CN109301373A - A kind of device and method of lead-acid accumulator electrolyte cycling and reutilization - Google Patents
A kind of device and method of lead-acid accumulator electrolyte cycling and reutilization Download PDFInfo
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- CN109301373A CN109301373A CN201811368963.1A CN201811368963A CN109301373A CN 109301373 A CN109301373 A CN 109301373A CN 201811368963 A CN201811368963 A CN 201811368963A CN 109301373 A CN109301373 A CN 109301373A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 121
- 239000002253 acid Substances 0.000 title claims abstract description 110
- 230000001351 cycling effect Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 22
- 239000012528 membrane Substances 0.000 claims abstract description 344
- 238000001728 nano-filtration Methods 0.000 claims abstract description 249
- 239000007788 liquid Substances 0.000 claims abstract description 131
- 239000000919 ceramic Substances 0.000 claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 42
- 239000012141 concentrate Substances 0.000 claims description 32
- 238000003860 storage Methods 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- -1 phosphoric acid hydrogen Chemical class 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 7
- 229920001249 ethyl cellulose Polymers 0.000 claims description 7
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004579 marble Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 239000011269 tar Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 229910052742 iron Inorganic materials 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 13
- 229910001431 copper ion Inorganic materials 0.000 description 13
- 229910001437 manganese ion Inorganic materials 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 3
- 238000004879 turbidimetry Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to lead-acid accumulator recovery technology fields, disclose a kind of device of lead-acid accumulator electrolyte cycling and reutilization, it successively include pretreatment unit, sheet frame booster pump, plate and frame filter press, sheet frame produces flow container, for producing the pre-heating system of liquid the pre-heat treatment to sheet frame, ceramic membrane booster pump, ceramic membrane group, ceramic membrane produces flow container, nanofiltration membrane NB1 booster pump, nanofiltration membrane NB1 group, nanofiltration membrane NB1 produces flow container, nanofiltration membrane NB2 booster pump, nanofiltration membrane NB2 group, nanofiltration membrane NB2 produces flow container, nanofiltration membrane NC film booster pump, nanofiltration membrane NC film, nanofiltration membrane NC film produces flow container and matched deionized water production equipment.Utilize the device of the lead-acid accumulator electrolyte cycling and reutilization, pass through the adjustment of technological parameter, the qualified liquid that produces of output is routed directly to lead-acid accumulator complex acid station, carry out the preparation of new battery electrolyte, device is efficient, stable, feasible, the high efficiente callback of lead-acid accumulator electrolyte is realized, the construction of lead-acid accumulator circulation industrial chain is promoted.
Description
Technical field
The invention belongs to lead-acid accumulator utilization technology field, in particular to a kind of lead-acid accumulator electrolyte follows
The device and method that ring recycles.
Technical background
China has become maximum lead-acid storage battery production state in the world, and annual waste lead accumulator yield is more than
260x104t.Lead-acid accumulator is mainly by waste electrolyte (11%~30%), metal (24%~30%), lead plaster (30%
~40%) and other substances (22%~30%) form.Therefore, every 100t lead-acid accumulator will generate the useless electricity of 11~30t
It solves liquid and will lead to the acidification of soil and the heavy metal of groundwater resources if being directly discharged in natural environment without processing
Pollution.In terms of solving acid waste water, membrane separation technique has in the industries such as smelting, plating, mining and metal surface processing
It is widely applied, is a kind of novel, efficient fluid separation techniques, there is low energy consumption, good separating effect is easily operated to wait spies
Point.In addition, membrane separation technique plays an important role in terms of energy-saving, clean manufacturing, meet China's Economic Sustainability hair
The requirement of exhibition.
Notification number is that the Chinese patent of CN105186060B discloses a kind of waste lead storage battery electrolyte recycling and reusing
Device, the invention include waste and old lead acid accumulator electrolyte storage tank, waste lead storage battery electrolyte storage tank by pipeline once with
Acid-proof pump, filter are connected with the acid solution import of diffusion dialysis component, and waterpipe is connected with the water inlet of diffusion dialysis component, expand
The raffinate outlet of scattered electrodialysis stack is connected by pipeline with subsequent processing workshop section, reduction enterprise waste acid treatment simple with structure
Cost, while effectively spent acid can be recycled.The recycling of the waste lead storage battery electrolyte of above-mentioned patent disclosure is sharp again
With the development and implementation dependent on waste acid collecting device of device output, and equipment does not have electrolyte evolution facility, output it is useless
Rich in there is the foreign ions such as lead, iron, sodium, copper, calcium, tin, direct reuse can seriously affect the service life of battery, cause electrolyte
The accumulator products quality problems such as internal short-circuit of battery, pole plate heavy corrosion.Notification number is the Chinese patent of CN105712302B
The method for disclosing waste lead storage battery retrieval of sulfuric acid system and recycling sulfuric acid using it, the invention include passing through liquid-transport pipe-line phase
85% recycling of sulfuric acid is realized in the plate-frame filtering equipment of connection, micro-filtrate membrane filtration equipment, diffusion dialysis, nanofiltration membrane filter device
Rate.But the patent is using the waste and old sulfuric acid of membrane separation plant processing waste and old lead acid accumulator output, to the metal in waste and old sulfuric acid
Cation has apparent interception effect, can not intercept the anion in solution, and waste and old sulfuric acid contain chloride ion, phosphate radical from
The recovery acid impurity of the anion very harmful to lead-acid accumulator such as son, nitrate ion, output can exceed lead-acid accumulator
With sulfuric acid using standard, especially chloride ion far beyond standard national standard 0.00065.In equipment face, notification number is
Nanofiltration acid-resistant disintegration in the Chinese patent of CN105712302B, the sulfuric acid concentration of use are up to 30%, and nanofiltration membrane is in high-concentration sulfuric acid
In the case of be easily damaged, greatly reduce the service life of material.In addition, containing the gold such as lead, copper, iron, sodium, calcium, tin in waste and old sulfuric acid
Belong to cation, contain a large amount of sulfate anions, 5~40 DEG C of microfiltration membranes operation temperature, under the conditions of temperature is lower, spent acid is molten
Liquid can block microfiltration membrane system by the sulfuric acid leading crystal generated when microfiltration membranes, not have low temperature operational feasibility.
Summary of the invention
The object of the present invention is to provide a kind of devices of lead-acid accumulator electrolyte cycling and reutilization, have recycling sharp again
With lead-acid accumulator electrolyte, suitable for the effect of industrial use, solve the environmental pollution of lead-acid accumulator electrolyte and ask
Topic promotes the construction of lead-acid accumulator circulation industrial chain.
Above-mentioned technical purpose of the invention has the technical scheme that a kind of lead-acid accumulator electrolysis
The device of liquid cycling and reutilization, including be sequentially connected pretreatment unit, sheet frame booster pump, plate and frame filter press, sheet frame produce flow container,
Pre-heating system, ceramic membrane booster pump, ceramic membrane group, ceramic membrane for producing liquid the pre-heat treatment to sheet frame produce flow container, nanofiltration membrane NB1
Booster pump, nanofiltration membrane NB1 group, nanofiltration membrane NB1 produce flow container, nanofiltration membrane NB2 booster pump, nanofiltration membrane NB2 group, nanofiltration membrane NB2 and produce liquid
Tank, nanofiltration membrane NC film booster pump, nanofiltration membrane NC film, nanofiltration membrane NC film produce flow container.
By using above-mentioned technical proposal, pretreatment unit pre-processes lead-acid accumulator electrolyte, and sheet frame increases
Lead-acid accumulator electrolyte is pumped into plate and frame filter press by press pump, and sheet frame out produces liquid and enters in sheet frame production flow container.Pass through
Pre-heating system produces liquid to sheet frame and carries out the pre-heat treatment, and control sheet frame produces liquid temperature at 20-40 DEG C, extends membrane module such as nanofiltration membrane
Service life, certificates handling produce liquid flux, prevent metal sulfate Crystallization Plugging membrane module.
Sheet frame after preheating is produced liquid pump and enters ceramic membrane group by ceramic membrane booster pump, and ceramic membrane out produces liquid and enters ceramic membrane
It produces in flow container, nanofiltration membrane NB1 booster pump enters ceramic membrane production liquid pump in nanofiltration membrane NB1 group, and nanofiltration membrane NB1 out produces liquid and enters
Nanofiltration membrane NB1 is produced in flow container, and nanofiltration membrane NB2 booster pump enters nanofiltration membrane NB1 production liquid pump in nanofiltration membrane NB2 group, nanofiltration out
Film NB2 produces liquid and enters in nanofiltration membrane NB2 production flow container.Nanofiltration membrane NB2 production liquid pump is entered nanofiltration membrane NC film by nanofiltration membrane NC film booster pump
Interior, obtained nanofiltration membrane NC film produces liquid, can transport to battery complex acid station, the preparation for new battery electrolyte.Pass through multistage
The high efficiente callback of lead-acid accumulator electrolyte is realized in the filtering of membrane module and the optimization of technological parameter, can obtain qualified production
Liquid, device is efficient, stable, feasible, is suitable for industrial use.
The further setting of the present invention are as follows: the pretreatment unit is that bed is filled out in pretreatment, described to pre-process the filler for filling out bed
For one of quartz sand, active carbon or a variety of, the pretreatment fills out bed with a thickness of 30-60cm.
By using above-mentioned technical proposal, the filler that bed is filled out in pretreatment is one of quartz sand, active carbon or a variety of, is risen
To the effect of primary filtration, lead-acid accumulator electrolyte internal solid impurity such as ignition residue etc. is removed, avoids blocking membrane module,
Guarantee that device efficiently, is steadily run.
The further setting of the present invention are as follows: the pre-heating system is water-bath heat exchange system, the water-bath heat exchange system
Including plural serial stage U-tube road.
The further setting of the present invention are as follows: further include deionized water production equipment, the deionized water production equipment is successively
Water booster pump, level-one RO film group, second level RO film group, EDI device, deionized water storage tank are produced including MBR reactor, MBR.
By using above-mentioned technical proposal, in deionized water production equipment, MBR reactor is also known as membrane bioreactor, EDI
Equipment is also known as EDI pure water equipment.MBR reactor is connected with tap water pipe network, for carrying out primary treatment to tap water.MBP is produced
Water is entered by obtaining deionized water after sequentially entering level-one RO film group, second level RO film group, EDI device after MBR production water booster pump
It is stored in deionized water storage tank, for being diluted to lead-acid accumulator electrolyte.
The further setting of the present invention are as follows: further include flowing back for ceramic membrane concentrate to be flowed into the dope of plate and frame filter press
System one, is used for nanofiltration membrane the dope return-flow system two for nanofiltration membrane NB1 concentrate to be back in ceramic membrane production flow container
NB2 concentrate flows back into nanofiltration membrane NB1 and produces the dope return-flow system three of flow container, receives for flowing back into nanofiltration membrane NC film concentrate
Filter membrane NB2 produces the dope return-flow system four of flow container, the concentration for producing nanofiltration membrane NB1 in flow container produces liquid and is back to ceramic membrane group
The high dope return-flow system one of leading portion, the concentration for producing nanofiltration membrane NB2 in flow container produce liquid and flow back into ceramic membrane group leading portion
One of high dope return-flow system two is a variety of.
By using above-mentioned technical proposal, obtain producing liquid and concentrate after film filtering, concentrate is that impurity content is higher
Waste liquid.The present invention improves the circular regeneration amount of lead-acid accumulator electrolyte by the way of concentrate reflux.
Nanofiltration membrane NB1 produce flow container in concentration produce liquid formed it is as follows: nanofiltration membrane NB1 group out nanofiltration membrane NB1 production liquid into
Enter to nanofiltration membrane NB1 and produce flow container, nanofiltration membrane NB1 produces liquid and is pumped into nanofiltration membrane NB2 group by nanofiltration membrane NB2, and nanofiltration membrane NB2 produces liquid out
With nanofiltration membrane NB2 concentrate, nanofiltration membrane NB2 concentrate by dope return-flow system three flow back into nanofiltration membrane NB1 produce flow container, then by
Nanofiltration membrane NB2 booster pump is pumped into nanofiltration membrane NB2 group, and nanofiltration membrane NB2 produces liquid and nanofiltration membrane NB2 concentrate, nanofiltration out again
Film NB2 concentrate flows back into nanofiltration membrane NB1 by dope return-flow system three again and produces flow container, by repeatedly recycling, in nanofiltration membrane
NB1, which is produced, forms concentration production liquid in flow container.
Nanofiltration membrane NB2 produce flow container in concentration produce liquid formed it is as follows: nanofiltration membrane NB2 group out nanofiltration membrane NB2 production liquid into
Enter to nanofiltration membrane NB2 and produce in flow container, nanofiltration membrane NB2 produces liquid and is pumped into nanofiltration membrane NC film, out nanofiltration by nanofiltration membrane NC film booster pump
Film NC film produces liquid and nanofiltration membrane NC film concentrate, and nanofiltration membrane NC film concentrate is back to nanofiltration membrane by dope return-flow system four
NB2 produces flow container, then is pumped into nanofiltration membrane NC film by nanofiltration membrane NC film booster pump, and nanofiltration membrane NC film produces liquid and nanofiltration membrane NC out again
Film concentrate, nanofiltration membrane NC film concentrate flows back into nanofiltration membrane NB2 by dope return-flow system four again and produces in flow container, through excessive
Secondary circulation produces in nanofiltration membrane NB2 and forms concentration production liquid in flow container.
The further setting of the present invention are as follows: the aperture of the ceramic membrane in ceramic membrane group is at 50-100 microns, nanofiltration membrane NB1
The aperture of nanofiltration membrane NB2 of the aperture of nanofiltration membrane NB1 in group in 50-100nm, nanofiltration membrane NB2 group is in 50-100nm, nanofiltration
The aperture of film NC film is in 10-20nm；Ceramic membrane material in ceramic membrane group is aluminum oxide or zirconium dioxide, nanofiltration membrane NB1
Nanofiltration membrane NB1 material in group is one of polysulfones nanofiltration membrane, polyether sulfone filtering film, polyamide nanofiltration membrane, nanofiltration membrane NB2 group
Interior nanofiltration membrane NB2 material is identical as nanofiltration membrane NB1 material in nanofiltration membrane NB1 group, and nanofiltration membrane NC membrane material is polysulfones nanofiltration membrane, gathers
One of ether sulfone nanofiltration membrane, polyamide nanofiltration membrane.
By using above-mentioned technical proposal, nanofiltration membrane NB1, nanofiltration membrane NB2, nanofiltration membrane NC film use polysulfones, polyether sulfone, gather
One of amide is acidproof nanofiltration membrane.
The further setting of the present invention are as follows: further include waste electrolyte collecting pit, the waste electrolyte that is connected with pretreatment unit
Inlet valve, the waste electrolyte collecting pit material are marble.
By using above-mentioned technical proposal, waste electrolyte collecting pit material is marble, corrosion-resistant, avoids useless lead acid storage battery
Impurity is mixed into the electrolyte of pond.
The further setting of the present invention are as follows: the pretreatment unit is that bed is filled out in pretreatment, described to pre-process the thickness for filling out bed
For 30-60cm, it is composite adsorbing material that the filler in bed is filled out in the pretreatment, and the composite adsorbing material preparation method is as follows,
According to parts by weight, 4-5 parts of phosphoric acid hydrogen zirconiums, 3-4 parts of 2- amino terephthalic acid (TPA)s, 8-10 parts of DMF are taken, 1- is stirring evenly and then adding into
3 parts of nano barium sulfates are warming up to 90 DEG C of heat preservation 12h after being again stirring for uniformly, after being cooled to room temperature, are washed after centrifugation with dehydrated alcohol
It washs, after vacuum drying, 3-5 parts of terpinols, 2-4 parts of ethyl celluloses, 1-2 parts of dehydrated alcohols is added, is uniformly mixed, is placed in 130-
150 DEG C of sintering 30-40min, obtain granular composite adsorbing material.
By using above-mentioned technical proposal, in the cycling and reutilization of the electrolyte of lead-acid accumulator, need to remove wherein
Metal cation, such as iron ion, manganese ion, copper ion.The alloys such as iron, copper especially in lead-acid accumulator material are molten
After its electrolyte, cause the metal cation concentration in lead-acid accumulator electrolyte higher.Although nanofiltration membrane can be to metal
Cation plays the role of retention and separation, but retains by membrane separation technique to metal cation merely, on the one hand needs
More nanofiltration membrane being set, it is repeatedly retained, process flow is partially long, inefficiency, and causes installation cost higher,
The electrolyte metal cation concentration of another aspect lead-acid accumulator is higher, it is easy to the blocking and loss of nanofiltration membrane are caused,
The loss of nanofiltration membrane is caused to increase, therefore, it is necessary to selectively go before the electrolyte contacts nanofiltration membrane of lead-acid accumulator
These three metal cations of iron ions, copper ion and manganese ion.
Pretreatment unit is that bed is filled out in pretreatment, and it is composite adsorbing material that the filler in bed is filled out in pretreatment, and phosphoric acid hydrogen zirconium is one
Kind of mesoporous material forms framework material by the way that nano barium sulfate to be carried on phosphoric acid hydrogen zirconium, then with terpinol, ethyl cellulose
Element, dehydrated alcohol coat it, obtain granular composite adsorbing material after sintering.Ethyl cellulose is first is that have viscous
Various components are bonded together by the effect of conjunction, form particle, second is that ethyl cellulose has good film forming, compound
Film forming, can provide adsorption site for the absorption of metal cation, and in phosphoric acid in the hole of material surface and phosphoric acid hydrogen zirconium
The transmittability of metal cation can be effectively improved in the hole of hydrogen zirconium after film forming.Pretreatment fills out bed to lead-acid accumulator electricity
When solving liquid pretreatment, the metal cations such as iron ion, copper ion, manganese ion are first adsorbed in composite adsorbing material surface, then along multiple
The hole of adsorbent material is closed further to spreading inside composite adsorbing material, can preferably adsorb iron ion, copper ion and manganese from
Son effectively removes iron ion, copper ion and manganese ion in lead-acid accumulator electrolyte.
The present invention also provides a kind of methods of lead-acid accumulator electrolyte cycling and reutilization, including, by useless lead acid storage battery
Pond electrolyte is pre-processed by pretreatment unit, and lead-acid accumulator electrolyte is pumped into sheet frame pressure by sheet frame booster pump
Filter is filtered, and the sheet frame of output produces liquid and enters sheet frame production flow container；When environment temperature is lower than 20 DEG C, pre-heating system is opened,
Sheet frame produces the sheet frame production liquid in flow container and enters pre-heating system, and the production liquid temperature for controlling out is between 20-40 DEG C；Liquid is produced to pass through again
Ceramic membrane booster pump enters ceramic membrane group, and the ceramic membrane of output produces liquid and enters ceramic membrane production flow container, in deionized water storage tank
Deionized water to ceramic membrane produce flow container in ceramic membrane produce liquid be diluted, until ceramic membrane produce liquid in sulfuric acid concentration exist
16% or less；Ceramic membrane after dilution is produced liquid pump and enters nanofiltration membrane NB1 group by nanofiltration membrane NB1 booster pump, and the nanofiltration membrane NB1 of output is produced
Liquid enters nanofiltration membrane NB1 and produces flow container, and nanofiltration membrane NB1 production liquid pump is entered nanofiltration membrane NB2 group by nanofiltration membrane NB2 booster pump, and output is received
Filter membrane NB2 produces liquid and enters nanofiltration membrane NB2 production flow container；Nanofiltration membrane NB2 production liquid pump is entered nanofiltration membrane NC film by nanofiltration membrane NC film booster pump,
The nanofiltration membrane NC film of output produces liquid and enters in nanofiltration membrane NC film production flow container, and nanofiltration membrane NC film production liquid is transported to battery complex acid station and waits for
With.
The further setting of the present invention are as follows: further include falling sour machine with battery to collect the electrolyte of lead-acid accumulator, row
Enter waste electrolyte collecting pit, the lead-acid accumulator electrolyte in waste electrolyte collecting pit enters pretreatment unit；Ceramic membrane group
Concentrate flow back into plate and frame filter press, the concentrate of nanofiltration membrane NB1 group flow back into ceramic membrane produce flow container in, nanofiltration membrane NB2
The concentrate of group flows back into nanofiltration membrane NB1 and produces in flow container, and the concentrate of nanofiltration membrane NC film flows back into nanofiltration membrane NB2 and produces in flow container,
Nanofiltration membrane NB1 produces the concentration that production liquid flows back into ceramic membrane group leading portion, nanofiltration membrane NB2 is produced in flow container that is concentrated in flow container and produces liquid reflux
To ceramic membrane group leading portion；Nanofiltration membrane NB1 group produces the production liquid in flow container to ceramic membrane and is concentrated, and the high impurity of concentration out is useless
As in sewage plant, the high impurity waste liquid of discharge is no more than the 12% of lead-acid accumulator electrolyte for liquid discharge.
The beneficial effects of the present invention are: 1, using multistage membrane module lead-acid accumulator electrolyte is filtered, intercept
Metal cation therein, the nanofiltration membrane NC film of output produce the electrolyte quota that liquid can be used for new accumulator, realize that scrap lead acid stores
The circular regeneration of battery electrolyte；2, equipment includes pretreatment unit and water-bath heat exchange system, and pretreatment unit is to scrap lead acid
Battery liquid carries out primary filtration, the solid-states sundries such as removal ignition residue, and water-bath heat exchange system plays control scrap lead acid
The temperature of battery liquid, control temperature makes membrane module be in the optimal level of performance, and can adapt under low temperature environment
Lead-acid accumulator electrolyte cycling and reutilization, keep stabilization of equipment performance good；3, sour machine is fallen to useless lead acid storage battery with battery
Pond carries out down acid, and waste electrolyte collecting pit material uses corrosion resistant marble, and the pollution that waste electrolyte is controlled from source is asked
Topic, it is ensured that the content that nanofiltration membrane NC produces chloride ion in liquid meets battery dilute sulfuric acid quality standard；4, it is used in membrane filtration processes
Reasonable dope reflux type, maximizes the circular regeneration amount for improving lead-acid accumulator electrolyte；5, film process scrap lead acid stores
Battery electrolyte, for acidic electrolysis bath by pipeline, membrane module processing, site environment is neatly pollution-free.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the structural schematic diagram of embodiment 1.
Fig. 2 is the process flow chart of embodiment 1.
In figure, 1, waste electrolyte inlet valve；2, pretreatment unit；3, sheet frame booster pump；4, plate and frame filter press；5, sheet frame produces
Flow container；6, pre-heating system；7, ceramic membrane booster pump；8, ceramic membrane group；9, ceramic membrane produces flow container；10, nanofiltration membrane NB1 booster pump；
11, nanofiltration membrane NB1 group；12, nanofiltration membrane NB1 produces flow container；13, nanofiltration membrane NB2 booster pump；14, nanofiltration membrane NB2 group；15, nanofiltration membrane
NB2 produces flow container；16, nanofiltration membrane NC film booster pump；17, nanofiltration membrane NC film；18, nanofiltration membrane NC film produces flow container；19, NC produces liquid outlet
Valve；20, tap water pipe network inlet valve；21, MBR reactor；22, MBR produces water booster pump；23, level-one RO film group；24, second level RO
Film group；25, EDI device；26, deionized water storage tank.
Specific embodiment
Embodiment 1: a kind of device of lead-acid accumulator electrolyte cycling and reutilization, as shown in Figure 1, including being sequentially connected
Waste electrolyte inlet valve 1, pretreatment unit 2, sheet frame booster pump 3, plate and frame filter press 4, sheet frame produce flow container 5, for sheet frame
Pre-heating system 6, ceramic membrane booster pump 7, ceramic membrane group 8, the ceramic membrane for producing liquid the pre-heat treatment produce flow container 9, nanofiltration membrane NB1 booster pump
10, nanofiltration membrane NB1 group 11, nanofiltration membrane NB1 produce flow container 12, nanofiltration membrane NB2 booster pump 13, nanofiltration membrane NB2 group 14, nanofiltration membrane NB2
It produces flow container 15, nanofiltration membrane NC film booster pump 16, nanofiltration membrane NC film 17, nanofiltration membrane NC film and produces flow container 18.It further include that waste electrolyte is received
Ji Chi, waste electrolyte collecting pit material are marble, and waste electrolyte inlet valve 1 is connected by pipeline with waste electrolyte collecting pit.
Pretreatment unit 2 is that bed is filled out in pretreatment, and it is the filler that a layer thickness is 30cm that bed is filled out in pretreatment, and filler is quartz sand and active carbon
Mixture.Pre-heating system 6 is water-bath heat exchange system, and water-bath heat exchange system includes the plural serial stage U-tube being placed in water
Road, U-tube road material are PVC material, and inside is flowed through for lead-acid accumulator electrolyte.By the control of bath temperature, guarantee
Fluid temperature out is between 20-40 DEG C.
Ceramic membrane in ceramic membrane group 8 uses aluminum oxide inorganic ceramic membrane, and aperture is at 50-100 microns.Nanofiltration membrane
Nanofiltration membrane NB1 in NB1 group 11 uses the nanofiltration membrane of polysulfones material, aperture 50-100nm.Nanofiltration membrane in nanofiltration membrane NB2 group 14
NB2 material is identical as nanofiltration membrane NB1, using the nanofiltration membrane of polysulfones material, aperture 50-100nm.Nanofiltration membrane NC film 17 uses polyethers
Sulfone nanofiltration membrane, aperture 10-20nm.
The device of lead-acid accumulator electrolyte cycling and reutilization further includes deionized water production equipment, deionized water production
Equipment successively include MBR reactor 21, MBR produce water booster pump 22, level-one RO film group 23, second level RO film group 24, EDI device 25,
Deionized water storage tank 26.MBR reactor 21 is connected by tap water pipe network inlet valve 20 with tap water pipe network, and deionized water is deposited
Storage tank 26 produces flow container 9 with ceramic membrane by pipeline and is connected.After opening tap water pipe network inlet valve 20, tap water pipe network is originally
Water passes sequentially through MBR reactor 21, MBR is obtained after producing water booster pump 22, level-one RO film group 23, second level RO film group 24, EDI device 25
To deionized water, it is stored in deionized water storage tank 26.
Lead-acid accumulator electrolyte can generate concentrate in film filtering, to improve electrolyte circular regeneration amount, scrap lead acid
The device of battery liquid cycling and reutilization further includes flowing back for ceramic membrane concentrate to be flowed into the dope of plate and frame filter press 4
System one, for by 11 concentrate of nanofiltration membrane NB1 group be back to ceramic membrane produce flow container 9 in dope return-flow system two, be used for by
14 concentrate of nanofiltration membrane NB2 group flows back into nanofiltration membrane NB1 and produces the dope return-flow system three of flow container 12, is used for nanofiltration membrane NC film 17
Concentrate flows back into nanofiltration membrane NB2 and produces the dope return-flow system four of flow container 15, for nanofiltration membrane NB1 to be produced to the concentration in flow container 12
It produces liquid and is back to the high dope return-flow system one of 8 leading portion of ceramic membrane group, for nanofiltration membrane NB2 to be produced to the concentration production liquid in flow container 15
Flow back into the high dope return-flow system two of 8 leading portion of ceramic membrane group.Return-flow system one, return-flow system two, return-flow system three, reflux system
System four, high dope return-flow system one, high dope return-flow system two by pipeline and pump group at.Wherein 11 pairs of nanofiltration membrane NB1 group potteries
Porcelain film produces the ceramic membrane production liquid in flow container 9 and is filtered, and the waste liquid of high foreign ion is discharged into sewage plant, is discharged into the waste liquid of sewage plant
No more than the 12% of lead-acid accumulator electrolyte, to realize that the circulation of 88% or more lead-acid accumulator electrolyte is sharp again
With.
The method of lead-acid accumulator electrolyte cycling and reutilization is as follows: as shown in Fig. 2, sour machine collection is useless with battery
The electrolyte of lead-acid accumulator is discharged into waste electrolyte collecting pit.The lead-acid accumulator electrolyte of waste electrolyte collecting pit passes through
Waste electrolyte inlet valve 1 enters pretreatment unit 2, and pretreatment unit 2 is to lead-acid accumulator electrolyte primary filtration, out
Lead-acid accumulator electrolyte is pumped to plate and frame filter press 4 by sheet frame booster pump 3 and carries out filters pressing, and obtained sheet frame produces liquid and enters
Sheet frame produces flow container 5.
When environment temperature is lower than 20 DEG C, water-bath heat exchange system is opened, sheet frame produces the sheet frame production liquid in flow container 5 and enters water
Heat-exchange system is bathed, the production liquid temperature for controlling out is between 20-40 DEG C.Production liquid out pass through again ceramic membrane booster pump 7 into
Enter ceramic membrane group 8, ceramic membrane out produces liquid and enters ceramic membrane production flow container 9, spends the deionized water pair in ion storage tank 26
Ceramic membrane produces the ceramic membrane production liquid in flow container 9 and is diluted, until ceramic membrane produces the sulfuric acid concentration in liquid below 16%.
Ceramic membrane after dilution is produced liquid pump and enters nanofiltration membrane NB1 group 11, the nanofiltration membrane of output by nanofiltration membrane NB1 booster pump 10
NB1 produces liquid and enters nanofiltration membrane NB1 production flow container 12.Nanofiltration membrane NB1 production liquid pump is entered nanofiltration membrane NB2 group by nanofiltration membrane NB2 booster pump 13
14, the nanofiltration membrane NB2 of output produce liquid and enter nanofiltration membrane NB2 production flow container 15.Nanofiltration membrane NB2 is produced liquid by nanofiltration membrane NC film booster pump 16
It is pumped into nanofiltration membrane NC film 17, the nanofiltration membrane NC film of output produces liquid and enters nanofiltration membrane NC film production flow container 18, and nanofiltration membrane NC film produces flow container
It is provided with NC and produces liquid outlet valve, NC produces liquid outlet valve and is connected by pipeline with battery complex acid station, the qualified nanofiltration membrane of output
It is stand-by that NC film production liquid is delivered to battery complex acid station.
Embodiment 2: a kind of device of lead-acid accumulator electrolyte cycling and reutilization, the difference from embodiment 1 is that, in advance
It is the filler that a layer thickness is 60cm that bed is filled out in processing, and filler is active carbon.Ceramic membrane in ceramic membrane group 8 is zirconia ceramic
Film, the nanofiltration membrane NB1 in nanofiltration membrane NB1 group 11 are polyether sulfone filtering film or polyamide nanofiltration membrane, receiving in nanofiltration membrane NB2 group 14
Filter membrane NB2 material is identical as nanofiltration membrane NB1.Nanofiltration membrane NC film 17 is polysulfones nanofiltration membrane or polyamide nanofiltration membrane.
Embodiment 3: a kind of device of lead-acid accumulator electrolyte cycling and reutilization, the difference from embodiment 1 is that, in advance
It is filler of a layer thickness between 30-60cm that bed is filled out in processing, and filler is composite adsorbing material, composite adsorbing material preparation method
It is as follows, 2- amino terephthalic acid (TPA), the 8kgDMF of 4kg phosphoric acid hydrogen zirconium, 3kg are taken, 1kg nano barium sulfate is stirring evenly and then adding into,
90 DEG C of heat preservation 12h are warming up to after being again stirring for uniformly, after being cooled to room temperature, are washed after centrifugation with dehydrated alcohol, after vacuum drying,
3kg terpinol, 2kg ethyl cellulose, 1kg dehydrated alcohol is added, is uniformly mixed, is placed in 130-150 DEG C of sintering 30min, obtains
Granular composite adsorbing material.
Embodiment 4: a kind of device of lead-acid accumulator electrolyte cycling and reutilization, the difference from embodiment 1 is that, in advance
It is filler of a layer thickness between 30-60cm that bed is filled out in processing, and filler is composite adsorbing material, composite adsorbing material preparation method
It is as follows, 2- amino terephthalic acid (TPA), the 10kgDMF of 5kg phosphoric acid hydrogen zirconium, 4kg are taken, 3kg nano barium sulfate is stirring evenly and then adding into,
90 DEG C of heat preservation 12h are warming up to after being again stirring for uniformly, after being cooled to room temperature, are washed after centrifugation with dehydrated alcohol, after vacuum drying,
5kg terpinol, 4kg ethyl cellulose, 2kg dehydrated alcohol is added, is uniformly mixed, is placed in 130-150 DEG C of sintering 40min, obtains
Granular composite adsorbing material.
Experimental section:
Experimental group 1: using the device and method of the lead-acid accumulator electrolyte cycling and reutilization in embodiment 1 to certain lead
Lead-acid accumulator electrolyte in battery cycle industrial garden is handled, and electrolyte sulfuric acid concentration is 32%, temperature 5
DEG C, iron concentration 0.25%, copper ion concentration 0.0050%, chlorine ion concentration 0.0004%.Waste electrolyte is pressed
Pretreatment unit, plate and frame filter press, pre-heating system, ceramic membranous system, nanofiltration membrane NB1 group, nanofiltration are sequentially entered according to process flow
Film NB2 group, nanofiltration membrane NC film, output qualification produce liquid and deliver into the preparation that battery complex acid station carries out battery liquid.Its
In, it is 25 DEG C by the controller of water-bath heat exchange system setting outlet temperature to control the temperature of electrolyte at 20~30 DEG C.For
Ceramic membrane production liquid is diluted to 16% hereinafter, 1 volumes of deionized water need to be added in 1 cube of electrolyte is diluted.It is inhaled using atom
Receive spectrum to produce liquid detect, produce liquid iron concentration be 0.0003%, copper ion concentration 0.0001%, manganese ion concentration
It is 0.00003%, testing chloride ion content by turbidimetry is 0.0002%, and titrimetry test reduzate SO2 meets country
Standard, product are qualified.
Experimental group 2: using the device and method of lead-acid accumulator electrolyte cycling and reutilization in embodiment 1, to certain lead
Lead-acid accumulator electrolyte in battery cycle industrial garden is handled, and electrolyte sulfuric acid concentration is 25%, temperature is
10 DEG C, iron concentration 0.20%, copper ion concentration 0.0030%, chlorine ion concentration 0.0003%.By waste electrolyte
Pretreatment unit, plate and frame filter press, pre-heating system, ceramic membranous system, nanofiltration membrane NB1 are sequentially entered according to above-mentioned process flow
Group, nanofiltration membrane NB2 group, nanofiltration membrane NC film, output qualification produce liquid and deliver into battery complex acid station progress battery liquid
It prepares.Wherein, it is the temperature of control electrolyte at 20~30 DEG C, is by the controller setting outlet temperature of water-bath heat exchange system
25℃.For ceramic membrane production liquid is diluted to 16% hereinafter, 0.7 volumes of deionized water need to be added in 1 cube of electrolyte is diluted.It adopts
With atomic absorption spectrum to produce liquid detect, produce liquid iron concentration be 0.00025%, copper ion concentration 0.00008%,
Manganese ion concentration is 0.000025%, and testing chloride ion content by turbidimetry is 0.00017%, and reduzate is tested in titrimetry
SO2 meets national standard, and product is qualified.
Experimental group 3: using the device and method of lead-acid accumulator electrolyte cycling and reutilization in embodiment 1, to certain lead
Lead-acid accumulator electrolyte in battery cycle industrial garden is handled, and electrolyte sulfuric acid concentration is 20%, temperature is
22 DEG C, iron concentration 0.16%, copper ion concentration 0.001%, chlorine ion concentration 0.0002%.Waste electrolyte is pressed
According to above-mentioned process flow sequentially enter pretreatment unit, plate and frame filter press, pre-heating system, ceramic membranous system, nanofiltration membrane NB1 group,
Nanofiltration membrane NB2 group, nanofiltration membrane NC film, output qualification produce liquid and deliver into matching for battery complex acid station progress battery liquid
System.Pre-heating system is closed, the pre-heat treatment is not necessarily to.For ceramic membrane production liquid is diluted to 16% hereinafter, 1 cube of electrolyte needs to be added
0.3 volumes of deionized water is diluted.It is detected using atomic absorption spectrum to liquid is produced, producing liquid iron concentration is
0.0001%, copper ion concentration 0.00005%, manganese ion concentration 0.000015% are tested chloride ion by turbidimetry and are contained
Amount is 0.00013%, and titrimetry test reduzate SO2 meets national standard, and product is qualified.
Experimental group 4: filling out bed using the pretreatment in embodiment 3, stores to the scrap lead acid in certain lead storage battery cycle industrial garden
Battery electrolyte is handled, and electrolyte sulfuric acid concentration is 32%, temperature is 5 DEG C, iron concentration 0.25%, copper ion
Concentration is 0.0050%, manganese ion concentration 0.001%.It lead-acid accumulator electrolyte is placed in pretreatment fills out in bed and handle
200min, the production liquid of output.Using atomic absorption spectrum to produce liquid detect, produce liquid iron concentration be 0.05%, copper from
Sub- concentration is 0.001%, manganese ion concentration 0.0005%.
Experimental group 5: filling out bed using the pretreatment in embodiment 4, stores to the scrap lead acid in certain lead storage battery cycle industrial garden
Battery electrolyte is handled, electrolyte sulfuric acid concentration is 25%, temperature is 10 DEG C, iron concentration 0.20%, copper from
Sub- concentration is 0.0030%, manganese ion concentration 0.0008%.Lead-acid accumulator electrolyte is placed in pretreatment to fill out in bed
Manage 200min, the production liquid of output.It is detected using atomic absorption spectrum to liquid is produced, producing liquid iron concentration is 0.04%, copper
Ion concentration is 0.0015%, manganese ion concentration 0.0001%.
Experimental group 6: filling out bed using the pretreatment in embodiment 4, stores to the scrap lead acid in certain lead storage battery cycle industrial garden
Battery electrolyte is handled, electrolyte sulfuric acid concentration is 20%, temperature is 22 DEG C, iron concentration 0.16%, copper from
Sub- concentration is 0.001%, manganese ion concentration 0.0007%.It lead-acid accumulator electrolyte is placed in pretreatment fills out in bed and handle
200min, the production liquid of output.Using atomic absorption spectrum to produce liquid detect, produce liquid iron concentration be 0.02%, copper from
Sub- concentration is 0.0007%, manganese ion concentration 0.00015%.
Impurity content and lead-acid accumulator dilute sulfuric acid national standard in 1 lead-acid accumulator electrolyte of table
Claims (10)
1. a kind of device of lead-acid accumulator electrolyte cycling and reutilization, it is characterised in that: including the pretreatment being sequentially connected
Unit (2), sheet frame booster pump (3), plate and frame filter press (4), sheet frame produce flow container (5), for producing the pre- of liquid the pre-heat treatment to sheet frame
Hot systems (6), ceramic membrane booster pump (7), ceramic membrane group (8), ceramic membrane produce flow container (9), nanofiltration membrane NB1 booster pump (10), receive
Filter membrane NB1 group (11), nanofiltration membrane NB1 produce flow container (12), nanofiltration membrane NB2 booster pump (13), nanofiltration membrane NB2 group (14), nanofiltration membrane
NB2 produces flow container (15), nanofiltration membrane NC film booster pump (16), nanofiltration membrane NC film (17), nanofiltration membrane NC film production flow container (18).
2. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: institute
It states pretreatment unit (2) and fills out bed for pretreatment, the filler that bed is filled out in the pretreatment is one of quartz sand, active carbon or more
Kind, the pretreatment fills out bed with a thickness of 30-60cm.
3. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: institute
Stating pre-heating system (6) is water-bath heat exchange system, and the water-bath heat exchange system includes plural serial stage U-tube road.
4. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: also
Including deionized water production equipment, the deionized water production equipment successively includes MBR reactor (21), MBR production water booster pump
(22), level-one RO film group (23), second level RO film group (24), EDI device (25), deionized water storage tank (26).
5. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: also
Including being used to flow into ceramic membrane concentrate the dope return-flow system one of plate and frame filter press (4), being used for nanofiltration membrane NB1 concentrate
Be back to ceramic membrane produce flow container (9) in dope return-flow system two, for nanofiltration membrane NB2 concentrate to be flowed back into nanofiltration membrane NB1
It produces the dope return-flow system three of flow container (12), produce flow container (15) for nanofiltration membrane NC film concentrate to be flowed back into nanofiltration membrane NB2
Dope return-flow system four, the concentration for producing nanofiltration membrane NB1 in flow container (12) produce the height that liquid is back to ceramic membrane group (8) leading portion
Dope return-flow system one, the concentration for producing nanofiltration membrane NB2 in flow container (15) produce the height that liquid flows back into ceramic membrane group (8) leading portion
One of dope return-flow system two is a variety of.
6. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: pottery
The aperture of nanofiltration membrane NB1 of the aperture of ceramic membrane in porcelain film group (8) in 50-100 microns, nanofiltration membrane NB1 group (11) is in 50-
The aperture of nanofiltration membrane NB2 in 100nm, nanofiltration membrane NB2 group (14) is in 50-100nm, and the aperture of nanofiltration membrane NC film (17) is in 10-
20nm；Ceramic membrane material in ceramic membrane group (8) is aluminum oxide or zirconium dioxide, the nanofiltration in nanofiltration membrane NB1 group (11)
Film NB1 material is one of polysulfones nanofiltration membrane, polyether sulfone filtering film, polyamide nanofiltration membrane, nanofiltration membrane NB2 group (14) interior nanofiltration
Film NB2 material is identical as the interior nanofiltration membrane NB1 material of nanofiltration membrane NB1 group (11), nanofiltration membrane NC film (17) material be polysulfones nanofiltration membrane,
One of polyether sulfone filtering film, polyamide nanofiltration membrane.
7. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: also
Including waste electrolyte collecting pit, the waste electrolyte inlet valve (1) being connected with pretreatment unit (2), the waste electrolyte collecting pit
Material is marble.
8. a kind of device of lead-acid accumulator electrolyte cycling and reutilization according to claim 1, it is characterised in that: institute
State pretreatment unit (2) and fill out bed for pretreatment, it is described pre-process fill out bed with a thickness of 30-60cm, the pretreatment is filled out in bed
Filler is composite adsorbing material, and the composite adsorbing material preparation method is as follows, according to parts by weight, take 4-5 parts of phosphoric acid hydrogen zirconiums,
3-4 parts of 2- amino terephthalic acid (TPA)s, 8-10 parts of DMF, are stirring evenly and then adding into 1-3 parts of nano barium sulfates, after being again stirring for uniformly
90 DEG C of heat preservation 12h are warming up to, after being cooled to room temperature, are washed after centrifugation with dehydrated alcohol, after vacuum drying, 3-5 parts of pine tars are added
Alcohol, 2-4 part ethyl cellulose, 1-2 parts of dehydrated alcohols are uniformly mixed, are placed in 130-150 DEG C of sintering 30-40min, obtain particle
The composite adsorbing material of shape.
9. it is a kind of recycled again with the device of claim 1-8 any one lead-acid accumulator electrolyte cycling and reutilization it is sharp
Method, it is characterised in that: including,
Lead-acid accumulator electrolyte is pre-processed by pretreatment unit (2), it is by sheet frame booster pump (3) that scrap lead is sour
Battery liquid is pumped into plate and frame filter press (4) and is filtered, and the sheet frame of output produces liquid and enters sheet frame production flow container (5)；
It when environment temperature is lower than 20 DEG C, opens pre-heating system (6), sheet frame produces the sheet frame production liquid in flow container (5) and enters preheating system
It unites (6), the production liquid temperature for controlling out is between 20-40 DEG C；
It produces liquid and passes through ceramic membrane booster pump (7) again into ceramic membrane group (8), the ceramic membrane of output produces liquid and enters ceramic membrane production flow container
(9), the ceramic membrane production liquid in flow container (9) is produced to ceramic membrane with the deionized water in deionized water storage tank (26) to be diluted,
Until ceramic membrane produces the sulfuric acid concentration in liquid below 16%；
Ceramic membrane after dilution is produced liquid pump and enters nanofiltration membrane NB1 group (11), the nanofiltration membrane of output by nanofiltration membrane NB1 booster pump (10)
NB1 produces liquid and enters nanofiltration membrane NB1 production flow container (12), and nanofiltration membrane NB1 production liquid pump is entered nanofiltration membrane by nanofiltration membrane NB2 booster pump (13)
NB2 group (14), the nanofiltration membrane NB2 of output produce liquid and enter nanofiltration membrane NB2 production flow container (15)；
Nanofiltration membrane NB2 production liquid pump is entered nanofiltration membrane NC film (17) by nanofiltration membrane NC film booster pump (16), and the nanofiltration membrane NC film of output produces
Liquid enters nanofiltration membrane NC film and produces in flow container (18), and it is stand-by that nanofiltration membrane NC film production liquid is transported to battery complex acid station.
10. a kind of method of lead-acid accumulator electrolyte cycling and reutilization according to claim 9, it is characterised in that:
Further include falling sour machine with battery to collect the electrolyte of lead-acid accumulator, is discharged into waste electrolyte collecting pit, waste electrolyte is collected
Lead-acid accumulator electrolyte in pond enters pretreatment unit (2)；The concentrate of ceramic membrane group (8) flows back into plate and frame filter press
(4) in, the concentrate of nanofiltration membrane NB1 group (11) flows back into ceramic membrane and produces in flow container (9), the concentrate of nanofiltration membrane NB2 group (14)
It flows back into nanofiltration membrane NB1 to produce in flow container (12), the concentrate of nanofiltration membrane NC film (17) flows back into nanofiltration membrane NB2 and produces flow container (15)
In, the concentration production liquid in nanofiltration membrane NB1 production flow container (15) flows back into ceramic membrane group (8) leading portion, nanofiltration membrane NB2 is produced in flow container (15)
Concentration produce liquid flow back into ceramic membrane group (8) leading portion；Nanofiltration membrane NB1 group (11) produces the production liquid in flow container (9) to ceramic membrane and carries out
It is concentrated, in the high impurity discharging of waste liquid such as sewage plant of concentration out, the high impurity waste liquid of discharge is no more than lead-acid accumulator
The 12% of electrolyte.
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