CN101456637A - Treatment process and method of electroplating wastewater - Google Patents
Treatment process and method of electroplating wastewater Download PDFInfo
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Abstract
The invention discloses a process and a method for comprehensively treating electroplating waste water. Based on the microelectrolysis-fenton reagent treatment method, the chemical deposition method and the comprehensive application of the membrane technique, the method comprises: firstly, heavy metal ions in the waste water are replaced by replacement action of iron carbon, metal resources are recovered, and simultaneously organic matters are oxidized to remove COD and break complex compounds; secondly, by the combination of the hydroxide deposition method and the sulfide deposition method, the excessive metal ions are deposited, so that the waste water is made to meet the discharge standards; and thirdly, on the basis, by the joint action of ultrafiltration-reverse osmosis membranes, the discharged water is made to meet the Hygienic Standard For Domestic Drinking Water, and according to electroplating process requirements, the total hardness and electrical conductivity of the discharged water are better than those of tap water, and simultaneously, by the microelectrolysis replacement action of the iron carbon, the majority of heavy metals contained in the waste water are recovered, and the recovered heavy metals are higher in purity. The process and the method have the advantages of simple flow, low water treatment and recycling cost, short investment recovery period and the realization of the recycling of the water resources and the heavy metal resources.
Description
Technical field
The invention belongs to the treatment technology of electroplating wastewater, particularly relate to a kind of that multiple electroplating wastewater processing is up to standard and reclaim the technology of heavy metal resources simultaneously.
Background technology
Will carry out nickel plating, copper facing, chromium plating, multiple production technique such as zinc-plated as everyone knows in electroplating industry, wastewater produced kind is also varied, as the plating piece Cleaning Wastewater; Electroplating effluent; Wash away mill floor, scrub floor and ventilation installation water of condensation and because coating bath seepage or the improper draining that causes of operational administrative etc.Wherein, the plating piece rinse water almost accounts for more than 80% of tool wastewater discharge.And containing a large amount of heavy metal ion and the contour pollution substance of prussiate in the electroplating wastewater, toxicity is bigger.
Because the composition of electroplating wastewater is complicated, its treatment technology also is varied, chemically is main at present.Cyanide wastewater makes heavy metal precipitation and adds coagulating agent, polymer coagulant aids etc. with removals such as metal ion, suspended substance and COD by adjusting the pH value or adding sodium sulphite with soda acid copper nickel waste water through chromium reduction back through broken cyanide, chromate waste water, makes effluent quality reach emission standard.Handling the mud that produces disposes through outward transport after the thickening.The advantage of this method is that less investment, processing costs are low, treatment capacity is bigger.But raising along with the Environmental Protection in China standard.The qualified discharge standard is strict day by day, and owing to the continuous development of electroplating industry production technology, the application of various new medicaments emerges in an endless stream simultaneously, and this method can't reach the predetermined process standard, more can't reach production reuse requirements in water quality.In addition different heavy metals mixes and has caused serious secondary pollution in the mud that is produced by this kind method.
How to address the above problem, and realizing that electroplating wastewater processing can realize that again the extraction recovery of heavy metal is exactly a problem to be solved by this invention in up to standard.
Summary of the invention
The purpose of this invention is to provide a kind of electroplating waste processing process, electroplating wastewater is carried out the up to standard and realization recycle of comprehensive treating process, the while is the technology of recyclable heavy metal resources again.
The present invention is based on the integrated use of little electrolysis-Fenton reagent facture, chemical precipitation method and membrane technique.Its principle is at first by the heavy metal ion in the metathesis displacement water outlet of iron carbon, recovery metals resources.Simultaneous oxidation organic matter removal COD also abolishes complex compound.Secondly by the combination utilization of hydroxide precipitation method and sulphide precipitation,, make it to reach emission standard with unnecessary precipitation by metallic ion.Combined action by ultrafiltration-reverse osmosis membrane makes water outlet reach " drinking water sanitary standard " (GB5749-2006) on this basis, and according to the electroplating technology requirement, total hardness and specific conductivity are better than tap water quality.
To electroplating wastewater treatment reclaiming and precious metal its recovery method as resource, its processing step comprises:
(1) adopting the separate system network of drains, is three kinds of cyanide wastewater, chromate waste water, soda acid copper nickel comprehensive wastewater according to the different moisture in the future of electroplating technology, and various waste water all enter in the different equalizing tanks.
(2) cyanide wastewater in the step (1) is adopted the oxidation of secondary broken cyanide, chromate waste water adopts the reductive agent reduction and regulates pH value to 7.5～8 coagulating sedimentation, and water outlet all enters same acid-base integration wastewater equalization pond, is referred to as comprehensive wastewater.
(3) comprehensive wastewater in the step (2) is promoted enter little electrolysis-Fenton reagent reaction tank, utilize the metathesis of iron to make it to be cemented in the heavy metal ion displacement in mud and the carbon granules and utilize the electrode effect of iron carbon microelectrode and the oxygenizement oxidation contact break of hydroxyl radical free radical, remove COD.Regulate the pH value afterwards and enter air flotation pool or one-level settling tank, water outlet enters second-level settling pond through the pH value adjusting second time and after adding the sodium sulphite coagulation, again qualified discharge after sand filter.
(4) sewage that reaches emission standard in the step (3) is entered the ultra-filtration membrane device through security personnel's strainer, water outlet through entering reverse osmosis unit after security personnel's filter, realizes reuse again.The dense waste liquid that film is handled enters in the described acid-base integration wastewater equalization pond of step (2).
Chromate waste water is through fully reducing and regulate pH value coagulating sedimentation in the step (2), and the chromium hydroxide precipitation of generation enters independent sludge thickener with the form of mud, reclaims metal through high-temperature calcination.
Micro cell iron carbon volume ratio is got 1:1 in the step (3), water intake mode, perforated pipe water distribution are so that water distribution is even under adopting, cooperation perforated pipe aerating regulation in service, gas-water ratio is that 30:1 aeration time every day is got 2-3h, prevent Fe-C plate knot and Chi Zhongyin is consumed excessively and the iron carbon space that produces is closely knit, guarantee to stablize its duration of contact with sewage by the regular iron carbon of adding.Mud and surplus carbon in the periodic cleaning in service pond reclaim copper nickel metal after calcining.
Fenton reagent comprises hydrogen peroxide and ferrous sulfate in the step (3), wherein concentration of hydrogen peroxide gets 30%, hydrogen peroxide and ferrous sulfate mol ratio are got 10:1, guarantee to have the catalyzer ferrous ion that q.s produces hydroxyl radical free radical on the one hand, simultaneously also avoided because of ferric throwing out causes sludge quantity big blocking pipeline.
Air flotation pool (one-level settling tank) control pH guarantees that at 7.5-8 remaining most of heavy metal ion forms precipitation in the step (3).
Second-level settling pond control pH is about 10.5 in the step (3), and the sodium sulphite dosage is decided on copper ion concentration.Guarantee that all heavy metal ion form precipitation, and enter sludge thickener with the form of mud.
Sand filter adopts and goes up water inlet conventional monolayers rapid filter, air water back flushing simultaneously in the step (3).Remove remaining suspended substance, simple to operate and effect is better.
The film system adopts programmable logic controller (PLC) to finish electric simultaneously and automatic control and monitoring instrument in the step (4), and the reusing sewage rate reaches more than 75%.
Implement concrete mode
The present invention is described further below in conjunction with case history and with reference to the treating processes of accompanying drawing.Shenzhen's Treatment of Industrial Park of Plating has comprised various plating platings, its sewage day quantity discharged be 3000 tons, influent quality index such as table 1:
The sewage quality unit of three kinds of sewage of table 1: mg/L
1. contain cyanogen and chromate waste water
Cyanide wastewater adopts secondary broken cyanide oxide treatment, and water outlet enters the acid-base integration wastewater equalization pond; Chromate waste water adopts the reductive agent oxidation, and after regulating pH value, coagulating sedimentation, supernatant liquor enters the acid-base integration wastewater equalization pond and handles with soda acid copper nickel waste water, and mud is through calcining recovery chromium sesquioxide wherein.
2. soda acid copper nickel waste water and the above-mentioned treat effluent that contains the cyanogen chromate waste water are handled through following treatment process:
(1) little electrolysis-Fenton reagent treatment process
Adopt the use in parallel of three micro cells, the perforated pipe water distribution aeration.Left and right sides periodic cleaning pond body every other month.Iron carbon admission space is than for 1:1 surplus carbon calcining being obtained a large amount of copper nickel metals.Concentration of hydrogen peroxide gets 30% in the Fenton reagent, and dosage is 1.2L/m
3Sewage, hydrogen peroxide and ferrous sulfate mol ratio are got 10:1.
(2) coagulation air-float (coagulation-settlement process)
Regulating pH is 7.6, and most of extraneous copper ion and a part of nickel ion are removed, and coagulating agent adopts poly-aluminium, and flocculation agent adopts polyacrylamide.Mud enters sludge thickener.
(3) secondary sedimentation
Regulating pH is 10.5, with remaining nickel ion precipitation.Add a certain amount of sodium sulphite simultaneously, the precipitated copper ion.Coagulating agent adopts poly-aluminium, and flocculation agent adopts polyacrylamide.Mud enters sludge thickener.
(4) sand filtration technology
Also may contain a spot of suspended substance and colloid in the waste water after air supporting and coagulating sedimentation processing, can filter by sand filter and remove, use water security and enter the film system.Sand filter adopts goes up water inlet individual layer tradition sand filter, air water back flushing simultaneously.Water distribution is the strainer head small resistance water wiring system.The sand filter water outlet can reach the requirement of the first discharge standard of second period of the provincial standard DB4426-2001 of Guangdong Province after the pH readjustment
(5) membrane treatment process
Step (4) is described to be satisfied qualified discharge requirement water outlet and enters intermediate pool, after the force (forcing) pump supercharging, enter security personnel's strainer, after handling through the ultra-filtration membrane device again, enter reverse osmosis unit through the high-pressure pump pressurization, the reverse osmosis water outlet enters in the clean water basin, and use in power supply plating workshop.The dense waste liquid of ultrafiltration and reverse osmosis enters in the comprehensive wastewater equalizing tank.
Total system adopts upper computer that the operation of system is monitored, and programmable logic controller (PLC) is finished electric and automatic control and monitoring instrument simultaneously, the equal on-line monitoring pH of each grade concentration systems, total dissolved solid, temperature and flow.And liquid level, pressure, temperature, electrical ball valve are chain with carrying out between the pump.Water tank is provided with low liquid level control, and the control topping-up pump was out of service automatically when high water tank was too low.Low-tension switch is set before the high-pressure pump, and when feedwater flow and pressure appearance abnormality, high-pressure pump will stop automatically, with protection high-pressure pump and membrane element.At the dense water side of the film configuration electrical ball valve of control automatically, before the operation of film system, after shutting down, carry out low-pressure washing, removing the pollutent on film surface, the dense water in the displacement penstock and drive air in the membrane element away.The film system regularly sees through liquid flushing 2～5min with film, and concentration polarization takes place and flushing face cumulative pollutent to reduce.
Table 2 reuse water effluent quality detected result unit: mg/L
Beneficial effect of the present invention and characteristics are, utilize the heavy metal ion in the metathesis displacement water outlet of iron carbon, reclaim Metals resources uses by the combination of hydroxide precipitation method and sulphide precipitation simultaneously, has realized integrative electroplating waste Qualified discharge, cooperate the synergy of ultrafiltration-reverse osmosis membrane to make water outlet reach " drinking water sanitary standard " And according to the electroplating technology requirement, total hardness and electrical conductivity are better than tap water quality (GB5749-2006). That reclaims is useless Its heavy metal purity is higher in the water, has good recovery value. Technological process of the present invention is simple, water treatment and waste water return The recycling of water resource and heavy metal resources is lacked and can be realized to, the investment payback time low with expense. But extensive use is with comprehensive The processing reuse of electroplating wastewater.
Claims (10)
1. the treatment process of integrative electroplating waste and method, adopt the separate system network of drains, in the future moisture is three kinds of cyanide wastewater, chromate waste water, soda acid copper nickel comprehensive wastewater, various waste water enter in the different equalizing tanks, cyanide wastewater adopts secondary broken cyanide oxide treatment, and water outlet enters the acid-base integration wastewater equalization pond; Chromate waste water adopts the reductive agent oxidation, through regulating the pH value, coagulating sedimentation, its supernatant liquor also enters the acid-base integration wastewater equalization pond, mud behind the coagulating sedimentation is through calcining recovery chromium sesquioxide wherein, it is characterized in that: the cyanogen that contains that enters the acid-base integration wastewater equalization pond, chromate waste water and the composite wastewater that contains soda acid copper nickel are through little electrolysis and Fenton reagent treatment process, coagulation air-float or coagulating sedimentation are after secondary sedimentation basins, the comprehensive treating process of sand filtration technology and membrane treatment process realizes reusing sewage
2. the treatment process of integrative electroplating waste according to claim 1 and method, it is characterized in that described little electrolysis process is to adopt iron plane flower and carbon granules to mix to fill micro cell, the iron plane flower is selected industrial scrap iron for use, and carbon granules is selected gac for use, and the admission space of iron plane flower and carbon granules is than being 1:1;
3. the treatment process of integrative electroplating waste according to claim 1 and 2 and method is characterized in that its composite wastewater water intake mode of described little electrolysis process adopts the perforated pipe water distribution and cooperates perforated pipe aerating regulation, and gas-water ratio is got 30:1;
4. according to the treatment process and the method for the described integrative electroplating waste of one of claim 1 to 3, it is characterized in that the surplus carbon of gained was calcined after described little electrolysis process was to the micro cell cleaning, reclaim copper nickel metal,
5. the treatment process of integrative electroplating waste according to claim 1 and method is characterized in that the concentration of hydrogen peroxide in the described Fenton reagent gets 30%, and hydrogen peroxide and ferrous sulfate mol ratio were got 10: 1,
6. the treatment process of integrative electroplating waste according to claim 1 and method is characterized in that described coagulation air-float or coagulating sedimentation treatment process, and the coagulating agent of employing is poly-aluminium, and the flocculation agent of employing is a polyacrylamide, and control sewage pH is 7.5～8,
7. according to the treatment process and the method for claim 1 or 6 described integrative electroplating wastes, it is characterized in that described secondary sedimentation basins need add: described poly-aluminium coagulating agent, described polyacrylamide flocculant, sodium sulphite co-precipitation, the pH value of control settling tank water inlet is 10～11
8. the treatment process of integrative electroplating waste according to claim 1 and method is characterized in that described sand filter adopts upward water inlet conventional monolayers rapid filter, air water back flushing simultaneously,
9. the treatment process of integrative electroplating waste according to claim 1 and method is characterized in that the film in the described membrane treatment process adopts ultra-filtration membrane and reverse osmosis membrane series connection,
10. the treatment process of integrative electroplating waste according to claim 9 and method, it is characterized in that described membrane treatment process process all adopts upper computer that the operation of system is monitored, by programmable logic controller processing parameter is controlled automatically and monitored, to the equal on-line monitoring pH of each grade treating processes, total dissolved solid, temperature and flow.
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