CN103936190A - Barium hydroxide treatment method with zero discharging of lead-acid storage battery wastewater - Google Patents
Barium hydroxide treatment method with zero discharging of lead-acid storage battery wastewater Download PDFInfo
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- CN103936190A CN103936190A CN201410128498.XA CN201410128498A CN103936190A CN 103936190 A CN103936190 A CN 103936190A CN 201410128498 A CN201410128498 A CN 201410128498A CN 103936190 A CN103936190 A CN 103936190A
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Abstract
The invention discloses a barium hydroxide treatment method with zero discharging of lead-acid storage battery wastewater. According to the method, barium hydroxide is adopted for neutralization and lead precipitation reaction which are accomplished at one time, two harmful waste matters are directly transformed into precipitate, the precipitate is subjected to flocculated by using a flocculating agent so as to obtain clean water with very low salt content and impurity content, the clean water can be recycled, and the desalting cost is low; by utilizing the property that barium sulfate is hard to dissolve, lead in the precipitate is dissolved out through a lead solvent, and then barium sulfate is left; the dissolved-out lead is reused as electrolytic lead after electrolysis; the barium sulfate is converted into barium hydroxide for circulation after being treated. The method is free of wastewater discharge in the whole treatment process, achieves zero discharging and is low in production cost, low in energy consumption, small in environmental pollution and applicable to industrial production.
Description
Technical field
The present invention relates to a kind for the treatment of process of lead acid cell waste water, particularly a kind of hydrated barta treatment process of lead acid cell wastewater zero discharge.
Background technology
Lead acid cell is manufactured in production process and is produced a large amount of acid heavy metal trade effluents, if unprocessed any discharge brings great harm must to environment and society.Lead in waste water, cadmium are heavy metal element; it is first kinds of pollution matter; in workshop or workshop treatment facility discharge outlet must reach emission request; therefore the improvement of the Storage Battery Industry in China waste water is a vital task of environment protection with comprehensive utilization, and it has great significance to the orderly development that ensures people's health and industrial and agricultural production.
At present the treatment process of heavy metal wastewater thereby is mainly comprised to chemical precipitation method, ion-exchange-resin process, electrolytic process, active carbon adsorption, reverse osmosis method, electroosmose process, evaporation concentration method and biological process etc., wherein chemical precipitation method is simple, be widely used, by adding NaOH, lime or Na
2cO
3deng the pH that regulates waste water, make heavy metal ion form precipitation, then adopt the subsequent techniques such as precipitation or filtration that throw out is separated with waste water, thereby reach the object of purifying liquid waste.
Common lead acid cell waste water chemical precipitation method is as Ca(OH)
2in and method of wastewater treatment.
Ca(OH)
2in and method of wastewater treatment main process be:
1, preliminary sedimentation: lead acid cell waste water is introduced in settling tank and carried out preliminary sedimentation, make the leaded refuse precipitation in waste water.
2, unslaked lime dissolves: unslaked lime is placed in to dissolving tank, its unslaked lime is fully reacted by gas stirring or gas stirring mode with water, because unslaked lime reacts generation Ca(OH with water)
2, and Ca(OH)
2solubleness is very little, therefore needs to add excessive unslaked lime to use while stirring in water.
3, pH value regulates: by entering equalizing tank through settling tank precipitation lead acid cell waste water later, by adding Ca(OH)
2and water mixture, one time PH regulates, and makes the heavy metal element (as lead, cadmium etc.) in waste water form throw out, also generates CaSO simultaneously
4throw out, after sediment separate out, clear water discharge.
The shortcoming that the method exists is: Ca(OH)
2solubleness is low, with excessive Ca(OH)
2just can play good neutralization and make the lead ion precipitation in water; A large amount of CaSO
4precipitation and Ca(OH)
2solid and leaded thing precipitation mix, and cannot separate, and cause a large amount of leaded refuses to produce; Operation cannot realize automatization; Cannot carry out nanofiltration or other purifying treatment, reusing rate is very low.
The disclosure of the invention of CN101197458A a kind of recovery and processing technique for waste lead acid accumulator, lead waste water is directly imported to common Waste Water Treatment and carry out wastewater treatment, simple to operate, but because common Waste Water Treatment mostly is activated sludge process, the microorganism lead of can not degrading, be enriched in microbe the cleaning action of meeting destroy microorganisms.
Summary of the invention
The object of the present invention is to provide a kind of hydrated barta treatment process of lead acid cell wastewater zero discharge, carry out acid-base neutralisation and plumbous precipitin reaction with hydrated barta, one step completes, directly two kinds of refuses are formed to throw out, and use flocculation agent flocculation sediment, obtain the clear water that salts contg and foreign matter content are very low, clear water can be used as reuse water, and desalination cost is low; The character of utilizing barium sulfate indissoluble by the lead in throw out by plumbous lysate stripping, remaining barium sulfate; Dissolve the lead, by electrolysis, scrap lead is electrolyzed to produce to electrolytic lead re-using; Barium sulfate can again change into hydrated barta and recycle.
The technical solution adopted for the present invention to solve the technical problems is:
A hydrated barta treatment process for lead acid cell wastewater zero discharge, comprises the steps:
(1) primary sedimentation: lead acid cell waste water is passed into by primary sedimentation basin bottom, through tube settling district, discharge and enter equalizing tank from primary sedimentation basin top, collect the plumbous mud in primary sedimentation basin bottom, form mud cake through plate-and-frame filter press press filtration, filtrate enters equalizing tank;
Primary sedimentation is that lead acid cell waste water is carried out to preliminary sedimentation, and oarse-grained leaded refuse in waste water is precipitated by the mode of natural subsidence.The leaded particle of macrobead first precipitates and alleviates subsequent disposal difficulty.
(2) PH regulate: to the PH to 5-7 that passes into barium hydroxide solution in equalizing tank and regulate waste water;
It is in order to prevent Ba(OH that a PH regulates)
2excessive, need in PH equalizing tank, carry out fine setting to pH value between 5-7, avoided barium ion excessive.In the process of a PH adjusting, hydrated barta not only carries out acid-base neutralisation reaction, and while and plumbous precipitin reaction, and a step completes, and forms plumbous precipitation and barium sulfate precipitate simultaneously.
(3) secondary sedimentation: staticly settle 1-2 hour, then plate-and-frame filter press once filters, collects the mud cake separating, and filtrate enters next step.
(4) secondary PH regulate: to once filter after filtrate in pass into sodium hydroxide solution regulate PH to 7-9, leave standstill 1-2h.
Secondary PH regulates, and pH value ensures at 7-9, be for ensure a PH regulate after in filtrate still residual a small amount of lead ion can be generated lead hydroxide precipitation by reaction and remove, ensure the validity of deleading, leave standstill 1-2h and ensure the abundant formation of lead hydroxide precipitation.
(5) flocculation reaction: add flocculation agent, stirring and evenly mixing in the filtrate after regulating to secondary PH.While adjusting due to secondary PH, the lead ion of the overwhelming majority has been converted into macrobead precipitation and has been removed, therefore the deposit seeds that secondary PH produces after regulating is little, precipitation capacity is also less, and then add flocculation agent flocculation reaction, after can effectively secondary PH being regulated, producing the effective flocculation sediment of small-particle solid substance gets off, in addition flocculation agent also can be removed colloidalmaterial and some other detrimental impurity in waste water, ensures clear water water quality.
(6) three precipitations: staticly settle 2-10 hour, then plate-and-frame filter press carries out secondary filtration, collect the mud cake separating, and filtrate enters in clean water basin as reuse water.
Filtrate enters the effect that has realized zero release in clean water basin as reuse water, two kinds of method reuses of this reuse moisture, can direct reuse as water coolant, rinse water etc. in store battery production process, (wherein salts contg is lower, therefore can be directly used in water coolant, rinse water etc.), also can adopt the membrane processing method desalting treatment of electrodialysis or reverse osmosis to need the operation production and applications such as pure water for the preparation of lead acid cell lead plaster, electrolyte quota etc.
(7) plumbous stripping: combining step (1), step (3) and step (6) gained mud cake, in mud cake, add plumbous lysate, stir 30-300 minute, then leave standstill 10-200 minute, to filter, filtrate is plumbous dissolution fluid, filter residue is barium sulfate;
(8) electrolytic recovery lead: by plumbous dissolution fluid electrolysis, separate out electrolytic lead at negative electrode, the remaining liq after recovery electrolysis, to storage tank, comes back to step (7) and uses as plumbous lysate.
As preferably, the Ba(OH adding in step (2))
2solution temperature is controlled at 40 DEG C-90 DEG C, and mass concentration is 5-40%.Ba(OH)
2solubleness at 40 DEG C-90 DEG C is higher, therefore, and Ba(OH)
2solution temperature is controlled at 40 DEG C-90 DEG C, like this at same Ba(OH)
2under consumption, can reduce as much as possible the consumption of water.
As preferably, in step (4), sodium hydroxide solution mass concentration is 10-50%.
As preferably, one or more described in step (5) in selection of polymeric flocculants polymerize aluminum chloride, polyacrylamide, tertiary sodium phosphate, by every 100 tons of waste water, flocculation agent addition is: polymerize aluminum chloride 0.3-0.6kg, polyacrylamide 0.05-0.07kg, tertiary sodium phosphate 0.5-1kg.
As preferably, in step (7), plumbous lysate is selected H
2siF
6solution, HBF
4one in solution, NaOH solution, H
2siF
6solution and HBF
4the mass concentration of solution is 15-25%, and the mass concentration of NaOH solution is 10%-40%.
As preferably, the consumption of described plumbous lysate is the plumbous lysate of every kilogram of mud cake 3-6L.The consumption of plumbous lysate will ensure abundant the lead in mud cake stripping, again can not be too much.
As preferably, in step (8), electrolytic parameter is: voltage 1.8-2.6 V, current density 150-200A/m
2, electrolyte temperature is controlled at 25-60 DEG C, and electrolysis time is controlled at 4 hours-6 hours.
As preferably, step (7) gained barium sulfate is prepared into Ba(OH)
2solution recycling, concrete steps are:
Under a, 40-60 DEG C condition, the sodium carbonate solution of preparation 40-50wt%, is then cooled to 30-40 DEG C and forms saturated sodium carbonate solution.
Being cooled to 30-40 DEG C, to form saturated sodium carbonate solution be the participation reaction that sodium carbonate solution is still state of saturation when ensureing that next step reaction temperature is 25-30 DEG C.
B, barium sulfate is added in reactor, then add the saturated sodium carbonate solution of step a, control temperature of reaction is 25-30 DEG C, barium sulfate: the mol ratio=1:25-30 of sodium carbonate, and stirring reaction 10-60 minute, static 30-60 minute, filters, and collects solids.
Control barium sulfate: the mol ratio=1:25-30 of sodium carbonate, it is in order to ensure that barium sulfate can be converted into barium carbonate that temperature of reaction is 25-30 DEG C.C (CO3
2-)/c (SO4
2-) be greater than Ksp (BaCO
3)/Ksp (BaSO
4), (at 25 DEG C, the solubility product Ksp of barium sulfate is 1.07 × 10
-10, the solubility product 2.58 × 10 of barium carbonate
-9, 2.58 × 10
-9) ÷ (1.07 × 10
-10)=24.1, work as CO3
2-concentration be SO4
2-more than 24.1 times, BaSO
4just can be converted into BaCO
3.
C, solids is rejoined in reactor, then add and the saturated sodium carbonate solution of step b equivalent, control temperature of reaction is 25-30 DEG C, stirring reaction 10-60 minute, and static 30-60 minute, filters, and collects solids; Repeat like this, by solids saturated sodium carbonate solution processing, just barium sulfate to be converted into barium carbonate completely;
The operation of d, repeating step c 1-3 time, collects solids and is barium carbonate, and barium carbonate, through calcining, obtains Ba(OH after adding water)
2solution.Approximately 1450 DEG C-1800 DEG C of calcining temperatures.
E, combining step b, to the filtrate that steps d produces, pass into excess carbon dioxide, are cooled to 0-10 DEG C of crystallisation by cooling, filter, and collect crystallization and are sodium bicarbonate, and sodium bicarbonate thermal degradation obtains sodium carbonate for step a preparation sodium carbonate solution.In filtrate, be the solution that contains a large amount of sodium carbonate and a small amount of sodium sulfate, due to sodium carbonate and sodium sulfate dissolubility difference little, and therefore, sodium bicarbonate and sodium sulfate poor solubility, apart from large, pass into excess carbon dioxide and transfer sodium carbonate to sodium bicarbonate, then cooling, sodium bicarbonate can be separated out in a large number, and then sodium bicarbonate thermal degradation is sodium carbonate, and most sodium carbonate can recycle, be filled into the filtrate evaporate to dryness after sodium bicarbonate, can not produce discharge of wastewater.
Barium sulfate precipitate is prepared into Ba(OH by the present invention)
2solution recycling, the utilization ratio of raising resource.Barium sulfate precipitate is prepared into Ba(OH)
2the method of solution is simple, and production cost is low, is applicable to suitability for industrialized production.
As preferably, once filter and the filter screen size of secondary filtration at 300-800 order.
The invention has the beneficial effects as follows:
1, only can neutralize and plumbous precipitin reaction with hydrated barta, a step completes simultaneously, directly two kinds of refuses of sulfuric acid and lead ion is formed to throw outs, the character of utilizing barium sulfate indissoluble by the lead in throw out by plumbous lysate stripping, simple.
2, use flocculation agent flocculation sediment, obtain the clear water that salts contg and foreign matter content are very low, clear water can be used as reuse water, and desalination cost is low.
3, dissolve the lead, by electrolysis, scrap lead is electrolyzed to produce to electrolytic lead re-using; Barium sulfate can again change into hydrated barta and recycle.
4, whole treating processes non-wastewater discharge, has realized zero release, and production cost is low, and energy consumption is low, little to environmental hazard, is suitable for suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the present invention's process flow sheet of the present invention.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, raw material and the equipment etc. adopting all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Embodiment 1:
A hydrated barta treatment process for lead acid cell wastewater zero discharge, as shown in Figure 1, comprises the steps:
(1) primary sedimentation: lead acid cell waste water is passed into by primary sedimentation basin bottom, through tube settling district (adopting the method for arranging of existing routine), discharge and enter equalizing tank from primary sedimentation basin top, collect the plumbous mud in primary sedimentation basin bottom, form mud cake (water ratio 10% left and right) through plate-and-frame filter press press filtration, filtrate enters equalizing tank.
(2) PH regulate: to the PH to 5 that passes into barium hydroxide solution in equalizing tank and regulate waste water; The Ba(OH adding)
2solution temperature is controlled at 40 DEG C, and mass concentration is 5%.
(3) secondary sedimentation: staticly settle 2 hours, then plate-and-frame filter press once filters, filter screen size, at 300 orders, is collected the mud cake (water ratio 10% left and right) separating, and filtrate enters next step.
(4) secondary PH regulate: to once filter after filtrate in pass into mass concentration be 10% sodium hydroxide solution regulate PH to 7, leave standstill 2h.
(5) flocculation reaction: add flocculation agent, stirring and evenly mixing in the filtrate after regulating to secondary PH; Flocculation agent is polymerize aluminum chloride, and by every 100 tons of waste water, polymerize aluminum chloride addition is 0.6kg.
(6) three precipitations: staticly settle 2 hours, then plate-and-frame filter press carries out secondary filtration, filter screen size is at 300 orders, collect the mud cake (water ratio 10% left and right) separating, filtrate enters in clean water basin as reuse water, two kinds of method reuses of this reuse moisture: can direct reuse as water coolant, rinse water etc. in store battery production process, also can adopt membrane processing method (existing technique) desalting treatment of electrodialysis or reverse osmosis to need the operation production and applications such as pure water for the preparation of lead acid cell lead plaster, electrolyte quota etc.
(7) plumbous stripping: combining step (1), step (3) and step (6) gained mud cake, in mud cake, add plumbous lysate, stir 30 minutes, then leave standstill 200 minutes, to filter, filtrate is plumbous dissolution fluid, filter residue is barium sulfate; Plumbous lysate is selected H
2siF
6solution, H
2siF
6concentration of polymer solution is 25%, H
2siF
6the consumption of solution is every kilogram of mud cake 3L.
(8) electrolytic recovery lead: by plumbous dissolution fluid electrolysis, separate out electrolytic lead at negative electrode, the remaining liq after recovery electrolysis, to storage tank, comes back to step (7) and uses as plumbous lysate, this the meeting loss to some extent in electrolytic process of plumbous lysate, the outer leading lysate of part of loss is supplied.Electrolytic parameter is: voltage 1.8V, current density 150A/m
2, electrolyte temperature is controlled at 25 DEG C, and electrolysis time is controlled at 6 hours.
Embodiment 2:
A hydrated barta treatment process for lead acid cell wastewater zero discharge, as shown in Figure 1, comprises the steps:
(1) primary sedimentation: lead acid cell waste water is passed into by primary sedimentation basin bottom, through tube settling district (adopting the method for arranging of existing routine), discharge and enter equalizing tank from primary sedimentation basin top, collect the plumbous mud in primary sedimentation basin bottom, form mud cake (water ratio 10% left and right) through plate-and-frame filter press press filtration, filtrate enters equalizing tank.
(2) PH regulate: to the PH to 7 that passes into barium hydroxide solution in equalizing tank and regulate waste water; The Ba(OH adding)
2solution temperature is controlled at 90 DEG C, and mass concentration is 40%.
(3) secondary sedimentation: staticly settle 1 hour, then plate-and-frame filter press once filters, filter screen size, at 800 orders, is collected the mud cake (water ratio 10% left and right) separating, and filtrate enters next step.
(4) secondary PH regulate: to once filter after filtrate in pass into mass concentration be 50% sodium hydroxide solution regulate PH to 9, leave standstill 1h.
(5) flocculation reaction: add flocculation agent, stirring and evenly mixing in the filtrate after regulating to secondary PH; Flocculation agent is polyacrylamide+tertiary sodium phosphate, and by every 100 tons of waste water, polyacrylamide addition is 0.05kg, and tertiary sodium phosphate addition is that 0.5-1kg(the present embodiment is 0.6kg).
(6) three precipitations: staticly settle 10 hours, then plate-and-frame filter press carries out secondary filtration, filter screen size is at 800 orders, collect the mud cake (water ratio 10% left and right) separating, filtrate enters in clean water basin as reuse water, two kinds of method reuses of this reuse moisture: can direct reuse as water coolant, rinse water etc. in store battery production process, also can adopt membrane processing method (existing technique) desalting treatment of electrodialysis or reverse osmosis to need the operation production and applications such as pure water for the preparation of lead acid cell lead plaster, electrolyte quota etc.
(7) plumbous stripping: combining step (1), step (3) and step (6) gained mud cake, in mud cake, add plumbous lysate, stir 300 minutes, then leave standstill 10 minutes, to filter, filtrate is plumbous dissolution fluid, filter residue is barium sulfate; Plumbous lysate is selected HBF
4solution, HBF
4the mass concentration of solution is 15%, HBF
4the consumption of solution is every kilogram of mud cake 4.5L.
(8) electrolytic recovery lead: by plumbous dissolution fluid electrolysis, separate out electrolytic lead at negative electrode, the remaining liq after recovery electrolysis, to storage tank, comes back to step (7) and uses as plumbous lysate, this the meeting loss to some extent in electrolytic process of plumbous lysate, the outer leading lysate of part of loss is supplied.Electrolytic parameter is: voltage 2.6 V, current density 200A/m
2, electrolyte temperature is controlled at 60 DEG C, and electrolysis time is controlled at 4 hours.
Step (7) gained barium sulfate precipitate is prepared into Ba(OH)
2solution recycling, concrete steps are:
Under a, 40 DEG C of conditions, the sodium carbonate solution of preparation 40wt%, is then cooled to 30 DEG C and forms saturated sodium carbonate solution;
B, barium sulfate is added in reactor, then add the saturated sodium carbonate solution of step a, controlling temperature of reaction is 25 DEG C, barium sulfate: the mol ratio=1:25 of sodium carbonate, and stirring reaction 10 minutes, static 60 minutes, filter, collect solids;
C, solids is rejoined in reactor, then add and the saturated sodium carbonate solution of step b equivalent, controlling temperature of reaction is 25 DEG C, stirring reaction 60 minutes, and static 30 minutes, filter, collect solids;
The operation of d, repeating step c 3 times, collects solids and is barium carbonate, and barium carbonate, through calcining, obtains Ba(OH after adding water)
2solution, is reused for step (5);
E, combining step b, to the filtrate that steps d produces, pass into excess carbon dioxide, are cooled to 0 DEG C of crystallisation by cooling, filter, and collect crystallization and be sodium bicarbonate, filtrate evaporate to dryness, sodium bicarbonate thermal degradation obtains sodium carbonate for step a preparation sodium carbonate solution.
Embodiment 3:
A hydrated barta treatment process for lead acid cell wastewater zero discharge, as shown in Figure 1, comprises the steps:
(1) primary sedimentation: lead acid cell waste water is passed into by primary sedimentation basin bottom, through tube settling district (adopting the method for arranging of existing routine), discharge and enter equalizing tank from primary sedimentation basin top, collect the plumbous mud in primary sedimentation basin bottom, form mud cake (water ratio 10% left and right) through plate-and-frame filter press press filtration, filtrate enters equalizing tank.
(2) PH regulate: to the PH to 6 that passes into barium hydroxide solution in equalizing tank and regulate waste water; The Ba(OH adding)
2solution temperature is controlled at 60 DEG C, and mass concentration is 20%.
(3) secondary sedimentation: staticly settle 1.5 hours, then plate-and-frame filter press once filters, filter screen size, at 500 orders, is collected the mud cake (water ratio 10% left and right) separating, and filtrate enters next step.
(4) secondary PH regulate: to once filter after filtrate in pass into mass concentration be 30% sodium hydroxide solution regulate PH to 8, leave standstill 1.5h.
(5) flocculation reaction: add flocculation agent, stirring and evenly mixing in the filtrate after regulating to secondary PH; The combination of selection of polymeric flocculants polymerize aluminum chloride and polyacrylamide, by every 100 tons of waste water, polymerize aluminum chloride addition is 0.3kg, polyacrylamide addition is 0.07kg.
(6) three precipitations: staticly settle 5 hours, then plate-and-frame filter press carries out secondary filtration, filter screen size is at 500 orders, collect the mud cake (water ratio 10% left and right) separating, filtrate enters in clean water basin as reuse water, two kinds of method reuses of this reuse moisture: can direct reuse as water coolant, rinse water etc. in store battery production process, also can adopt membrane processing method (existing technique) desalting treatment of electrodialysis or reverse osmosis to need the operation production and applications such as pure water for the preparation of lead acid cell lead plaster, electrolyte quota etc.
(7) plumbous stripping: combining step (1), step (3) and step (6) gained mud cake, in mud cake, add plumbous lysate, stir 60 minutes, then leave standstill 100 minutes, to filter, filtrate is plumbous dissolution fluid, filter residue is barium sulfate; Plumbous lysate is NaOH solution, and the mass concentration of NaOH solution is that 10%-40%(the present embodiment selects 30%), the consumption of NaOH solution is every kilogram of mud cake 6L.
(8) electrolytic recovery lead: by plumbous dissolution fluid electrolysis, separate out electrolytic lead at negative electrode, the remaining liq after recovery electrolysis, to storage tank, comes back to step (7) and uses as plumbous lysate, this the meeting loss to some extent in electrolytic process of plumbous lysate, the outer leading lysate of part of loss is supplied.Electrolytic parameter is: voltage 2V, current density 180A/m
2, electrolyte temperature is controlled at 50 DEG C, and electrolysis time is controlled at 5 hours.
Step (7) gained barium sulfate precipitate is prepared into Ba(OH)
2solution recycling, concrete steps are:
Under a, 60 DEG C of conditions, the sodium carbonate solution of preparation 50wt%, is then cooled to 40 DEG C and forms saturated sodium carbonate solution;
B, barium sulfate is added in reactor, then add the saturated sodium carbonate solution of step a, controlling temperature of reaction is 30 DEG C, barium sulfate: the mol ratio=1:30 of sodium carbonate, and stirring reaction 60 minutes, static 30 minutes, filter, collect solids;
C, solids is rejoined in reactor, then add and the saturated sodium carbonate solution of step b equivalent, controlling temperature of reaction is 30 DEG C, stirring reaction 10 minutes, and static 60 minutes, filter, collect solids;
The operation of d, repeating step c 1 time, collects solids and is barium carbonate, and barium carbonate, through calcining, obtains Ba(OH after adding water)
2solution, is reused for step (5);
E, combining step b, to the filtrate that steps d produces, pass into excess carbon dioxide, are cooled to 10 DEG C of crystallisation by cooling, filter, and collect crystallization and be sodium bicarbonate, filtrate evaporate to dryness, sodium bicarbonate thermal degradation obtains sodium carbonate for step a preparation sodium carbonate solution.
Flocculation sediment gained clear water water quality of the present invention meets " urban sewage reutilization industry water standard " (GB/T19923-2005) requirement of standard, and method of the present invention can realize the target of lead storage battery production process wastewater zero discharge.
The present invention only can neutralize and plumbous precipitin reaction with hydrated barta simultaneously, and a step completes, and directly sulfuric acid and two kinds of refuses of lead ion is formed to throw outs, the character of utilizing barium sulfate indissoluble by the lead in throw out by plumbous lysate stripping, simple.Use flocculation agent flocculation sediment, obtain the clear water that salts contg and foreign matter content are very low, clear water can be used as reuse water, and desalination cost is low.Dissolve the lead, by electrolysis, scrap lead is electrolyzed to produce to electrolytic lead re-using; Barium sulfate can again change into hydrated barta and recycle.Whole treating processes non-wastewater discharge, has realized zero release, and production cost is low, and energy consumption is low, little to environmental hazard, is suitable for suitability for industrialized production.
Above-described embodiment is preferably scheme of one of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (9)
1. a hydrated barta treatment process for lead acid cell wastewater zero discharge, is characterized in that, comprises the steps:
(1) primary sedimentation: lead acid cell waste water is passed into by primary sedimentation basin bottom, through tube settling district, discharge and enter equalizing tank from primary sedimentation basin top, collect the plumbous mud in primary sedimentation basin bottom, form mud cake through plate-and-frame filter press press filtration, filtrate enters equalizing tank;
(2) PH regulate: to the PH to 5-7 that passes into barium hydroxide solution in equalizing tank and regulate waste water;
(3) secondary sedimentation: staticly settle 1-2 hour, then plate-and-frame filter press once filters, collects the mud cake separating, and filtrate enters next step;
(4) secondary PH regulate: to once filter after filtrate in pass into sodium hydroxide solution regulate PH to 7-9, leave standstill 1-2h;
(5) flocculation reaction: add flocculation agent, stirring and evenly mixing in the filtrate after regulating to secondary PH;
(6) three precipitations: staticly settle 2-10 hour, then plate-and-frame filter press carries out secondary filtration, collect the mud cake separating, and filtrate enters in clean water basin as reuse water;
(7) plumbous stripping: combining step (1), step (3) and step (6) gained mud cake, in mud cake, add plumbous lysate, stir 30-300 minute, then leave standstill 10-200 minute, to filter, filtrate is plumbous dissolution fluid, filter residue is barium sulfate;
(8) electrolytic recovery lead: by plumbous dissolution fluid electrolysis, separate out electrolytic lead at negative electrode, the remaining liq after recovery electrolysis, to storage tank, comes back to step (7) and uses as plumbous lysate.
2. hydrated barta treatment process according to claim 1, is characterized in that: the Ba(OH adding in step (2))
2solution temperature is controlled at 40 DEG C-90 DEG C, and mass concentration is 5-40%.
3. hydrated barta treatment process according to claim 1 and 2, is characterized in that: in step (4), sodium hydroxide solution mass concentration is 10-50%.
4. hydrated barta treatment process according to claim 1 and 2, it is characterized in that: one or more described in step (5) in selection of polymeric flocculants polymerize aluminum chloride, polyacrylamide, tertiary sodium phosphate, by every 100 tons of waste water, flocculation agent addition is: polymerize aluminum chloride 0.3-0.6kg, polyacrylamide 0.05-0.07kg, tertiary sodium phosphate 0.5-1kg.
5. hydrated barta treatment process according to claim 1 and 2, is characterized in that: in step (7), plumbous lysate is selected H
2siF
6solution, HBF
4one in solution, NaOH solution, H
2siF
6solution and HBF
4the mass concentration of solution is 12-25%, and the mass concentration of NaOH solution is 10%-40%.
6. hydrated barta treatment process according to claim 5, is characterized in that: the consumption of described plumbous lysate is the plumbous lysate of every kilogram of mud cake 3-6L.
7. hydrated barta treatment process according to claim 1 and 2, is characterized in that: in step (8), electrolytic parameter is: voltage 1.8-2.6 V, current density 150-200A/m
2, electrolyte temperature is controlled at 25-60 DEG C, and electrolysis time is controlled at 4 hours-6 hours.
8. hydrated barta treatment process according to claim 1 and 2, is characterized in that: step (7) gained barium sulfate is prepared into Ba(OH)
2solution recycling, concrete steps are:
Under a, 40-60 DEG C condition, the sodium carbonate solution of preparation 40-50wt%, is then cooled to 30-40 DEG C and forms saturated sodium carbonate solution;
B, barium sulfate is added in reactor, then add the saturated sodium carbonate solution of step a, control temperature of reaction is 25-30 DEG C, barium sulfate: the mol ratio=1:25-30 of sodium carbonate, and stirring reaction 10-60 minute, static 30-60 minute, filters, and collects solids;
C, solids is rejoined in reactor, then add and the saturated sodium carbonate solution of step b equivalent, control temperature of reaction is 25-30 DEG C, stirring reaction 10-60 minute, and static 30-60 minute, filters, and collects solids;
The operation of d, repeating step c 1-3 time, collects solids and is barium carbonate, and barium carbonate, through calcining, obtains Ba(OH after adding water)
2solution;
E, combining step b, to the filtrate that steps d produces, pass into excess carbon dioxide, are cooled to 0-10 DEG C of crystallisation by cooling, filter, and collect crystallization and are sodium bicarbonate, and sodium bicarbonate thermal degradation obtains sodium carbonate for step a preparation sodium carbonate solution.
9. hydrated barta treatment process according to claim 1 and 2, is characterized in that: once the filter screen size of filtration and secondary filtration is at 300-800 order.
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| CN115353143A (en) * | 2022-08-29 | 2022-11-18 | 太和县大华能源科技有限公司 | Treatment method for extracting lead acid from waste acid of waste lead-acid battery |
| CN115353143B (en) * | 2022-08-29 | 2023-04-25 | 太和县大华能源科技有限公司 | Treatment method for extracting lead acid from waste acid of waste lead acid battery |
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