CN104671507A - Comprehensive recycling method for trimanganese tetraoxide industrial wastewater - Google Patents
Comprehensive recycling method for trimanganese tetraoxide industrial wastewater Download PDFInfo
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- CN104671507A CN104671507A CN201510121416.3A CN201510121416A CN104671507A CN 104671507 A CN104671507 A CN 104671507A CN 201510121416 A CN201510121416 A CN 201510121416A CN 104671507 A CN104671507 A CN 104671507A
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Abstract
The invention discloses a comprehensive recycling method for trimanganese tetraoxide industrial wastewater. The comprehensive recycling method comprises the following steps: firstly collecting and standing the trimanganese tetraoxide industrial wastewater, wherein the trimanganese tetraoxide particles are suspended in the precipitated wastewater; adding alkali liquor and a flocculating agent into a supernatant of the wastewater; monitoring the situation that the pH value is lower than 11 to adjust the adding speed of the alkali liquor; meanwhile feeding air or oxygen as an oxidizing agent, and performing a primary manganese deposition; purifying the supernatant after the primary manganese deposition; performing solid-liquid separation to the residual precipitated slurry to obtain trimanganese tetraoxide precipitate; returning the trimanganese tetraoxide precipitate to a trimanganese tetraoxide production system. The method disclosed by the invention has the advantages of being resource-saving, environment-friendly, simple in process, low in cost and the like, and can be used for sufficiently recycling the manganese resource and the water resource.
Description
Technical field
The invention belongs to hydrometallurgy and technical field of environmental protection in chemical industry, be specifically related to a kind of comprehensive processing technique of trimanganese tetroxide factory effluent.
Background technology
Along with the rapid emergence of the industries such as the whole world electromechanics, electronics, information, communication, household electrical appliance, computer, its product is fast-developing towards the direction of high-performance, miniaturization, and the cycle of model change is shorter and shorter.To the base mateiral of electronics, electromechanical industries---the performance of soft magnetic ferrite is had higher requirement.Therefore trimanganese tetroxide progressively instead of the basic raw material that manganous carbonate becomes soft magnetic ferrite.The states such as the U.S., Japan, Belgium, South Africa successively achieve the suitability for industrialized production of trimanganese tetroxide the eighties in 20th century.A little later, early 1990s just starts to carry out back yard industry test in the development starting of China's trimanganese tetroxide, and its trial production scale is less than 1000t/a.But trimanganese tetroxide tempo is at home but very surprising, substantially achieves suitability for industrialized production to nineteen ninety-five.The yearly capacity of domestic trimanganese tetroxide in 1999 reaches 1.5 ten thousand t, to the yearly capacity of domestic trimanganese tetroxide in 2010 more than 120,000 t.Manufacturer also develops into tens of today by initial two or three.Industrial scale and the output of present China trimanganese tetroxide all occupy first place in the world.In the production process of trimanganese tetroxide, trimanganese tetroxide production per ton can produce the processing wastewater of 5 ~ 8 tons, wherein containing manganese suspended substance 0.1 ~ 0.5g/L, Mn
2+0.4 ~ 0.8g/L.These contain the trade effluent directly outer row of manganese suspended substance and mn ion, have both caused the serious waste of promoter manganese and water resources, and have caused certain pollution again to environment.
In recent years, along with the requirement of country to environmental protection is more and more higher, trimanganese tetroxide factory all starts to process factory effluent.Most widely used technique is the heavy manganese of carbide slag (alkali) process.But the method can only precipitate the manganese in factory effluent as slag muck slagging field, manganese slag is not because recycling containing a large amount of lime, waste water after heavy manganese is the extremely neutral rear outer row of acid adding readjustment pH value again, This reduces both manganese recovery ratio, cause the wasting of resources, process manganese slag can cause secondary pollution to environment again.Pei Fei etc. develop biotechnological formulation hydrous water solution to process the method for Mn-bearing waste water, Ou Yangyuzhu have studied and utilizes iron chipping microelectrolysis process Mn-bearing waste water, all achieves qualified discharge after wastewater treatment, but complex disposal process, running cost is high, is difficult to realize industrialization.
Summary of the invention
Technical problem to be solved by this invention is, the complex treatment process existed for current trimanganese tetroxide industrial wastewater treatment technique, running cost are high, promoter manganese can not fully be recycled and produce a large amount of carbide slags and cause secondary pollution problems, particularly processed waste water can not the defect such as recycle, provides a kind of resources conservation, environmental friendliness, technique is simple, cost is low, can realize the comprehensive reutilization method of the trimanganese tetroxide factory effluent that promoter manganese and water resources are fully recycled.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of comprehensive reutilization method of trimanganese tetroxide factory effluent, comprises the following steps:
(1) first carry out collection to trimanganese tetroxide factory effluent to leave standstill, the trimanganese tetroxide particle suspended in precipitation waste water;
(2) in the supernatant liquor of above-mentioned steps (1) waste water afterwards, add alkali lye and flocculation agent, by monitoring pH value below 11 adjust the interpolation speed of alkali lye, while blowing air or oxygen make oxygenant, once sink manganese;
(3) by after above-mentioned steps (2) once the supernatant liquor of heavy manganese carry out purifying treatment, remaining sediment slurry carries out solid-liquid separation, obtains trimanganese tetroxide throw out, and this trimanganese tetroxide throw out is back to trimanganese tetroxide production system.
Above-mentioned trimanganese tetroxide factory effluent includes, but are not limited to the Mn-bearing waste water that discharge produced by trimanganese tetroxide, this Mn-bearing waste water particularly preferably bath water, unnecessary mother liquor overflow water, reaction workshop section equipment failure maintenance time the cleaning equipment waste water, at least one in production process in the waste water such as evaporating, emitting, dripping or leaking of liquid or gas that produce.Preferred, the manganese ion concentration in this Mn-bearing waste water is at 0.5 ~ 3g/L, and pH value controls 5 ~ 7.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferred: described alkali lye is sodium hydroxide solution or ammoniacal liquor, and after adding alkali lye, regulate pH value to 9 ~ 10 of waste water, and to make in waste water 95% (if no special instructions, the massfraction that all percentage ratio all refers to) more than manganese be recycled, and control once Mg in the supernatant liquor after heavy manganese
2+eR for emission rate reaches more than 75%.By being optimized pH value, object avoids other impurity (as Ca, Mg) in waste water and manganese coprecipitation out, ensures the rate of recovery of manganese simultaneously.In addition, in once heavy manganese process of the present invention, after removing the flocculation agent (polyacrylamide) adding sodium hydroxide solution (or ammoniacal liquor) and trace, no longer include other chemical reagent and add; Sodium hydroxide is easy to washing, can reach control criterion, and ammonium radical ion can play the effect of catalyzer in trimanganese tetroxide production process in trimanganese tetroxide production process by washing, also can not produce harm to final trimanganese tetroxide product.These consider the purity that all ensure that recovered material, make final trimanganese tetroxide product be unlikely to increase other harmful impurity.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferred: the process of described once heavy manganese first makes the mn ion in waste water change into manganous hydroxide, then manganous hydroxide is oxidized to trimanganese tetroxide.The reaction principle of this once heavy manganese process is as follows:
Add alkali and sink the reaction principle of manganese: Mn
2++ 2OH
-=Mn (OH)
2↓;
Generate trimanganese tetroxide reaction principle: 3Mn (OH)
2+ 1/2O
2=Mn
3o
4+ 3H
2o.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferred: in described step (3), carry out purifying treatment to supernatant liquor specifically to comprise the following steps: this supernatant liquor is first filtered, then a sewage reverse osmosis membrane processing device is entered, after supernatant liquor after the process of sewage reverse osmosis membrane processing device mixes with tap water, enter a RO reverse osmosis membrane treatment system, the pure water after the process of RO reverse osmosis membrane system is back to trimanganese tetroxide production system as water of productive use.Reverse osmosis membrane apparatus can reclaim the water of more than 65% as industrial tap water, returns trimanganese tetroxide production system and uses.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, flocculation agent and caustic soda is added in dense water after the process of described sewage reverse osmosis membrane processing device, carry out secondary and sink manganese, secondary sinks acid liquid in the supernatant liquor after manganese and is adjusted to neutrality (such as pH value to 7 ~ 8) outer row afterwards, Fe content now in waste water generally can be less than 2mg/L, reaches discharging standards.Secondary sinks the sediment slurry after manganese then to carry out press filtration process and obtains Mn-rich slag, and a small amount of Mn-rich slag (manganese content is more than 25%) be settled out, can be supplied to electrolytic manganese production producer as raw material.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferably, the pH value after adding flocculation agent and caustic soda in described dense water is adjusted to 11 ~ 13.
Preferred, described flocculation agent is polyacrylamide, and the consumption of each flocculation agent is only 0.001% ~ 0.002% of wastewater treatment capacity.Feed way unique in the present invention and gas distribution mode make the consumption of flocculation agent be only 0.001% ~ 0.002% of wastewater treatment capacity, and settling velocity reaches 20cm/ minute, compared with prior art substantially increases the utilization ratio of flocculation agent.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferably, described once heavy manganese carries out in a settlement treatment groove, settlement treatment groove is externally connected with alkali lye adding trough and flocculation agent adding trough, breather is provided with in described settlement treatment groove, the bottom of described settlement treatment groove is provided with sediment slurry discharge port, and described sediment slurry discharge port is communicated to trimanganese tetroxide production system, and the supernatant liquor liquid outlet of described settlement treatment groove is communicated to heavy manganese supernatant liquor purification system; Described heavy manganese supernatant liquor purification system comprises the filtering system, sewage reverse osmosis membrane processing device and the RO reverse osmosis membrane treatment system that are communicated with successively, and the pure water outlet of described RO reverse osmosis membrane treatment system is to trimanganese tetroxide production system.In preferred technical scheme, in waste water recycling process, have employed the unique design scheme of sewage reverse osmosis membrane processing device and RO reverse osmosis membrane treatment system conbined usage.Although because the waste water through the process of sewage reverse osmosis membrane processing device is very nearly the same with industrial tap water in conductance, but due to sink at waste water manganese process in add a large amount of sodium hydroxide, so the Na contained in industrial pure water after the process of sewage reverse osmosis membrane processing device
+, K
+, Mn
2+plasma is higher than industrial tap water, but Ca
2+, Mg
2+ion content is but better than industrial tap water.In order to make its final utilization water quality reach optimization, two groups of reverse osmosis membranes are connected by the present invention, and will carry out used in combination, to ensure that final water quality reaches industrial requirement through the industrial pure water of sewage reverse osmosis membrane processing device and industrial tap water.In addition, the purifying treatment mode of ion exchange resin etc. compared to existing technology, it is a physical process that the reverse osmosis method that the present invention adopts produces desalination, there is not other impurity and gets involved, compare environmental protection; Can effectively tackle the detrimental impurity that the trimanganese tetroxide products such as Si are abstained from, and treating processes is simple to operation, automatic degreeization is high, and manual intervention amount is little, and the management and utilization of system is simple simultaneously.Waste water after the process of reverse osmosis membrane processing device has more than 50% to return industrial production, thus greatly reduces secondary and sink the pressure of manganese, reduces the quantity discharged of waste water, is conducive to saving water resource.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferably, breather in described settlement treatment groove comprises ventpipe and is located at the air-spreading disk of below in settlement treatment groove cavity volume, and described ventpipe is communicated to air-spreading disk, and described air-spreading disk evenly offers qi-emitting hole.Simultaneously waste water of the present invention and alkali lye, flocculation agent add in settlement treatment groove, aforementioned breather is opened while adding, what adjust alkali lye by monitoring pH places speed, liquid can be made by the breather of this optimization, solid, gas three-phase evenly combines under flow dynamic and aerodynamic effect, eliminate the setting of whipping appts, reduce energy consumption.Feed way unique in the present invention and gas distribution mode also make the consumption of flocculation agent be only 0.001% ~ 0.002% of wastewater treatment capacity, and settling velocity reaches 30cm/ minute, compared with prior art substantially increases the utilization ratio of flocculation agent.Preferred, the fluid inlet of described settlement treatment groove is communicated to one and leaves standstill pond, and described supernatant liquor liquid outlet is provided with multiple, and multiple supernatant liquor liquid outlets is located at the sidepiece of settlement treatment groove, and is arranged on different height.Described settlement treatment groove, by adopting multistage overflow manner, saves energy consumption, improves the efficiency of process waste water.Preferred, the hypomere of described settlement treatment groove adopts inverted cone-shaped structure.The bottom of settlement treatment groove adopts centrum to be designed with and is beneficial to material sedimentation and improves the concentration precipitating material, directly can return production plant, save solid-liquid separation, simplify operating process, be beneficial to suitability for industrialized production when concentration is suitable.
The comprehensive reutilization method of above-mentioned trimanganese tetroxide factory effluent, preferably, described filtering system comprises the first sand filtering device, deep bed filter, water storage device, spiral-flow filter, laminated filter and the cartridge filter that are communicated with successively; The industrial pure water outlet of described sewage reverse osmosis membrane processing device is to described RO reverse osmosis membrane treatment system, and described RO reverse osmosis membrane treatment system comprises the second sand filtering device, carbon post and the RO reverse osmosis membrane that are communicated with successively; The dense water out of described sewage reverse osmosis membrane processing device is communicated to a dense depositing in water manganese treatment system, and described dense depositing in water manganese treatment system comprises secondary settlement tower, and described secondary settlement tower is provided with dense water fluid inlet, alkali lye adds mouth and flocculation agent adds mouth.Owing to also having the Mn of trace in the once heavy manganese treating processes of first stage
2+remain in waste water with tiny manganous hydroxide precipitation, if these waste water directly enter the work-ing life that follow-up sewage reverse osmosis membrane processing device and RO reverse osmosis membrane treatment system can affect film, reduce final water quality.Therefore, in waste water recycling pretreatment stage, the present invention adds the filtering system be made up of the first sand filtering device, deep bed filter, water storage device, spiral-flow filter, laminated filter and cartridge filter especially, to guarantee the interception to residual impurity in waste water, thus ensure result of use and the life-span of follow-up reverse osmosis membrane.
Technical scheme after above-mentioned optimization adopts the Mn in two-stage method process recovery waste water
2+, particularly reach different objects by the control of different steps to pH value.Once sinking the manganese stage: because contain detrimental impurity such as trimanganese tetroxide Index Influence very large Mg, Ca in trimanganese tetroxide factory effluent, Mg
2+concentration can up to about 35mg/L, and Mg precipitation pH value and Mn are closely, if pH controls too high (as pH value is greater than 11), although can process the Mn in waste water completely, make its qualified discharge, Mg, Ca in waste water also can be precipitated out completely, if these slips return trimanganese tetroxide production system, make the impurity such as Mg, Ca in its trimanganese tetroxide production process define closed cycle, thus cause the alkali metal content in reclaimed materials too high, can not production system be returned.Therefore, once the target in heavy manganese stage is exactly by regulating and controlling the manganese that pH value reclaims in waste water more than 95% as far as possible, ensures the Mg in waste water simultaneously
2+eR for emission rate reaches more than 75%, can return the object of trimanganese tetroxide production system use with the trimanganese tetroxide throw out reaching recovery.Sink the manganese stage at follow-up secondary: by control ph to 11 ~ 13 after adding flocculation agent and caustic soda to precipitate residue manganese in waste water and basic metal, its qualified discharge can be made.Because not relating to the control of magnesium elements in electrolytic manganese national standard (YB/T051-2003), and in manganor manganic oxide used for soft magnetic ferrite standard (GB/T21836-2008), relate to the strict control criterion of calcium, magnesium elements, therefore the present invention is according to the requirement of the feature of trimanganese tetroxide industry and various operational path, through meticulously considering and design, determining above-mentioned two benches and sinking the process optimization thinking of manganese.The closed cycle of detrimental impurity can not only be prevented like this, avoid the enrichment in the product of these detrimental impurity, and valuable metal manganese can be made fully to be reclaimed and utilize, improve the quality of product.
Compared with prior art, the invention has the advantages that:
1. the manganese suspended substance in method energy effective recycling trimanganese tetroxide factory effluent of the present invention and mn ion, through detecting, manganese recovery ratio is all greater than 95%, and the manganese reclaimed can become electronic-grade trimanganese tetroxide through peroxidation, reach manganor manganic oxide used for soft magnetic ferrite standard (GB/T21836-2008), a small amount of Mn-rich slag obtained after optimizing further can return electrolytic manganese factory as raw materials for production.
2. the waste water after the inventive method process can reach following index: Mn≤2mg/L, reach national wastewater discharge standard (GR8978-1996) completely, the more important thing is, the waste water once after heavy manganese is applied to production system by the water that can reclaim more than 50% after reverse osmosis membrane processing as industrial tap water.
In general, comprehensive reutilization method of the present invention is simple for process, easy handling, facility investment and cost for wastewater treatment lower, resource reclaim efficiency is high, be a kind of resources conservation, environmental friendliness, technique is simple, cost is low, have the water of productive use treatment process of broad prospect of application, can bring good economic benefit, social benefit and environmental benefit for trimanganese tetroxide manufacturing enterprise, also can provide good reference for the process of other similar Mn-bearing waste waters simultaneously.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the process operation schematic diagram of comprehensive reutilization method in the specific embodiment of the invention.
Fig. 2 is the structural representation sketch of the comprehensive reutilization treatment system of trimanganese tetroxide factory effluent in the specific embodiment of the invention.
Marginal data:
1, pond is left standstill; 2, alkali lye adding trough; 3, flocculation agent adding trough; 4, settlement treatment groove; 41, ventpipe; 42, sediment slurry discharge port; 43, air-spreading disk; 44, supernatant liquor liquid outlet; 5, sewage lagoon; 6, the first sand filtering device; 7, deep bed filter; 8, water storage device; 9, spiral-flow filter; 10, laminated filter; 11, cartridge filter; 12, sewage reverse osmosis membrane processing device; 13, RO reverse osmosis membrane; 14, carbon post; 15, secondary settlement tower; 16, filter-pressing device; 17, filtering system; 18, RO reverse osmosis membrane treatment system; 19, the second sand filtering device; 20, liquid storage tank; 21, equalizing tank.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Use the comprehensive reutilization treatment system of trimanganese tetroxide factory effluent of the present invention as shown in Figure 2 in following examples, this comprehensive reutilization treatment system comprises waste water and sinks manganese treatment system and heavy manganese supernatant liquor purification system.This waste water sinks manganese treatment system and includes one and leave standstill pond 1 and settlement treatment groove 4, and the fluid inlet of settlement treatment groove 4 is communicated to standing pond 1, and settlement treatment groove 4 is externally connected with alkali lye adding trough 2 and flocculation agent adding trough 3.The bottom of settlement treatment groove 4 is provided with sediment slurry discharge port 42, and sediment slurry discharge port 42 is communicated to trimanganese tetroxide production system; The sidepiece of settlement treatment groove 4 is also provided with three supernatant liquor liquid outlets, 44, three supernatant liquor liquid outlets 44 and is arranged on the different heights of settlement treatment groove 4 side, and each supernatant liquor liquid outlet 44 is all communicated to heavy manganese supernatant liquor purification system.Also breather is provided with in the settlement treatment groove 4 of the present embodiment, breather in settlement treatment groove 4 comprises ventpipe 41 and is located at the air-spreading disk 43 of below in settlement treatment groove cavity volume, ventpipe 41 is communicated to air-spreading disk 43, and air-spreading disk 43 evenly offers qi-emitting hole.
The heavy manganese supernatant liquor purification system of the present embodiment comprises the sewage lagoon 5, filtering system 17, sewage reverse osmosis membrane processing device 12 and the RO reverse osmosis membrane treatment system 18 that are communicated with successively.The filtering system 17 of the present embodiment comprises the first sand filtering device 6 (sand tower), deep bed filter 7, water storage device 8 (water tank), spiral-flow filter 9, laminated filter 10 and the cartridge filter 11 that are communicated with successively.
Industrial pure water outlet to RO reverse osmosis membrane treatment system 18, the RO reverse osmosis membrane treatment system 18 of above-mentioned sewage reverse osmosis membrane processing device 12 comprises the second sand filtering device 19 (sand tower), carbon post 14, cartridge filter 11 and the RO reverse osmosis membrane 13 that are communicated with successively.The pure water outlet of RO reverse osmosis membrane treatment system 18 is to trimanganese tetroxide production system.
The dense water out of above-mentioned sewage reverse osmosis membrane processing device 12 is communicated to a dense depositing in water manganese treatment system, the secondary settlement tower 15 that the dense depositing in water manganese treatment system of the present embodiment comprises a liquid storage tank 20 and is communicated with liquid storage tank 20, secondary settlement tower 15 is provided with dense water fluid inlet, alkali lye adds mouth and flocculation agent adds mouth.The bottom of secondary settlement tower 15 is provided with sediment slurry outlet, and this sediment slurry outlet to filter-pressing device 16 (plate-and-frame filter press), the liquid outlet of filter-pressing device 16 returns and is communicated to liquid storage tank 20.Secondary settlement tower 15 is also provided with supernatant liquor outlet, this supernatant liquor outlet to equalizing tank 21, equalizing tank 21 is provided with vitriol oil spout.
Embodiment 1:
A kind of comprehensive reutilization method of trimanganese tetroxide factory effluent of the present invention as shown in Figure 1 and Figure 2, trimanganese tetroxide factory effluent in the present embodiment comprises washing overflow water in certain trimanganese tetroxide factory production process and trimanganese tetroxide production plant cleaning equipment water, its Mn after testing
2+content reaches 0.7g/L, and pH value is 6 ~ 7; This comprehensive reutilization method specifically comprises the following steps:
1. the trimanganese tetroxide factory effluent in the present embodiment pumps into 30m through leaving standstill after pond 1 collection leaves standstill
3in settlement treatment groove 4, add sodium hydroxide solution (also ammoniacal liquor can be added) and flocculation agent (consumption controlling flocculation agent polyacrylamide is about 0.001% of wastewater treatment capacity) to the supernatant liquor in settlement treatment groove 4 by alkali lye adding trough 2 and flocculation agent adding trough 3 simultaneously, about 9.5 (such as 9 ~ 10) are remained on to adjust the interpolation speed of sodium hydroxide solution by the pH value monitoring waste water, in settlement treatment groove 4, pass into air by ventpipe 41 and air-spreading disk 43 in this process to carry out being oxidized once heavy manganese (this process can save the whipping appts in treatment trough simultaneously, energy efficient), fill rear continuation blowing air in settlement treatment groove 4 to be oxidized and at least to stop ventilation after 30min, after leaving standstill 45min, discharge supernatant liquor by supernatant liquor liquid outlet 44.After testing, Mn in the supernatant liquor of discharge
2+content is down to about 30mg/L, and pH value is 8.5 ~ 9.In waste water, the manganese of more than 95% is recycled, and controls once Mg in the supernatant liquor after heavy manganese
2+eR for emission rate reaches 82.16%.This process of once sinking manganese first makes the mn ion in waste water change into manganous hydroxide, then manganous hydroxide is oxidized to trimanganese tetroxide.
2. the sediment slurry of above-mentioned settlement treatment groove 4 inner bottom part obtains trimanganese tetroxide throw out by sediment slurry discharge port 42 after press filtration, returns trimanganese tetroxide production system and carries out subsequent oxidation washing.The sediment slurry every physical and chemical indexes after washing drying returning production system all reaches manganor manganic oxide used for soft magnetic ferrite standard (GB/T21836-2008).Supernatant liquor once after heavy manganese enters a sewage lagoon 5 after supernatant liquor liquid outlet 44, enter into filtering system 17 again, successively by the first sand filtering device 6, deep bed filter 7, water storage device 8, spiral-flow filter 9, sewage reverse osmosis membrane processing device 12 is entered after laminated filter 10 and cartridge filter 11, after sewage reverse osmosis membrane processing, there is the supernatant liquor of more than 50% to be converted into industrial pure water, its conductance is 240us/cm (tap water conductance about 200 ~ 300us/cm), industrial pure water after sewage reverse osmosis membrane processing can mix with tap water, then RO reverse osmosis membrane treatment system 18 is entered, produce trimanganese tetroxide production system pure water used (conductance≤80us/cm), successively by the second sand filtering device 19 in RO reverse osmosis membrane treatment system 18, carbon post 14 and RO reverse osmosis membrane 13, the trimanganese tetroxide production system that is back to the pure water finally obtained continues to recycle, the dense water finally obtained then is back to aforesaid sewage lagoon 5.Dense water power after sewage reverse osmosis membrane processing is led as 6790us/cm, pH value is 8.5, sodium hydroxide solution (also ammoniacal liquor can be added) and flocculation agent (consumption controlling flocculation agent polyacrylamide is about 0.0015% of wastewater treatment capacity) is added collect dense water in a liquid storage tank 20 after, adjust ph to 11 ~ 12 are carried out secondary and are sunk manganese, supernatant liquor outlet drain supernatant liquor is passed through in equalizing tank 21 after leaving standstill for some time, vitriol oil adjust ph to 7 ~ 8 are added in this supernatant liquor, in supernatant liquor, Mn content is only 0.98mg/L after testing, reach GB8978-1966 " composite wastewater emission standard " prescribed value.Secondary is sunk the sediment slurry after manganese and is delivered in filter-pressing device 16 by sediment slurry outlet and carries out press filtration process, and the Mn-rich slag obtained can return electrolytic manganese factory and recycle manganese element wherein separately as raw materials for production.
Embodiment 2:
A kind of comprehensive reutilization method of trimanganese tetroxide factory effluent of the present invention as shown in Figure 1 and Figure 2, trimanganese tetroxide factory effluent in the present embodiment comprises the waste water such as outer row's mother liquor and evaporating, emitting, dripping or leaking of liquid or gas in certain trimanganese tetroxide factory production process, its Mn after testing
2+content reaches 2.68g/L, and pH value is 5.5 ~ 7; This comprehensive reutilization method specifically comprises the following steps:
1. the trimanganese tetroxide factory effluent in the present embodiment pumps into 30m through leaving standstill after pond 1 collection leaves standstill
3in settlement treatment groove 4, add sodium hydroxide solution (also ammoniacal liquor can be added) and flocculation agent (consumption controlling flocculation agent polyacrylamide is about 0.001% of wastewater treatment capacity) to the supernatant liquor in settlement treatment groove 4 by alkali lye adding trough 2 and flocculation agent adding trough 3 simultaneously, about 9.5 (such as 9 ~ 10) are remained on to adjust the interpolation speed of sodium hydroxide solution by the pH value monitoring waste water, in settlement treatment groove 4, pass into air by ventpipe 41 and air-spreading disk 43 in this process to carry out being oxidized once heavy manganese (this process can save the whipping appts in treatment trough simultaneously, energy efficient), fill rear continuation blowing air in settlement treatment groove 4 to be oxidized and at least to stop ventilation after 30min, after leaving standstill 45min, discharge supernatant liquor by supernatant liquor liquid outlet 44.After testing, Mn in the supernatant liquor of discharge
2+content is down to about 84mg/L, and pH value is 9.In waste water, the manganese of more than 95% is recycled, and controls once Mg in the supernatant liquor after heavy manganese
2+eR for emission rate reaches 76.26%, and this process of once sinking manganese first makes the mn ion in waste water change into manganous hydroxide, then manganous hydroxide is oxidized to trimanganese tetroxide.
2. the sediment slurry of above-mentioned settlement treatment groove 4 inner bottom part obtains trimanganese tetroxide throw out by sediment slurry discharge port 42 after press filtration, returns trimanganese tetroxide production system and carries out subsequent oxidation washing.The sediment slurry every physical and chemical indexes after washing drying returning production system all reaches manganor manganic oxide used for soft magnetic ferrite standard (GB/T21836-2008).Supernatant liquor once after heavy manganese enters a sewage lagoon 5 after supernatant liquor liquid outlet 44, enter into filtering system 17 again, successively by the first sand filtering device 6, deep bed filter 7, water storage device 8, spiral-flow filter 9, sewage reverse osmosis membrane processing device 12 is entered after laminated filter 10 and cartridge filter 11, after sewage reverse osmosis membrane processing, there is the supernatant liquor of more than 50% to be converted into industrial pure water, its conductance is 300 ~ 400us/cm (tap water conductance about 200 ~ 300us/cm), industrial pure water after sewage reverse osmosis membrane processing can mix with tap water, then RO reverse osmosis membrane treatment system 18 is entered, produce trimanganese tetroxide production system pure water used (conductance≤80us/cm), successively by the second sand filtering device 19 in RO reverse osmosis membrane treatment system 18, carbon post 14 and RO reverse osmosis membrane 13, the trimanganese tetroxide production system that is back to the pure water finally obtained continues to recycle, the dense water finally obtained then is back to aforesaid sewage lagoon 5.Dense water power after sewage reverse osmosis membrane processing is led as 6790us/cm, pH value is 8.5, sodium hydroxide solution (also ammoniacal liquor can be added) and flocculation agent (consumption controlling flocculation agent polyacrylamide is about 0.0015% of wastewater treatment capacity) is added collect dense water in a liquid storage tank 20 after, adjust ph to 11 ~ 12 are carried out secondary and are sunk manganese, supernatant liquor outlet drain supernatant liquor is passed through in equalizing tank 21 after leaving standstill for some time, add vitriol oil adjust ph to 7 in this supernatant liquor about, in supernatant liquor, Mn content is only 1.12mg/L after testing, reach GB8978-1966 " composite wastewater emission standard " prescribed value.Secondary is sunk the sediment slurry after manganese and is delivered in filter-pressing device 16 by sediment slurry outlet and carries out press filtration process, and the Mn-rich slag obtained can return electrolytic manganese factory and recycle manganese element wherein separately as raw materials for production.
Claims (10)
1. a comprehensive reutilization method for trimanganese tetroxide factory effluent, comprises the following steps:
(1) first carry out collection to trimanganese tetroxide factory effluent to leave standstill, the trimanganese tetroxide particle suspended in precipitation waste water;
(2) in the supernatant liquor of above-mentioned steps (1) waste water afterwards, add alkali lye and flocculation agent, by monitoring pH value below 11 adjust the interpolation speed of alkali lye, while blowing air or oxygen make oxygenant, once sink manganese;
(3) by after above-mentioned steps (2) once the supernatant liquor of heavy manganese carry out purifying treatment, remaining sediment slurry carries out solid-liquid separation, obtains trimanganese tetroxide throw out, and this trimanganese tetroxide throw out is back to trimanganese tetroxide production system.
2. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 1, it is characterized in that: described alkali lye is sodium hydroxide solution or ammoniacal liquor, and after adding alkali lye, regulate pH value to 9 ~ 10 of waste water, and the manganese of in waste water more than 95% is recycled, and control once Mg in the supernatant liquor after heavy manganese
2+eR for emission rate reaches more than 75%.
3. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 1, is characterized in that: the process of described once heavy manganese first makes the mn ion in waste water change into manganous hydroxide, then manganous hydroxide is oxidized to trimanganese tetroxide.
4. the comprehensive reutilization method of the trimanganese tetroxide factory effluent according to claim 1,2 or 3, it is characterized in that, in described step (3), carry out purifying treatment to supernatant liquor specifically to comprise the following steps: this supernatant liquor is first filtered, then a sewage reverse osmosis membrane processing device is entered, after supernatant liquor after the process of sewage reverse osmosis membrane processing device mixes with tap water, enter a RO reverse osmosis membrane treatment system, the pure water after the process of RO reverse osmosis membrane system is back to trimanganese tetroxide production system as water of productive use.
5. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 4, it is characterized in that, flocculation agent and caustic soda is added in dense water after the process of described sewage reverse osmosis membrane processing device, carry out secondary and sink manganese, secondary sink acid liquid in the supernatant liquor after manganese be adjusted to neutral after outer row, secondary sinks the sediment slurry after manganese to carry out press filtration process and obtains Mn-rich slag.
6. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 5, is characterized in that, the pH value after adding flocculation agent and caustic soda in described dense water is adjusted to 11 ~ 13; Described flocculation agent is polyacrylamide, and the consumption of flocculation agent is only 0.001% ~ 0.002% of wastewater treatment capacity.
7. the comprehensive reutilization method of the trimanganese tetroxide factory effluent according to any one of claim 1 ~ 6, it is characterized in that, described trimanganese tetroxide factory effluent comprises at least one in the bath water in trimanganese tetroxide production process, unnecessary mother liquor overflow water, the waste water reacting cleaning equipment generation when workshop section's equipment failure is keeped in repair, production process in evaporating, emitting, dripping or leaking of liquid or gas waste water, this Manganese in Waste Water ionic concn is at 0.5 ~ 3g/L, and pH value is 5 ~ 7.
8. the comprehensive reutilization method of the trimanganese tetroxide factory effluent according to any one of claim 1 ~ 6, it is characterized in that, described once heavy manganese carries out in a settlement treatment groove, settlement treatment groove is externally connected with alkali lye adding trough and flocculation agent adding trough, breather is provided with in described settlement treatment groove, the bottom of described settlement treatment groove is provided with sediment slurry discharge port, described sediment slurry discharge port is communicated to trimanganese tetroxide production system, and the supernatant liquor liquid outlet of described settlement treatment groove is communicated to heavy manganese supernatant liquor purification system; Described heavy manganese supernatant liquor purification system comprises the filtering system, sewage reverse osmosis membrane processing device and the RO reverse osmosis membrane treatment system that are communicated with successively, and the pure water outlet of described RO reverse osmosis membrane treatment system is to trimanganese tetroxide production system.
9. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 8, it is characterized in that, the breather of described settlement treatment groove comprises ventpipe and is located at the air-spreading disk of below in settlement treatment groove cavity volume, described ventpipe is communicated to air-spreading disk, and described air-spreading disk evenly offers qi-emitting hole; Described settlement treatment groove supernatant liquor liquid outlet be provided with multiple, and multiple supernatant liquor liquid outlets is located at the sidepiece of settlement treatment groove, and is arranged on different height; The hypomere of described settlement treatment groove adopts inverted cone-shaped structure.
10. the comprehensive reutilization method of trimanganese tetroxide factory effluent according to claim 8, it is characterized in that, described filtering system comprises the first sand filtering device, deep bed filter, water storage device, spiral-flow filter, laminated filter and the cartridge filter that are communicated with successively; The industrial pure water outlet of described sewage reverse osmosis membrane processing device is to described RO reverse osmosis membrane treatment system, and described RO reverse osmosis membrane treatment system comprises the second sand filtering device, carbon post and the RO reverse osmosis membrane that are communicated with successively; The dense water out of described sewage reverse osmosis membrane processing device is communicated to a dense depositing in water manganese treatment system, and described dense depositing in water manganese treatment system comprises secondary settlement tower, and described secondary settlement tower is provided with dense water fluid inlet, alkali lye adds mouth and flocculation agent adds mouth.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236636A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Gold ore manganese-containing wastewater treatment method |
| CN106399701A (en) * | 2016-08-31 | 2017-02-15 | 中信大锰矿业有限责任公司 | Recycling method for soluble manganese in electrolytic manganese slag |
| CN107488787A (en) * | 2017-08-10 | 2017-12-19 | 云南龙蕴科技环保股份有限公司 | A kind of method that manganese is reclaimed in sewage containing manganese |
| CN109179794A (en) * | 2018-11-19 | 2019-01-11 | 四川中哲新材料科技有限公司 | A kind of waste water treatment process of mangano-manganic oxide |
| CN109231584A (en) * | 2018-11-19 | 2019-01-18 | 四川中哲新材料科技有限公司 | A kind of mangano-manganic oxide production waste discharge processing system |
| CN111606487A (en) * | 2020-05-27 | 2020-09-01 | 长沙矿冶研究院有限责任公司 | Method for continuously treating and recycling manganese and ammonia nitrogen resources from electrolytic manganese wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0976684A1 (en) * | 1998-07-31 | 2000-02-02 | Gesellschaft für Biotechnologische Forschung mbH (GBF) | Pilot water treatment plant |
| JP2006255671A (en) * | 2005-03-18 | 2006-09-28 | Kurita Water Ind Ltd | Membrane separation method of manganese in soluble manganese-containing water |
| CN102417259A (en) * | 2011-12-07 | 2012-04-18 | 北京碧水源科技股份有限公司 | Method for removing iron and manganese from water body in membrane combination process |
| CN102424491A (en) * | 2011-10-27 | 2012-04-25 | 中南大学 | Treatment method for recovering and utilizing trimanganese tetroxide industrial wastewater |
| CN203683190U (en) * | 2013-12-19 | 2014-07-02 | 上海宝钢磁业有限公司 | Manganese removal device for high-manganese steel pickling waste liquid |
-
2015
- 2015-03-19 CN CN201510121416.3A patent/CN104671507B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0976684A1 (en) * | 1998-07-31 | 2000-02-02 | Gesellschaft für Biotechnologische Forschung mbH (GBF) | Pilot water treatment plant |
| JP2006255671A (en) * | 2005-03-18 | 2006-09-28 | Kurita Water Ind Ltd | Membrane separation method of manganese in soluble manganese-containing water |
| CN102424491A (en) * | 2011-10-27 | 2012-04-25 | 中南大学 | Treatment method for recovering and utilizing trimanganese tetroxide industrial wastewater |
| CN102417259A (en) * | 2011-12-07 | 2012-04-18 | 北京碧水源科技股份有限公司 | Method for removing iron and manganese from water body in membrane combination process |
| CN203683190U (en) * | 2013-12-19 | 2014-07-02 | 上海宝钢磁业有限公司 | Manganese removal device for high-manganese steel pickling waste liquid |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236636A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Gold ore manganese-containing wastewater treatment method |
| CN106399701A (en) * | 2016-08-31 | 2017-02-15 | 中信大锰矿业有限责任公司 | Recycling method for soluble manganese in electrolytic manganese slag |
| CN107488787A (en) * | 2017-08-10 | 2017-12-19 | 云南龙蕴科技环保股份有限公司 | A kind of method that manganese is reclaimed in sewage containing manganese |
| CN109179794A (en) * | 2018-11-19 | 2019-01-11 | 四川中哲新材料科技有限公司 | A kind of waste water treatment process of mangano-manganic oxide |
| CN109231584A (en) * | 2018-11-19 | 2019-01-18 | 四川中哲新材料科技有限公司 | A kind of mangano-manganic oxide production waste discharge processing system |
| CN109231584B (en) * | 2018-11-19 | 2021-12-07 | 四川中哲新材料科技有限公司 | Waste discharge treatment system for manganous manganic oxide production |
| CN111606487A (en) * | 2020-05-27 | 2020-09-01 | 长沙矿冶研究院有限责任公司 | Method for continuously treating and recycling manganese and ammonia nitrogen resources from electrolytic manganese wastewater |
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