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 PDF

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Publication number
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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China
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nanofiltration membrane
membrane
lead
group
liquid
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张行祥
舒绍明
高国兴
梅立寿
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HUBEI CHUKAI CO Ltd
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HUBEI CHUKAI CO Ltd
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Priority to CN201811368963.1A priority Critical patent/CN109301373A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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

A kind of device and method of lead-acid accumulator electrolyte cycling and reutilization
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.
CN201811368963.1A 2018-11-16 2018-11-16 A kind of device and method of lead-acid accumulator electrolyte cycling and reutilization Pending CN109301373A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586613A (en) * 2019-08-29 2019-12-20 浙江浙矿重工股份有限公司 Waste battery crushing and sorting method capable of directly recycling waste electrolyte
CN112786985A (en) * 2020-12-16 2021-05-11 杭州焘颐机械科技有限公司 Environment-friendly separation treatment device for recycling waste storage batteries

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586613A (en) * 2019-08-29 2019-12-20 浙江浙矿重工股份有限公司 Waste battery crushing and sorting method capable of directly recycling waste electrolyte
CN112786985A (en) * 2020-12-16 2021-05-11 杭州焘颐机械科技有限公司 Environment-friendly separation treatment device for recycling waste storage batteries

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