the invention
The present invention is intended to reach from the Electroplating Production waste water treatment angle incision of zero release, a kind of feasible program that adopts membrane separation technique is provided, it can be saved the Electroplating Production water consumption and alleviate the pollution of electroplating industry to water surrounding, in the hope of promoting and promote the Sustainable development of electroplating industry.
The present invention is based on the application of membrane separation technique, its theoretical foundation is that the reverse osmosis among the membrane separation technique can hold back the mineral ion and the organism overwhelming majority, only allows water molecules see through, and is about to water and other organism and mineral ion separately.Its theoretical foundation is that also the nanofiltration among the membrane separation technique has different holding back to monovalent ion in the mineral ion and divalent ion, is about to monovalence mineral ion and divalence mineral ion separately.
The membrane separating method of electroplating wastewater processing zero release of the present invention comprises on the technology liquid material processing, lifting, supercharging and transports routine, it is characterized in that its processing step also comprises:
1) pre-treatment of electroplating wastewater
Use the impurity of the thick anode sludge one class of strainer filtering earlier; The inferior organism of removing in the waste water that adsorbs with carbon fiber; Use the fine suspension in the microfiltration membrane filtering waste water of small-bore more again, and prevent that by the pH value of regulating rinse water the oxyhydroxide in the waste water from producing precipitation;
2), one-level nanofiltration membrane separation
Will be through pretreated waste water, holding back scope with relative molecular mass is that hundreds of nanofiltration membrane is carried out flash trapping stage, remove sodium ion, adopt flushing automatically regularly, making waste water concentrate 10 times is permitted, the rejection of heavy metal ion greater than 97%, is seen through liquid and is back to use after ion-exchange and makes rinse water usefulness in the production technique, and concentrated solution continues to enter the secondary membrane concentration to be separated;
3), secondary brackish water reverse osmosis membrane separation
Will be except that the waste water concentrated solution behind the sodium, filter with organic microfiltration membrane of 5 μ m earlier, be similarly the generation that prevents the precipitation of hydroxide thing, with carrying out secondary brackish water reverse osmosis membrane separation behind the acid for adjusting pH value again, adopt flushing automatically regularly, waste water concentrated solution reconcentration is permitted for 5 times, it is higher than 98% to the divalent ion rejection, see through liquid and get back to the waste water tank of one-level nanofiltration concentration systems, concentrated solution then continues to do three grades of concentration;
4), three grades of seawater reverse osmosis membranes separate
Same with organic microfiltration membrane of 5 μ m concentrated solution the filtration earlier, be similarly the generation that prevents the precipitation of hydroxide thing, separate with carrying out three grades of seawater reverse osmosis membranes behind the acid for adjusting pH value again, adopt flushing automatically regularly, make it to concentrate waste water more than 2 times or 2 times, rejection to mineral ion is higher than 99.5%, sees through liquid and gets back in the waste water tank of one-level nanofiltration membrane concentration systems, and concentrated solution is directly got back to plating tank and done reuse.
Concentrated solution also can obtain crystallized product behind vacuum distillation, as nickel sulfate hexahydrate crystal, can be used as byproduct and sell.
Positively effect of the present invention is:
1, because total system has adopted multistage membrane concentration method, reach more than 100 times electroplating wastewater is concentrated, concentrated solution is directly got back to plating tank, or get crystalline product through vacuum distillation and sell as byproduct, see through liquid and be back to use in the production technique, form the process for cleanly preparing of electroplating waste water resource, after pre-treatment as rinse water, technology has just thoroughly broken away from the pollution of electroplating wastewater to environment, realizes the zero release of electroplating wastewater.
2, process using nanofiltration of the present invention and reverse osmosis technology effectively make up, utilize nanofiltration to remove part monovalent salt in the electroplating wastewater, heavy metal ion is carried out pre-concentration, and the heavy metal feed liquid that contains behind the nanofiltration pre-concentration reclaims after reverse osmosis concentration again, and nanofiltration sees through liquid as the process water reuse.It has given full play to the speciality of nanofiltration and reverse osmosis technology.
3, be example with electronickelling waste water, after art breading of the present invention, quality of reused water can reach total dissolved solids＜10mg/L.Nickel-containing waste water can concentrate 100 times, and nickel ion finally can be concentrated to 30g/L, total reclamation rate 〉=95% of water, in the waste water rate of recovery of nickel ion can 〉=90%.
4, according to assessment measuring and calculating at present, containing nickel concentration in electronickelling waste water is 50～300mg/L, and treatment capacity is 50m
3The electronickelling waste water reclamation treatment system of/h, 2 years is recoverable system device material investment, has higher economic value.
Description of drawings
Fig. 1 is a process flow diagram.
Fig. 2 is the process unit synoptic diagram.
Embodiment
Be further described with embodiment with reference to the accompanying drawings below.
Figure 1 shows that the technical process of the embodiment of the invention, its base conditioning flow process is:
Electroplating wastewater → pre-treatment → supercharging → one-level nanofiltration membrane separation NF → supercharging → two-pass reverse osmosis membrane sepn BWRO → supercharging → three grades of reverse osmosis membrane separation SWRO
Earlier the suspended substances such as the micro-anode sludge that have in the electronickelling rinse water are carried out pre-treatment, cloth envelop collector, carbon fiber filter and organic microfiltration membrane are adopted in pre-treatment.Earlier carry out pre-concentration through pretreated electroplating wastewater through the nanofiltration membrane treatment system, the one-level nanofiltration see through liquid reuse after ion-exchange, the nanofiltration concentrated solution further concentrates through the two-pass reverse osmosis system after entering the dense water tank of one-level again.The liquid that sees through of two-pass reverse osmosis returns waste water tank, concentrated solution after two-pass reverse osmosis further concentrates enters the dense water tank of secondary, further concentrate again with three grades of reverse osmosis concentrated compression systems, the seawater film is adopted in three grades of reverse osmosiss, working pressure is higher, three grades of reverse osmosiss see through the waste water tank that liquid returns a level system, the concentrated solution of three grades of reverse osmosiss enters three grades of dense water tanks, make metal-salt (as nickel salt) again after the underpressure distillation and reclaim, thus the cleaning procedure that formation electroplate rinsing wastewater treating water reuse and resource reclaim.Diagram hydrochloric acid HCl adds do adjusting potential of hydrogen usefulness in the treatment solution, avoids oxyhydroxide to produce precipitation, influences membrane separating effect.
Figure 2 shows that process unit synoptic diagram of the present invention.Be illustrated below in conjunction with embodiment:
Embodiment 1: the electronickelling wastewater treatment
1, pre-treatment
At first get waste water stoste, be promoted to waste water tank 1, be pressurized to 0.4Mpa through topping-up pump 2 again, adopt 10 μ m cloth envelop collectors 3, under pressure, filter, with big suspended impurity elimination such as the anode sludge in the electronickelling waste water, foam fragment from the electronickelling wastewater disposal basin; Then adopt the fiber filter of activated carbon 4, utilize the petroleum-type organism in its carbon fiber absorption waste water, alleviate the pollution of organism membrane element; Existing again. adopting the higher aperture of precision in the precise microfiltration device 5 is that the organic microfiltration membrane of 5 μ m is further filtered waste water, removes fine suspension in the waste water, thereby plays the effect of protective membrane element, prolongation membrane element life cycle.In order to prevent to produce Ni (OH) in the concentration process
2Precipitation is regulated rinse water pH value.
2, one-level nanofiltration membrane separation
Waste water after treatment enters one-level nanofiltration membrane concentrating unit 7 by topping-up pump 6 superchargings under 0.4Mpa pressure separates, the pore diameter range of nanofiltration membrane is at nano level, it is hundreds of (dalton) that its relative molecular mass is held back scope, nanofiltration membrane surface bear, ion to different electric charges and different valence state has different Donann current potentials, and the aperture of nanofiltration membrane and surface characteristic have determined its particular performances.Nanofiltration membrane has different rejection to monovalent ion and divalent ion.Because of sodium ion in the bath solution is bigger to the quality influence of plating piece, sodium ion can make plating piece become substandard products above certain concentration in the tank liquor, thereby need select for use the nanofiltration membrane of different rejection to concentrate waste water to the different valence state ion.The nanofiltration membrane that native system adopts is lower to the rejection of sodium chloride nacl, has only 50%-70%, and stays rate higher to bivalent ions year, is generally more than 97%.Most sodium-chlor sees through the nanofiltration membrane element, and membrane concentration liquid is removed sodium ion, and it is multiplexing directly to return coating bath after back segment membrane concentration system continues to concentrate.The operating pressure of nanofiltration membrane is low, and flux is big, adopts nanofiltration system that working cost is greatly reduced.In order to alleviate the pollution of face, prolong the work-ing life of film, a level system adopts regularly flushing automatically.Through after the nanofiltration system, waste water is concentrated 10 times, and the rejection of heavy metal ion greater than 97%, is seen through liquid and returns production technique as rinse water use after ion-exchange, and concentrated solution enters the dense water tank 8 of one-level, then transfers the secondary membrane concentration system of back level to.
3, two-pass reverse osmosis membrane sepn
Before entering separating technology film device at the corresponding levels, carry out preposition filtration with organic microfiltration membrane of 5 μ m earlier, prevent that mechanical impurity causes film to stop up in pipeline, the water tank; Be pressurized to 1.0Mpa through topping-up pump 9 then, the brackish water reverse-osmosis membrane element with anti-elevated pressures in the reverse osmosis concentrated compression apparatus 10 of secondary brackish water carries out lock out operation., adopt hydrochloric acid that rinse water pH value is regulated therebetween, prevent sedimentary generations such as nickel hydroxide, adopt regularly flushing automatically, prolong the work-ing life of film to alleviate the pollution of face.The secondary concentration systems concentrates 5 times to waste water, and the liquid that sees through of secondary membrane concentration system is got back to one-level nanofiltration system continuation processing, and concentrated solution then enters three grades of concentration systems that the dense water tank 11 of secondary transfers the back level again to.Enter waste water at the corresponding levels behind 10 times of one-level membrane concentration, the ionic concn in the waste water is higher, causes osmotic pressure to improve, and selected brackish water reverse-osmosis membrane element at the corresponding levels is higher to the ionic rejection, its to the divalent ion rejection more than 98%.
4, three grades of reverse osmosis membrane separation
Before entering three grades of film devices, the same filtration with organic microfiltration membrane of 5 μ m earlier is pressurized to 2.5Mpa through topping-up pump 12 again, carries out lock out operation with the seawater reverse osmosis membrane element in three grades of saturating concentrating uniies 13 of seawater reverse osmosis., adopt hydrochloric acid that rinse water pH value is regulated therebetween, prevent the precipitation of nickel hydroxide, regularly flushing automatically.Three grades of concentration systems concentrate more than 2 times waste water, and concentrated solution enters three grades of dense water tanks 14, directly gets back to plating tank, or behind vacuum distillation nickel sulfate hexahydrate crystal is sold as byproduct, see through liquid and get back to one-level membrane concentration system and continue to handle.At the corresponding levels dense because of the waste water intermediate ion, waste water infiltration is pressed very high, thereby adopts the seawater reverse osmosis membrane element to concentrate waste water, and the seawater reverse osmosis membrane element stays rate very high to carrying of mineral ion, generally more than 99.5%.
Total system is operated at normal temperatures, concentrate more than 100 times to electronickelling waste water, concentrated solution is directly got back to plating tank, or after getting nickel sulfate hexahydrate crystal, sells vacuum distillation as byproduct, seeing through liquid is back to use in the production technique as rinse water, form the cleaning production technique of electronickelling waste water reclaiming, thoroughly stop the pollution of electroplating wastewater, realize the zero release of electroplating wastewater environment.Ion exchange unit 15 inserts the liquid that sees through of one-level nanofiltration, goes plating line to do the rinse water reuse after the processing.
Total system adopts programmable logic controller (PLC), realizes electric simultaneously and instrument control and monitoring automatically, adopts industrial computer, and the operation process state and the operating parameter of equipment are monitored.In addition, system regularly adopts and sees through the liquid flushing, with the pollutent of flushing face, protective membrane; And set up online chemical cleaning system, long-term, stable, the efficient operation of the system that can guarantee.
The method of the embodiment of the invention has certain for property.As directly being suitable for for electro-coppering, zinc wastewater treatment.
Embodiment 2:50m
3/ h electronickelling wastewater treatment and recycling thereof
Design system flooding quantity 50m
3/ h, the aperture of selecting the pre-treatment cloth envelop collector is 10um, behind the cloth bag filtration, the macrobead suspended substance in the waste water will be removed the waste water of electronickelling, again through activated carbon filtration earlier.Adopt the activated carbon fiber filter core in the activated charcoal filter, last waste water is through the accurate filter of 5um.Earlier carry out pre-concentration through pretreated electronickelling waste water through the nanofiltration membrane treatment system.
First step nanofiltration NF concentration systems adopts rolling NF membrane module, flooding quantity 50m
3/ h divides two groups of A, B, every group of independent operating.Waste water is concentrated 10 times after first step nanofiltration, membrane concentration liquid 5m
3/ h is as the water inlet of two-pass reverse osmosis film system.Nanofiltration membrane sees through liquid and get back to rinse water use point after ion exchange system.The nickel ion content of former water between 50mg/L～300mg/L, NF to the rejection of nickel ion more than 97%.
Second stage brackish water reverse osmosis BWRO concentration systems adopts coiled reverse osmosis membrane assembly, flooding quantity 5m
3/ h.Film sees through liquid 4m
3/ h turns back to raw water box, and waste water is concentrated 5 times again after the reverse osmosis of the second stage, membrane concentration liquid 1m
3/ h is as the water inlet of three grades of seawater reverse osmosis membrane systems.BWRO to the rejection of nickel ion more than 99%.
The saturating SWRO concentration systems of third stage seawater reverse osmosis adopts rolling seawater reverse osmosis membrane assembly, flooding quantity 1m
3/ h.Film sees through liquid 0.5m
3/ h turns back to raw water box, and waste water is concentrated 2 times again after third stage seawater reverse osmosis is saturating.SWRO to the rejection of nickel ion more than 99%.
After three grades of film systems, 50m
3The final membrane concentration liquid of the electronickelling waste water of/h has only 0.5m
3/ h.Membrane concentration liquid is sent to the vacuum distillation system again and makes the sale of single nickel salt crude salt.
This routine treatment capacity is 50m
3/ h, it is 50～300mg/L that the electronickelling waste water of use contains nickel concentration.
Claims (1)
1, the membrane separating method of electroplating wastewater processing zero release of the present invention comprises on the technology liquid material processing, lifting, supercharging and transports routine, it is characterized in that its processing step also comprises:
1), the pre-treatment of electroplating wastewater
Use the impurity of the thick anode sludge one class of strainer filtering earlier; The inferior organism of removing in the waste water that adsorbs with carbon fiber; Use the fine suspension in the microfiltration membrane filtering waste water of small-bore more again, and prevent that by the pH value of regulating rinse water the oxyhydroxide in the waste water from producing precipitation;
2), one-level nanofiltration membrane separation
Will be through pretreated waste water, holding back scope with relative molecular mass is that hundreds of nanofiltration membrane is carried out flash trapping stage, remove sodium ion, adopt flushing automatically regularly, making waste water concentrate 10 times is permitted, the rejection of heavy metal ion greater than 97%, is seen through liquid and is back to use after ion-exchange and makes rinse water usefulness in the production technique, and concentrated solution continues to enter the secondary membrane concentration to be separated;
3), secondary brackish water reverse osmosis membrane separation
Will be except that the waste water concentrated solution behind the sodium, filter with organic microfiltration membrane of 5 μ m earlier, be similarly the generation that prevents the precipitation of hydroxide thing, with carrying out secondary brackish water reverse osmosis membrane separation behind the acid for adjusting pH value again, adopt flushing automatically regularly, waste water concentrated solution reconcentration is permitted for 5 times, it is higher than 98% to the divalent ion rejection, see through liquid and get back to the waste water tank of one-level nanofiltration concentration systems, concentrated solution then continues to do three grades of concentration;
4), three grades of seawater reverse osmosis membranes separate
Same with organic microfiltration membrane of 5 μ m concentrated solution the filtration earlier, be similarly the generation that prevents the precipitation of hydroxide thing, separate with carrying out three grades of seawater reverse osmosis membranes behind the acid for adjusting pH value again, adopt flushing automatically regularly, make it to concentrate waste water more than 2 times or 2 times, rejection to mineral ion is higher than 99.5%, sees through liquid and gets back in the waste water tank of one-level nanofiltration membrane concentration systems, and concentrated solution is directly got back to plating tank and done reuse.
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