CN101786734A - Process for treating acid waste water containing copper, nickel and the like by membrane method - Google Patents
Process for treating acid waste water containing copper, nickel and the like by membrane method Download PDFInfo
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Abstract
The invention provides a process for treating acid waste water containing copper, nickel and the like by a membrane method, discloses a process for treating and recycling acid waste water containing noble metal ions for non-ferrous metal mine, smelting, ore dressing and the like through a sedimentation tank, a fiber filter, ultra-micro filtration and reverse osmosis/nano filtration, and belongs to the technical field of waste water treatment and resource recycle. The process is characterized by treating the waste water and furthest reclaiming valuable metal ions and water resources in the waste water at the same time so as to achieve the purposes of treating and recycling the waste water and basically realizing zero emission of the waste water. Moreover, the water produced by the reverse osmosis/nano filtration is used as back washing water for the filter and the ultra-micro filtration so as to improve the cleaning effect of the filter and the ultra-micro filtration and the reclaiming rate of valuable metals; the pollution and plugging of iron and silicon in the water to the membrane are effectively overcome by adopting ultra-micro filtration treatment, adding a reducing agent and using the produced water flushing function of the device; and the scaling problem of sulfate such as calcium, strontium, barium and the like in the thick water is effectively solved by adopting special design of a desalting system and special scale inhibiting technology, and the long-term stable operation of the system is ensured.
Description
Technical field:
A kind of technology of handling acid waste waters such as nonferrous metal mine, smelting, ore dressing, plating by combination procesies such as ultra filtration, reverse osmosis/nanofiltrations, belong to wastewater treatment and resource reusing technical field, its characteristics are when handling waste water, reclaimed valuable metal ions and the water resources in the waste water to greatest extent, accomplish the wastewater treatment resource utilization, realized the purpose of wastewater zero discharge basically.
Background technology:
Waste water such as acid cupric, nickel are that scope is wider in the waste water, the trade effluent that hazard rating is bigger, extensively be present in nonferrous metal mine, Metal smelting, ore dressing and electroplating industry, as the pit water of copper mine, from the raffinate of hydrometallurgy, mine ore dressing waste water etc.Traditional treatment process mainly contains lime neutralisation, sulphide precipitation, extraction process, biological process etc.The domestic at present improvement of acid waste water the practice still is confined to lime neutralisation and sulphide precipitation.Neutralisation is a method the most general in the same for treating acidic mine wastewater, and according to statistics, the engineering utility ratio surpasses 90%.But sediments such as the calcium sulfate that generates after handling, ferric oxide, heavy metal oxide are more and the dehydration difficulty, take up an area of big, storing up processing easily causes the heavy metal oxide secondary in the sediment to dissolve, cause the secondary pollution in water system basin, and operational condition is abominable, the most important thing is to reclaim the valuable metal in the waste water, cause waste.It is big that sulfurization-precipitation method has pH value subject range, but valuable metals such as the copper in the efficient recovery water, nickel, but the precipitation agent source is limited, the price comparison costliness, and the hydrogen sulfide foul smelling of generation has harm to human body, and improper use causes atmospheric pollution easily.In addition, owing in copper-containing acid waste water, often contain a large amount of ferric ions,, contain a large amount of elemental sulfurs in the water outlet, for the subsequent disposal of water is brought new pollutent because ferric oxygenizement can cause the sodium sulphite consumption excessive; On the other hand, generate the bad filtration of slag if processing condition control is bad, liquid-solid separation difficulty, strict to reaction process control, level of automation is low.Biological process (srb assay) is the fresh approach of at present domestic and international same for treating acidic mine wastewater, and this method is actual to be biological sulfuration method.SRB application case according to State of Arizona, US Bisbee#7 reactor project, the investment and the working cost of srb assay processing acid wastewater in mine are all higher, the sulfide precipitation added value that obtains is lower, and further processing of waste water needs thereby comprehensive treating process cost after the processing are also higher.
Embrane method is one of effective ways of acid waste water technology such as Treatment of Copper, nickel.The major advantage of embrane method technology is as follows:
1. do not have phase transformation in the reaction, keep original feed liquid physical properties, energy consumption is extremely low;
2. do not have chemical transformation, typical physical separating process need not to add chemical reagent and additive, and feed liquid character can not change;
3. selectivity is good, can carry out separating substances in the molecular level scope, and common filter material is incomparable;
4. adaptability is strong, and treatment scale is changeable, can be continuously or intermittent operation, and technology is simple, and is easy to operate, is easy to automatization control;
5. need not to change feed temperature, can reclaim the heat and the energy;
Since the nineties, embrane method Treatment of Copper waste water technology has the case of successful Application abroad.Though the domestic existing at present report of using, treatment process as the disclosed a kind of embrane method treatment of acidic wastewater of number of patent application-200610086878.7, its essence is a kind of molybdenum ore beneficiation wastewater, because it can't effectively overcome waste water after concentrating, (it is in the neutral range that the present polyacrylic acid or the Scale inhibitors of organophosphorus only can be operated in PH to the scale problems of metal difficulty soluble salts such as calcium sulfate, Strontium Sulphate, barium sulfate, scale-inhibiting properties forfeiture under acidic conditions) and the dirty stifled problem of the iron of film, its validity in industrial application is suspectable.And for example number of patent application 200610096133.9 is disclosed is a kind of technology that adopts nanofiltration to handle electroplating wastewater, because it is simple relatively to electroplate the acid waste water composition, copper removal in the waste water, outside the metal ion of nickel, other metal ion is gone up substantially and is trace, no calcium sulfate, strontium, the scale problems of barium, also problem is blocked up in the dirt of iron-free, therefore, this invention does not have comparability with the membrane technique of handling nonferrous metal mine and smelting wastewater, in addition, owing to adopt nanofiltration membrane to use film as handling, it produces and contains a large amount of acid and other univalent ion in the water, produce water and be not suitable for directly as the service water reuse, the secondary neutralization also will consume a large amount of alkali or lime.
Summary of the invention:
The objective of the invention is to be rich in the characteristics of copper, nickel, iron, zinc, lead, calcium, strontium, barium, arsenic according to mine, smelting cupric, nickel waste water, providing a kind of brand-new reverse osmosis/nanofiltration membrane treatment technology to remove to handle acid waste water such as cupric, nickel and reclaim the smithcraft height with hydrometallurgical processes, metal replacement or precipitation combines, in wastewater treatment, valuable metal copper and water resources in the waste water are reclaimed, realize the resource utilization of wastewater treatment; Simultaneously, adopt extraordinary design and scale inhibition, cleaning, guarantee the not stifled and fouling of reverse osmosis/nanofiltration membrane, guarantee long-term, the stable operation of film system by dirt.
System of the present invention mainly is made up of settling tank (or thickener), strainer, super (little) filter unit, reverse osmosis/nano-filtration unit and attached support equipment.The product water of system (the product water of reverse osmosis or nanofiltration) is owing to the ion in the water and other impurity are removed substantially, be very pure, little apparent tart water, the alkaline agent neutralization that only need add trace promptly can be used as excellent service water and uses, in addition, because hardness ionses such as calcium, magnesium are substantially by Ex-all in the product water, in and the time only otherwise introduce extra hardness components, also can be used as the feedwater of low pressure or hot water boiler; Dense water is owing to significantly concentrated and enrichment, copper, nickel, zinc plasma composition are usually up to 0.8-4g/l in the water, it is the qualified feed liquid of valuable metals such as a kind of extraction copper that is fit to extraction-electrodeposition process fully, nickel, zinc, dense water (being raffinate) after extraction-electrodeposition process reclaims valuable metal, can directly turn back to the stockyard of ores such as copper, zinc, enter the cycle stock liquid system in stockyard, also can discharging after neutralizations such as lime are up to standard.Because dense water is by enrichment, the acidity in the water, iron plasma have been the several times of former water, again when neutralizing treatment, because the co-precipitation effect, in will greatly improving and efficient, with the former water ratio of direct neutralization, will save 20%-40% lime dosage.As not adopting extraction-electrodeposition process to reclaim valuable metal in the dense water, and precipitation, iron replacing process such as employing sodium sulphite reclaim the valuable metal in the dense water, because dense water has only about the 1/3-1/10 of former volume of water, to significantly reduce unitary scale of sulfidizing and cost, the sulfurized utilization also will improve about 5%-20%, and the rate of recovery of valuable metals such as copper also will improve about 10%.
System flow of the present invention is seen figure one, and native system is made up of three processing units altogether, i.e. pre-filtration system, the smart filtration-super (little) filtering system and desalination and concentration system.Pre-filtration system is made up of settling tank and strainer, and the effect of pre-filtration system is the most suspended substances of removing in the water, reduces the processing load of super (little) filtering system, guarantees the steady running of ultra filtration system.Because waste water major parts such as mine and smelting cupric, nickel contain a large amount of suspended substances, particularly the pit waste water and the beneficiation wastewater of nonferrous metal mine, suspension content when rainy season in the waste water is up to hundreds of mg/litre, this waste water is as without preliminary precipitation and filtration treatment, directly carrying out ultra filtration filters, to cause the serious dirt of supermicro filtration membrane stifled, and can't works better.Certainly, if the suspension content in the waste water is lower, this unit can not established, and promptly former water can directly enter the ultra filtration system and carry out the essence filtration.Usually, through the precipitation process of several hours, raw water turbidity will be lower than 50ntu to former water in settling tank, because waste water is under low PH situation, contain a large amount of CIs and silicon in the water, traditional organic and inorganic coagulant aids all can not improve the settling velocity of suspended substance in the water.Former water is after precipitation process, and the suspension content in the water declines to a great extent, handles after filtration again, can significantly reduce and filter load, the cycle of operation of improving strainer; Because the effect of strainer in system is to use as coarse filter, actual delivery turbidity can determine that prerequisite is the steady running that its water outlet should be enough to guarantee the ultra filtration system according to the character of the supermicro filtration membrane of selecting for use.In addition, this strainer also has the effect of security personnel's strainer, can guarantee that water outlet does not contain particulate matter, and impurity can not damage supermicro filtration membrane in the water outlet.
The effect of ultra filtration in system is as system's fine filter, basically remove suspended substance nearly all in the water, colloid, bacterium, wet goods machinery and organic impurity, for follow-up reverse osmosis/nanofiltration system provides qualified water inlet, guarantee reverse osmosis/nanofiltration system can be for a long time, operation stably, avoid stifled from the dirt of above-mentioned impurity.Because the mechanical impurity in the acid waste waters such as mine is mainly the colloid of iron and silicon, and these colloids can cause serious dirt stifled to reverse osmosis/nanofiltration membrane, and therefore, the ultra filtration system must have good removal effect to these colloids.
The effect of reverse osmosis/nanofiltration system is desalination and concentrates that i.e. feedwater enters and is divided into two-way-product water and dense water in reverse osmosis/nanofiltration system, and the salinity in producing water is deviate from basically, and the salinity in the dense water is concentrated.In the treating processes of acid waste waters such as mine and smelting, produce water and dense water and be valuable resource, dense water is owing to be rich in copper, nickel plasma liquid, to be admitted to extraction-electrodeposition system as the feed liquid of extraction-electrodeposition, the spray liquid that will the dense water (raffinate) behind extracting copper, nickel can be used as the ore stockyard turns back to the stockyard, also can be directly as trade effluent qualified discharge after neutralizing; Produce water and can directly get back to production system as service water, also can be as the service water reuse after neutralizing.
Pretreatment system is made up of settling tank, strainer, filter backwash system, strainer chemical cleaning system etc.Settling tank can be settling tanks such as general spoke stream, advection, machinery acceleration, ramp type, also have all kinds of settling ponds of coagulation-precipitation function etc., the natural puddle with precipitating action is adopted in modular design of the present invention, owing to be seen everywhere in nonferrous metal mine regional nature puddle, utilize the puddle can reduce system cost as settling tank, and can not establish the concentrated and press filteration system of mud, after one the hole precipitating sludge acquires a certain degree naturally, can behind artificial clear mud, continue use.Strainer can adopt common quartz sand strainer, more medium filter, filter tank, V-arrangement filter tank, disc filter, metal grill strainer etc. have the filter plant of filtering function fast, high-efficiency fiber beam filter device (pond) is adopted in modular design of the present invention, adopts high-efficiency fiber filter to have the following advantages:
1) clearance of suspended substance can be near 100% in the water.When turbidity was 20ntu, filtering out water turbidity can be less than once.
2) filtering velocity is generally 30～50m/h, is 3～5 times of conventional filter.
4) retaining power is generally 5～10kg/m3 (filtrate), is 2～4 times of conventional filter.
5) produce the identical water yield, taking up an area of only is 1/3～1/2 of conventional filter.
6) ton water cost is lower than conventional filter.
7) filtering accuracy is adjustable
8) fiber filtering can be in acidity/alkaline environment steady operation
Use because strainer is only done coarse filtration in native system, its filtering accuracy can be adjusted according to subsequent technique, to guarantee the maximization of filtration capacity.The air water backwash process is adopted in the backwash of strainer (pond), air feed equipment can adopt equipment such as air compressor, roots blower, backwash water is different with traditional strainer rinse water employing strainer water outlet, the present invention adopts the product water of the reverse osmosis/nanofiltration system of desalination system, the backwash effect that this not only can improve fabric filter has also improved the utilization ratio of feedwater (cupric stoste).In addition, fabric filter is furnished with chemical cleaning system alone, when fibrous bundle is polluted by iron, silicon even depth and when adopting backwash that its inceptive filtering ability of efficient recovery can't be arranged, can adopt matting to recover its filtration capacity, chemical cleaning system is made up of security personnel's strainer, purge tank, scavenging pump etc.
Super (little) filtering system is by ultrafiltration working shaft, ultrafiltration feed cistern, ultrafiltration main frame, hyperfiltration reverse-rinsing pump, chemical cleaning system, compositions such as pneupress system.The principle of selecting for use that surpasses (little) filter: as the material grains diameter 〉=0.2um such as colloid in the water, can adopt microfiltration membrane, otherwise adopt ultra-filtration membrane.Supermicro filtration membrane element employing PVDF, polysulfones, polypropylene eyeball, PVC, tetrafluoroethylene etc. can be in the organic materials manufacturings of steady operation under the sour environment, the form of membrane element is tubular fibre or rolled film element, owing to cost, reason such as dirty stifled, be difficult for using pottery or stainless steel membrane element.The PVDF hollow fibre membrane component is adopted in modular design of the present invention, the external-compression type operation, and online water backwash and gas enclosure clean.Adopt the backwash of ultra filtration product water different with traditional ultra filtration backwash, the present invention adopts the backwash water of the product water of reverse osmosis/nanofiltration system as the ultra filtration system, because producing in the water, ultra filtration contains a large amount of ferrous ions, when containing dissolved oxygen in the water, ferrous ion can be oxidized to ferric iron, the latter in water with molecule, ion, three kinds of forms of colloid exist, adopt ultra filtration to produce water and carry out backwash, trace iron colloid in the water will cause the hollow-fibre membrane silk inboard dirty stifled, and easy cleaning not, the significantly decay of membrane flux will be caused, the product water water quality of employing reverse osmosis/nanofiltration system is better than the product water of ultra filtration, contains iron ion in the water hardly, can fully guarantee the backwash effect, be difficult for causing the hollow-fibre membrane silk inner dirty stifled, in addition, be rich copper bearing feedwater because water is produced in ultrafiltration, adopt the backwash water of the product water of reverse osmosis/nanofiltration system as ultra filtration, can improve the utilization ratio of feedwater effectively, promptly improve the rate of recovery of system copper.By the waterworks that the feed cistern and the working shaft of ultra filtration are formed the ultra filtration system, working shaft adopts variable frequency water supply, produces water constant current control; The ultra filtration main frame is made up of membrane element and film frame and matching instrument, valve etc.; The ultra filtration backwashing pump adopts low pressure impeller pump, variable frequency water supply; Chemical cleaning system is made up of security personnel's strainer, scavenging pump, purge tank etc.; Pneupress system is made up of air compressor, reducing valve, compressed air tank, strainer etc.The ultra filtration system adopts the cross flow filter mode, the cross-flow flow is the 10%-50% of flooding velocity, efflux flow and be about the 5%-20% of flooding velocity, cross-flow flow and efflux the performance of determining to depend on influent quality and film of flow is so that the ultra filtration system stable operation is design considerations.Modular design of the present invention is different with the feed cistern that traditional design cross-flow water turns back to ultra filtration, and the present invention is directly turned back to the feed cistern in fabric filter (pond) with cross-flow water, and system flow is seen Fig. 2.Cross-flow water is directly turned back to the strainer water supply pool can make cross-flow water carry out secondary filtration returning to strainer after regular hour cohesion, the suspended substance that can guarantee to enter the water inlet of ultra filtration like this remains on a relative low concentration with colloid, not because of cross-flow water turns back to the filtration load that concentrating behind the ultra micro filter tank improved the ultra filtration system, adopt the outer water displacement that can reduce the ultra filtration system after this design maybe can be reduced to below 5% the flow that effluxes of ultra filtration system or the outer water displacement of realization is zero.Because the water inlet and the draining of ultra filtration system are rich copper bearing feedwater, the outer water displacement that reduces the ultra filtration system promptly has been equivalent to improve the rate of recovery of the copper of feedwater, nickel etc., in addition, owing to significantly reduced the filtration load of ultra filtration system, the design flux of raising ultra filtration system that therefore can be by a relatively large margin, reduce the usage quantity of film, reduced the construction costs of ultra filtration system.Though this design has increased the filtration load of fabric filter, increased the cost of coarse filtration system (filter system), but because that the increase of the processed in units water yield cost of filter system accounts for the weight of total system cost is lower, this design still can make the cost decline of total system.Because this design has the total system of reduction cost and improves ultra filtration system operation stability, this design can be applied in the design of other engineering of water treatment and middle water reuse.Two kinds of forms that the water supply of ultra filtration system can adopt overall system to supply water (promptly a working shaft supplies water simultaneously to several frames) and single chassis supplies water.
Reverse osmosis/nanofiltration desalination system is made up of working shaft, security personnel's strainer, high-pressure pump, frame, chemical cleaning system etc.Membrane element of the present invention is acidproof membrane element, can have stable ratio of desalinization and can move steadily in the long term at PH1.0 and following acid range, do not cause the degraded of film because of the acidity of water, propping material and matrix material do not cause cracking because of the acidity of water yet.The principle of selecting for use of desalination system reverse osmosis membrane and nanofiltration membrane is to obtain better to produce water as needs, selects reverse osmosis membrane for use; Produce water water quality as needs and contain more acid, select nanofiltration membrane for use.The present invention adopts reverse-osmosis membrane element as desalination-concentrated film, and the reverse osmosis unit membrane module designs is arranged by feedwater one-level four segmented modes, and dense water is through the desalination and concentration of four sections films, and maximum can obtain 90% the rate of recovery.Wherein one, two section is a suite of racks, is equipped with independently working shaft, security personnel's strainer, high-pressure pump, frame, chemical cleaning system shared; Three, four sections groups are another set of frame, are equipped with independently working shaft, security personnel's strainer, high-pressure pump, frame, chemical cleaning system shared.The remarkable technical characterstic of this design is that first section is adopted big flux, low flow velocity design, and second section is adopted high-throughput, big flow velocity design, and three, four sections are adopted small throughput, big flow velocity design.In addition; each frame is independently operation architecture; one or two sections main frames and three or four sections main frames can not interdepend and independent operating; every group of main frame all has product water washing function; starting product water washing function in system's every operation for some time washes the film surface; promptly fouling and the dirty stifled material at film still do not have before the film surface forms the stifled thing of firm dirt; it is gone out outside the system; in addition; before the each shutdown of system, start washing function; intrasystem dense water is gone out system, generation keep to produce water in system, can prevent from that dense water from resting on system in for a long time film is caused dirty blocking up.The Scale inhibitors medicine system is set before the high-pressure pump of three, four sections frames, the purpose that adds Scale inhibitors is to prevent that fouling is separated out because the height of calcium, strontium, barium and sulfate ion concentrates in the enriching section of system, make film forming fouling, the Scale inhibitors that the present invention added is different with the Scale inhibitors that common reverse osmosis system adds, but be a kind of can be at steady operation under the sour environment and fouling salt such as CaF2 has scale-inhibiting properties in to water Scale inhibitors.In acid waste water treating processess such as mine cupric, the fouling of the reverse osmosis/nanofiltration system of normal generation is the fouling of vitriol, when the present invention in the film system above-mentioned fouling takes place, adopt extraordinary cleaning technique can clean above-mentioned scale forming matter effectively, and recover the serviceability of film effectively.In addition, the iron of controlling diaphragm dirty stifled aspect, the present invention adds reductive agent before the ultra filtration system, reduce the dissolved oxygen content in the water, prevent that dissolved oxygen in the waste water from before entering ultra filtration, reverse osmosis, nanofiltration membrane system, becoming trivalent ion with the oxidation of divalent iron ion in the water.
Embodiment 1
Adopt the example of acid reverse osmosis membrane processing copper mine pit copper-containing acid waste water, former water was pit sour water, through 10 hours post precipitations, filter through fabric filter and the accurate device of 1um, the reverse osmosis unit flooding velocity is 3.0m3/h, adopts big backflow of dense water, small part effluxes, and the rate of recovery is 90%.The waste water separating effect sees Table 1:
Table 1:
| The water quality project | The settling tank water outlet | The fabric filter water outlet | Reverse osmosis produced water | Reverse osmosis concentrated water | Unit |
| ??pH | ??2.2 | ??2.24 | ??2.98 | ??1.7 | |
| ??TDS | ??740 | ??741 | ??103 | ??3370 | ??mg/l |
| Specific conductivity | ??1504 | ??1510 | ??215 | ??6710 | ??us/cm |
| ??Fe2+ | ??12.5 | ??14.5 | Do not detect | ??134 | ??mg/l |
| ??Cu | ??128.5 | ??128.5 | ??2.12 | ??1020 | ??mg/l |
| ??Ca | ??4.16 | ??4.14 | ??0.01 | ??57.82 | ??mg/l |
| ??Mg | ??0.31 | ??0.31 | ??0.02 | ??3.02 | ??mg/l |
| ??K | ??2.54 | ??2.53 | ??0.52 | ??14.68 | ??mg/l |
| ??Na | ??22.34 | ??22.56 | ??6.39 | ??133.6 | ??mg/l |
| ??Zn | ??5.73 | ??4.76 | ??0.15 | ??34.82 | ??mg/l |
| The water quality project | The settling tank water outlet | The fabric filter water outlet | Reverse osmosis produced water | Reverse osmosis concentrated water | Unit |
| ??Sr | ??0.89 | ??0.87 | ??0.008 | ??7.80 | ??mg/l |
| ??Al | ??14.77 | ??14.39 | ??0.67 | ??112.14 | ??mg/l |
| ??As | ??0.059 | ??0.04 | ??0.07 | ??0.045 | ??mg/l |
| ??Cl- | ??11.49 | ??12.02 | ??6.41 | ??57.52 | ??mg/l |
| ??SO42- | ??580 | ??560 | ??20 | ??4680 | ??mg/l |
| ??Mn | ??0.34 | ??0.33 | Do not detect | ??2.08 | ??mg/l |
| Turbidity | ??35.6 | ??0.63 | ??0.1 | ??0.55 | ??ntu |
Embodiment 2
Former water is the raffinate of certain copper mine copper mine clitter field and the part rainwater from the stockyard, and big of this part water returns the stockyard as acid stockyard spray liquid, and part effluxes after neutralization, causes the heavy losses of copper.Deliver to the mine extracting system and reclaim copper adopting nanofiltration system that it is concentrated back concentrated solution (dense water), produce in the water and after efflux to keep the water balance of copper mine clitter field-extracting system.The nanofiltration system flooding quantity is 3.0m3/h, and partial reflux effluxes on a small quantity, and the rate of recovery of system is 50%, and table 3 is the separating effect of nanofiltration membrane to waste water.
Table 3
| Test item | Water inlet | Dense water | Produce water | Unit |
| ??pH | ??1.49 | ??1.44 | ??1.35 | |
| ??TDS | ??24100 | ??38000 | ??9800 | ??mg/l |
| ??Na | ??8.45 | ??11.65 | ??2.57 | ??mg/l |
| ??K | ??0.96 | ??1.31 | ??0.34 | ??mg/l |
| ??As | ??88.82 | ??140 | ??0.82 | ??mg/l |
| ??Pb | ??1.33 | ??1.96 | ??0.16 | ??mg/l |
| ??Cu | ??690 | ??1160 | ??3 | ??mg/l |
| ??Fe | ??10280 | ??16860 | ??27.98 | ??mg/l |
| Test item | Water inlet | Dense water | Produce water | Unit |
| ??Zn | ??280 | ??470 | ??0.9 | ??mg/l |
| ??Mg | ??54 | ??80.9 | ??0.2 | ??mg/l |
| ??Ca | ??122.1 | ??163.4 | ??1.21 | ??mg/l |
| ??SiO2 | ??291 | ??347 | ??191 | ??mg/l |
| Test item | Water inlet | Dense water | Produce water | Unit |
| ??SO42- | ??33.9 | ??53.89 | ??3.32 | ??g/l |
| ??Cl- | ??8.91 | ??10.28 | ??12.25 | ??mg/l |
By above-mentioned two case study on implementation as can be seen, acid waste water through reverse osmosis/nanofiltration concentrate and separating treatment after, content of copper ion in the dense water has surpassed 1.0g/l, the copper content that the biological lixiviation process of its copper content and hydrometallurgy low-grade copper ore is carried in the expensive liquid of leaching cupric of copper is suitable, be the expensive liquid of a kind of ideal cupric, can satisfy the requirement of the feeding liquid of hydrometallurgical extraction-electrodeposition system fully.Producing water because water quality is better, except that showing slightly acidity, is a kind of qualified service water, can be back to use production fields such as ore dressing, smelting, cleaning.
Description of drawings: Fig. 1 is process for treating acidic sewage schemas such as embrane method Treatment of Copper, nickel; Fig. 2 is the concentrate recirculation of ultra filtration system and effluxes schema; Fig. 3 is four sections reverse osmosis process schemas of one-level.
Claims (9)
1. a processing nonferrous metal mine of being made up of settling tank, fabric filter, ultra filtration, reverse osmosis/nanofiltration, smelting, ore dressing etc. contain the processing and the reuse technology of the acid waste water of precious metal ion.It is characterized in that waste water is through the separation of native system with concentrate, the dense water that is rich in precious metal is admitted to extraction-electrodeposition system or reclaims precious metals such as copper in the waste water, nickel by depositing technologies such as sodium sulphite, iron displacements, isolated product water is back to use production system as service water, be characterized in when handling waste water, can reclaim valuable metal ions and the water resources in the waste water to greatest extent, accomplish the wastewater treatment resource utilization;
2. according to claims 1 described technology, it is characterized in that filtrate, supermicro filtration membrane, the reverse osmosis/nanofiltration membrane in the technology is and can has the acid proof feature in the sour environment long-term stable operation;
3. according to claims 1 described technology, it is characterized in that precipitation, filtration, the ultra filtration pretreatment unit in its technology can be adjusted according to suspended substance, colloidal content in the water inlet, to reduce system cost.
4. according to claims 1 described technology, it is characterized in that adopting the backwash water of the product water of reverse osmosis or nanofiltration as strainer, can improve the backwash effect of strainer and the rate of recovery of metals such as raising copper, nickel, strainer is furnished with chemical cleaning system, can carry out matting to filter leaching material, to recover the strainability of filtrate.
5. according to claims 1 described technology, the backwash water that it is characterized in that the ultra filtration system adopts the product water of reverse osmosis/nanofiltration, can improve the backwash effect of ultra filtration and can prevent that hollow-fibre membrane is inboard dirty stifled and to improve to water use efficiency be the rate of recovery of valuable metal.
6. according to claims 1 described technology, it is characterized in that ultra filtration employing cross flow filter mode, its cross-flow water turns back to the pump sump (mouth) of strainer, carry out secondary filtration through filter, to guarantee that the water inlet suspended substance, the colloid that enter the ultra filtration system remain on low relatively level, be beneficial to the steady running of ultra filtration system, and can increase the design flux of supermicro filtration membrane.
7. according to claims 1 described technology, it is characterized in that before the ultra filtration system, adding reductive agent, reduce oxygen in water content, the dissolved oxygen in the anti-sealing generates the trivalent CI at the stop of water and the ferrous ion in the further oxidizing water of course of conveying.
8. according to claims 1 described technology, it is characterized in that reverse osmosis/nanofiltration system adopts four sections designs of one-level and is furnished with the water of producing washing function, can effectively reduce the stifled and fouling tendency of dirt of film, with the operation of guaranteeing system stability with have the higher rate of recovery.
9. according to claims 1 described technology, it is characterized in that adopting the Scale inhibitors that under sour environment, to work, be added to back segment, can effectively prevent the fouling of reverse osmosis/nanofiltration.
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| CN200910169015A CN101786734A (en) | 2009-09-08 | 2009-09-08 | Process for treating acid waste water containing copper, nickel and the like by membrane method |
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| CN200910169015A CN101786734A (en) | 2009-09-08 | 2009-09-08 | Process for treating acid waste water containing copper, nickel and the like by membrane method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070259A (en) * | 2010-12-10 | 2011-05-25 | 苏州海创电子有限公司 | Method and device for processing and recycling nickel plating waste water |
| CN102476885A (en) * | 2010-11-25 | 2012-05-30 | 昆山明宽环保节能科技有限公司 | Waste water processing system and method thereof |
| CN102515389A (en) * | 2011-12-09 | 2012-06-27 | 紫金矿业集团股份有限公司 | Harmless treatment process for acidic copper-containing wastewater |
| CN102730861A (en) * | 2012-08-02 | 2012-10-17 | 华夏新资源有限公司 | Recycling system for surface treatment of phosphorus-containing electroless nickel plating solution composition by wet process |
| CN103184335A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Low-grade multi-metal sulfide mineral selective bioleaching technology |
| CN103539294A (en) * | 2013-10-08 | 2014-01-29 | 南京源泉环保科技股份有限公司 | Method for recovering silver plating wastewater and silver |
| CN104743717A (en) * | 2015-03-11 | 2015-07-01 | 英诺伟霆（北京）环保技术有限公司 | Method and system for reduction of concentrated brine |
| CN104891704A (en) * | 2015-05-05 | 2015-09-09 | 岳嵩 | High-salt content waste water treatment method |
| CN104961197A (en) * | 2015-06-18 | 2015-10-07 | 广东嘉元科技股份有限公司 | Water-saving process and water-saving device for treating copper foil wastewater |
| CN105731682A (en) * | 2014-12-11 | 2016-07-06 | 苏州澄江环境科技有限公司 | System and method for treating acetic acid-containing wastewater |
| CN105800825A (en) * | 2016-04-08 | 2016-07-27 | 苏州市美能五金镀饰有限公司 | Treatment process for synthetic wastewater of chromium planting |
| CN106830194A (en) * | 2017-02-14 | 2017-06-13 | 莱特莱德（北京）环境技术股份有限公司 | One kind is applied to field of hydrometallurgy heavy metal concentration and recovery reuse means |
| CN107792916A (en) * | 2016-08-30 | 2018-03-13 | 广东益诺欧环保股份有限公司 | A kind of special film condensing device of spent acid |
| CN110282777A (en) * | 2019-06-24 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of processing method of kaolin waste water |
| CN110436673A (en) * | 2019-09-02 | 2019-11-12 | 宝武集团环境资源科技有限公司 | A kind of Treating Electroplate Wastewater Containing Nickel recycling and reusing method |
| CN111470649A (en) * | 2019-01-23 | 2020-07-31 | 上海旷宇环境科技有限公司 | Recovery treatment method of industrial acidic wastewater |
| CN112028347A (en) * | 2019-06-04 | 2020-12-04 | 核工业理化工程研究院 | Zero-discharge treatment system and treatment method for chemical nickel plating wastewater |
| CN114195310A (en) * | 2021-12-09 | 2022-03-18 | 中国铝业股份有限公司 | Treatment method of high-purity quartz acid wastewater |
| CN114368852A (en) * | 2021-12-14 | 2022-04-19 | 唐山钢铁集团有限责任公司 | Cold rolling acid-containing wastewater treatment system and process |
| CN116199360A (en) * | 2022-11-15 | 2023-06-02 | 厦门爱迪特环保科技有限公司 | System and method for recycling nickel and cobalt from ternary precursor wastewater |
| CN117509996A (en) * | 2024-01-05 | 2024-02-06 | 山东域潇锆钛矿业股份有限公司 | Wastewater treatment device and wastewater treatment method for perovskite flotation |
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2009
- 2009-09-08 CN CN200910169015A patent/CN101786734A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476885A (en) * | 2010-11-25 | 2012-05-30 | 昆山明宽环保节能科技有限公司 | Waste water processing system and method thereof |
| CN102070259A (en) * | 2010-12-10 | 2011-05-25 | 苏州海创电子有限公司 | Method and device for processing and recycling nickel plating waste water |
| CN102515389A (en) * | 2011-12-09 | 2012-06-27 | 紫金矿业集团股份有限公司 | Harmless treatment process for acidic copper-containing wastewater |
| CN103184335A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Low-grade multi-metal sulfide mineral selective bioleaching technology |
| CN103184335B (en) * | 2011-12-31 | 2014-07-16 | 北京有色金属研究总院 | Low-grade multi-metal sulfide mineral selective bioleaching technology |
| CN102730861A (en) * | 2012-08-02 | 2012-10-17 | 华夏新资源有限公司 | Recycling system for surface treatment of phosphorus-containing electroless nickel plating solution composition by wet process |
| CN103539294A (en) * | 2013-10-08 | 2014-01-29 | 南京源泉环保科技股份有限公司 | Method for recovering silver plating wastewater and silver |
| CN103539294B (en) * | 2013-10-08 | 2015-07-29 | 南京源泉环保科技股份有限公司 | Reclaim the method for silver-plated waste water and silver |
| CN105731682A (en) * | 2014-12-11 | 2016-07-06 | 苏州澄江环境科技有限公司 | System and method for treating acetic acid-containing wastewater |
| CN104743717A (en) * | 2015-03-11 | 2015-07-01 | 英诺伟霆（北京）环保技术有限公司 | Method and system for reduction of concentrated brine |
| CN104891704A (en) * | 2015-05-05 | 2015-09-09 | 岳嵩 | High-salt content waste water treatment method |
| CN104961197A (en) * | 2015-06-18 | 2015-10-07 | 广东嘉元科技股份有限公司 | Water-saving process and water-saving device for treating copper foil wastewater |
| CN105800825A (en) * | 2016-04-08 | 2016-07-27 | 苏州市美能五金镀饰有限公司 | Treatment process for synthetic wastewater of chromium planting |
| CN107792916A (en) * | 2016-08-30 | 2018-03-13 | 广东益诺欧环保股份有限公司 | A kind of special film condensing device of spent acid |
| CN106830194A (en) * | 2017-02-14 | 2017-06-13 | 莱特莱德（北京）环境技术股份有限公司 | One kind is applied to field of hydrometallurgy heavy metal concentration and recovery reuse means |
| CN111470649A (en) * | 2019-01-23 | 2020-07-31 | 上海旷宇环境科技有限公司 | Recovery treatment method of industrial acidic wastewater |
| CN112028347A (en) * | 2019-06-04 | 2020-12-04 | 核工业理化工程研究院 | Zero-discharge treatment system and treatment method for chemical nickel plating wastewater |
| CN110282777A (en) * | 2019-06-24 | 2019-09-27 | 三达膜科技（厦门）有限公司 | A kind of processing method of kaolin waste water |
| CN110436673A (en) * | 2019-09-02 | 2019-11-12 | 宝武集团环境资源科技有限公司 | A kind of Treating Electroplate Wastewater Containing Nickel recycling and reusing method |
| CN114195310A (en) * | 2021-12-09 | 2022-03-18 | 中国铝业股份有限公司 | Treatment method of high-purity quartz acid wastewater |
| CN114368852A (en) * | 2021-12-14 | 2022-04-19 | 唐山钢铁集团有限责任公司 | Cold rolling acid-containing wastewater treatment system and process |
| CN114368852B (en) * | 2021-12-14 | 2024-07-02 | 唐山钢铁集团有限责任公司 | Cold rolling acid-containing wastewater treatment system and process |
| CN116199360A (en) * | 2022-11-15 | 2023-06-02 | 厦门爱迪特环保科技有限公司 | System and method for recycling nickel and cobalt from ternary precursor wastewater |
| CN117509996A (en) * | 2024-01-05 | 2024-02-06 | 山东域潇锆钛矿业股份有限公司 | Wastewater treatment device and wastewater treatment method for perovskite flotation |
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