CN106277479A - Integrated retracting device containing metal acid pickle and method - Google Patents

Integrated retracting device containing metal acid pickle and method Download PDF

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Publication number
CN106277479A
CN106277479A CN201610659331.5A CN201610659331A CN106277479A CN 106277479 A CN106277479 A CN 106277479A CN 201610659331 A CN201610659331 A CN 201610659331A CN 106277479 A CN106277479 A CN 106277479A
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acid
diffusion dialysis
ion
tank
pickle
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张炜铭
王刚
吕路
潘丙才
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Nanjing University
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Nanjing University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses the integrated retracting device containing metal acid pickle and method, belong to field of waste recycle.The present invention utilizes diffusion dialysis device by the acid in metal ion acid pickle and separation of metal ions, acid solution after separating metal ions can utilize as reclaiming acid repetitive cycling, metal is reclaimed in metal ion waste liquid recycling electric deposition device reduction after separating acid, and final electro-deposition residual liquid enters Waste Water Treatment.The present invention combines two kinds of devices, both metal ion recycling problem in conventional unheeded diffusion dialysis residual liquid had been solved, considerably reduce again the acid concentration of metal ion acid pickle, create electric deposition device and reclaim the applicable elements of metal ion in diffusion dialysis residual liquid, utilize the complementary feature of diffusion dialysis and electro-deposition cell arrangement, it is achieved that acid and the efficient recovery of metal in metal ion acid pickle.

Description

Integrated retracting device containing metal acid pickle and method
Technical field
The present invention relates to field of waste recycle, more particularly, it relates to the integrated retracting device containing metal acid pickle And method.
Background technology
In the industries such as titanium material, iron and steel, plating, rare earth, generally use the mineral acids such as hydrochloric acid, sulphuric acid, nitric acid to clean gold Metal surface or the use mineral acid such as hydrochloric acid, sulphuric acid carry out regenerating resin, and the acid pickle therefore having a large amount of metal ion produces.Right If the most suitably processing in these acid pickles and directly discharging, not only environment can be wasted certainly simultaneously So resource.The method processing this kind of waste liquid at present has: medicament neutralization, acidic and alkaline waste water neutralization, evaporation and concentration etc., but in various degree Have that processing cost is high, easily produce secondary pollution, fail to realize the problems such as resource reclaim.Diffusion dialysis is a kind of with concentration ladder Spending the spontaneous membrane separating process as motive force, owing to it has, efficiency is high, install and operating cost is low, simple to operate, energy consumption The advantage such as low, has been successfully applied in the industries such as titanium dioxide processing, iron and steel production, non-ferrous metal metallurgy, is used for processing containing metal Ion acid pickle also reclaims mineral acid.But the diffusion dialysis method of report there is also some shortcomings, such as: acid pickle is through expanding After dissipating dialysis process, acid can be recycled, but the metal acidity diffusion dialysis residual liquid containing high concentration synchronizing to produce does not obtains Effectively processing, wherein high-concentration metallic ions fails to realize resource reclaim, thus all limits in Technological Economy aspect Diffusion dialysis method processes the extensive application of metal ion acid pickle.Electro-deposition method can utilize electroreduction to realize containing height The recovery of metal in concentration metal ion waste water, but the acid concentration of above-mentioned metal ion acid pickle is the highest, fills electro-deposition Put material and require harshness, and hydrionic evolving hydrogen reaction enlivens, and causes electro-deposition method to cannot be directly used in metal ion Metal recovery in acid pickle.Acid recovery and metal recovery are not carried out by prior art simultaneously, and recovering effect good this One scheme of sample.
Chinese patent application, application number 201510540264.0, publication date on November 18th, 2015, disclose that " one is not Rust steel pickling waste waters resource recycle method ", this patent uses diffusion dialysis technology separation dilute sulfuric acid, dust technology and dilute hydrogen fluorine Acid, uses in the method adding calcium oxide and unnecessary acid to diffusion dialysis residual liquid, and recycling sulphide precipitation is removed and reclaimed Various metals in waste liquid are not processed by the hybrid metal in diffusion dialysis residual liquid, and loss is big, and treatment effeciency is low.
Chinese patent application, application number 201110150938.8, publication date December in 2012 12 days, disclose " containing sexavalence The process process of chrome waste water ", this patent uses electro-deposition techniques to process chromyl acidic desorption solution, and reduction reclaims it Middle chromium metal.This patented technology does not accounts for using wherein acid recovery, but uses electricity heavy after directly neutralizing acidic desorption solution Wherein chromium metal is reclaimed in long-pending technology reduction, the sour exorbitant expenditure caused, and cost is high, and treatment effect is not enough.
Summary of the invention
1. to solve the technical problem that
Fail to realize resource reclaim, metal cannot be reclaimed for metal ion diffusion dialysis residual liquid present in prior art Problem, the invention provides the integrated retracting device containing metal acid pickle and method, it can be separately recovered containing metal give up Acid and metal in acid solution, it is achieved thereby that trade waste synthetical recovery.
2. technical scheme
The purpose of the present invention is achieved through the following technical solutions.
Integrated retracting device containing metal acid pickle, forms with electric deposition device including diffusion dialysis device, and diffusion is oozed Analysis apparatus is connected by intermediate buffer tank with electric deposition device.
Further, the membrane stack that described diffusion dialysis device is made up of some leafing proton exchanges, and be fixed on The front clamp plate of membrane stack both sides and rear clamping plate composition.
Further, described membrane stack is by the gripper shoe set gradually, sealing gasket, ion exchange membrane, sealing gasket, runner Filter, sealing gasket, ion exchange membrane, sealing gasket and gripper shoe are once overrided to form.
Further, diffusion dialysis device is provided with two runners, and a runner is acid pickle runner, acid pickle runner Import I be connected to inside spent acid flow container by pipeline, outlet I by pipeline and in diffusion dialysis residual liquid peristaltic pump is connected to Between inside surge tank, another runner, for reclaiming runner, reclaims tunnel inlets II and connects and receive tank, and outlet II is wriggled by reclaiming acid Pump connects recovery acid tank tank, receives the acid through diffusion dialysis device separation and recovery.Respectively by two runners reclaim acid and Next step process, convenient separation, the response rate is high.
Further, described electric deposition device include electrolysis bath, electrolyte bath be provided with minus plate, positive plate and on End cap, minus plate and positive plate connect positive pole and the negative pole of power supply, and the electrolysis bath import of electrolysis bath and electrolyzer outlet lead to respectively Piping is connected to intermediate buffer tank and the inside of electro-deposition residual liquid pond tank.
Further, in intermediate buffer tank and electro-deposition residual liquid pond tank, it is respectively arranged with immersible pump I and immersible pump II, and Control pipeline by valve I and valve II respectively to open, form the closed circuit of whole system.Can be controlled by arranging of the pump housing The processing sequence of acid pickle processed and time.
Further, described pipeline is silicone rubber tube or latex tubing.It is acidic materials owing to processing liquid, uses anti- Corrosive pipeline is attached, good stability, and easy for installation.
Utilizing the method that said apparatus processes metal ion acid pickle, step is as follows:
Step 1: irrigate tap water in tank toward receiving, to the 10-90% accounting for tank body volume;
Step 2: in spent acid flow container irrigate acid concentration be 0.5-10mol/L, concentration of metal ions be 0.1-10mol/L's Metal ion acid pickle, to the 10-90% accounting for tank body volume;
Step 3: receive the acid through diffusion dialysis device separation and recovery with reclaiming acid tank tank;
Step 4: receive the diffusion dialysis residual liquid after diffusion dialysis device with intermediate buffer tank;
Step 5: after diffusion dialysis, rinses the acid pickle runner of diffusion dialysis device respectively, rushes with tap water with acid pickle That washes diffusion dialysis device reclaims runner to get rid of the bubble in two runners, treats that diffusion dialysis plant running 60-120min arrives Reach after stablizing, open diffusion dialysis residual liquid peristaltic pump, and keep diffusion dialysis residual liquid peristaltic pump in whole Combined Treatment process In all the time with constant flow rate run;
Step 6: after opening import I isolated operation diffusion dialysis device, then in regulation intermediate buffer tank, diffusion dialysis is residual Liquid pH is 2-7, the valve I being then turned in intermediate buffer tank, makes diffusion dialysis residual liquid flow into electrolysis bath, is then turned on power supply and runs Electric deposition device, keeps diffusion dialysis device to run together with electric deposition device afterwards, carries out the one of metal ion acid pickle Bodyization recycles.
Further, the heavy metal ion in metal ion acid pickle be copper ion, nickel ion, zinc ion, cadmium from Son, chromium ion, lead ion, aluminium ion, iron ion, tin ion, mercury ion, silver ion, gold ion, or above-mentioned ion any two Mixture more than.Variation can be processed with many kinds of metal ions and mixture.
Further, acid is hydrochloric acid, sulphuric acid, nitric acid, or the mixture of any more than two of above-mentioned acid.Can process many Plant acid and mixture, process and reclaim variation.
Owing to the processing means of metal ion acid pickle of the present invention and processing method utilize the reduction of electric deposition device Metal in the diffusion dialysis residual liquid that the ability of heavy metal ion produces during making diffusion dialysis is reclaimed, with existing expansion Scattered electrodialysis apparatus is compared, and has not only reclaimed sour resource, has also reclaimed heavy metal resources, and whole device is rationally distributed, it is achieved contained Metal ion acid pickle circulating in whole device, at utmost reduces and contacts with external environment, reduce and pollute.
3. beneficial effect
Compared to prior art, it is an advantage of the current invention that:
(1) a kind of diffusion dialysis of the present invention and the method and apparatus of electro-deposition Combined Treatment metal ion acid pickle, Overcome process and the metal recovery problem of metal ion diffusion dialysis residual liquid when individually using diffusion dialysis method, and overcome During independent employing electro-deposition method, metal ion acid pickle acidity is the highest, it is impossible to the problem directly reclaiming metal, by expanding The waste liquid that scattered dialysis recycled, again through electrodeposition process, processes impact less, can directly avoid acid solution impact to useless Liquid carries out the process of metal ion, it is thus achieved that metal recovery rate be greatly improved, purity is not owing to having the impact of acid solution, and purity carries High;
(2) membrane stack of the employing multilamellar ion exchange membrane composition of the present invention, by the device that multilamellar is fixing, enters acid pickle Row processes, and reclaims acid solution efficiency high, selects the ion exchange membrane of the different number of plies according to the concentration of acid solution, process can be effectively ensured Efficiency and process life-span, the treatment effeciency of whole device is greatly improved;
(3) a kind of diffusion dialysis of the present invention and the device of electro-deposition Combined Treatment metal ion acid pickle, recyclable The acid of more than 95%, acid concentration reaches 0.4-10mol/L, the metal of recyclable more than 99.5%, metal purity reach 98% with On;
(4) diffusion dialysis device is provided with two runners, and a runner is acid pickle runner, and another runner is for reclaiming stream Road, reclaims acid and next step process, convenient separation by two runners respectively, and the response rate is high;
(5) include that the waste liquid acid that electrolysis bath carries out being electrolysed significantly is reclaimed due to electric deposition device, it is to avoid former The situation that when having process, power consumption is big, has been effectively ensured the electrolysis life-span, and electrolysis effectiveness is good, and care and maintenance expense drops significantly Low;
(6) it is respectively arranged with immersible pump I and immersible pump II in intermediate buffer tank and electro-deposition residual liquid pond tank, and passes through respectively Valve I and valve II controls pipeline and opens, and forms the closed circuit of whole system.Acid pickle can be controlled by arranging of the pump housing Processing sequence and the time;
(7) due to process liquid be acidic materials, use corrosion resistance pipeline be attached, silicone rubber tube or latex tubing Good stability, and easy for installation, low cost;
(8) this programme is by processing method targetedly, the acid in efficient recovery waste liquid and metal, organic efficiency Height, purity is good, and speed is fast, and controllability is good, can process for multiple acid and metal;
(9) a kind of diffusion dialysis of the present invention and the method and apparatus of electro-deposition Combined Treatment metal ion acid pickle, Reclaiming acid to be back to after mixing with commercial acid produce, reclaiming metal can be directly as by-product sale, through diffusion dialysis Remaining electrodialysis residual liquid final with electro-deposition Combined Treatment, its acidity is low, metal concentration is low, can use cost-effectiveization Learn qualified discharge after the sedimentation method process.
Accompanying drawing explanation
Fig. 1 is diffusion dialysis device schematic diagram;
Fig. 2 is electric deposition device schematic diagram;
Fig. 3 is diffusion dialysis-electro-deposition combined unit schematic diagram.
Label declaration in figure:
1, diffusion dialysis device;2, electric deposition device;3, intermediate buffer tank;4, acid tank tank is reclaimed;5, tank is received;6, spent acid Flow container;7, acid peristaltic pump is reclaimed;8, diffusion dialysis residual liquid peristaltic pump;9, outlet I;10, outlet II;11, import I;12, import II;13, minus plate;14, positive plate;15, power supply;16, membrane stack;17, front clamp plate;18, rear clamping plate;19, upper end cover;20、 Electrolysis bath;21, electrolysis bath import;22, electrolyzer outlet;23, electro-deposition residual liquid pond tank;24, immersible pump I;25, immersible pump II; 26, valve I;27, valve II.
Detailed description of the invention
Below in conjunction with Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1
The present invention is directed to utilize diffusion dialysis device to process containing metal acid pickle to reclaim acid, but produced containing high concentration Metal ion diffusion dialysis residual liquid fails to realize resource reclaim, and cause owing to the acid pickle acid concentration containing metal is the highest cannot profit Reclaim the problems such as metal with electric deposition device, the invention provides a kind of diffusion dialysis and electro-deposition Combined Treatment metal ion The method and apparatus of acid pickle, can solve the defect existed when above-mentioned processing unit is used alone, it is possible to be separately recovered containing gold Belong to acid and metal in acid pickle, it is achieved thereby that trade waste synthetical recovery.
As it is shown on figure 3, the integrated retracting device containing metal acid pickle, including diffusion dialysis device 1 and electric deposition device 2 Composition, diffusion dialysis device 1 is connected by intermediate buffer tank 3 with electric deposition device 2.Prior art be it is generally acknowledged diffusion dialysis Residual liquid acidity after process is the biggest, and about about 1%, this cannot be directly used in electro-deposition and reclaims metal, therefore Prior art does not all account for follow-up connect electro-deposition and continue with residual liquid, but, study discovery through inventor, exactly electricity Deposition recovery metal is also required to residual liquid certain salinity, so can improve power consumption efficiency, reduce cost, and can be big Width improves yield and reclaims purity;And diffusion dialysis residual liquid and about 1% residual acid in and after, generate salt, thus produce Electrical conductance electro-deposition exactly reclaim required for metal.Diffusion dialysis device 1 and electric deposition device 2 pass through intermediate buffer tank 3 connect, it is achieved that the effect both having that we are required and feature.
As it is shown in figure 1, diffusion dialysis device 1 is plate and frame, described diffusion dialysis device 1 is by some leafing proton exchanges The membrane stack 16 of composition, and it is fixed on the front clamp plate 17 of membrane stack 16 both sides and rear clamping plate 18 forms.Described membrane stack 16 by The gripper shoe that sets gradually, sealing gasket, ion exchange membrane, sealing gasket, runner filter, sealing gasket, ion exchange membrane, sealing gasket and Gripper shoe is once overrided to form.Ion exchange membrane is 5-50 layer, selects different ions according to different demands with acid strength The number of plies of exchange membrane;Ion exchange membrane, for different disposal ion, selects different types of ion exchange membrane, and the present embodiment processes Copper-containing waste acid liquid, this place uses the NDADF1 type anion exchange membrane that Nan great Environmental Protection Technology Co., Ltd provides, uses 20 tunics Processing, total effective film area of this device is about 20cm2
Diffusion dialysis device 1 is provided with two runners, and a runner is acid pickle runner, the import I11 of acid pickle runner Being connected to inside spent acid flow container by pipeline, outlet I9 is by pipeline and is connected to middle slow through diffusion dialysis residual liquid peristaltic pump 8 Rushing tank 3 internal, another runner, for reclaiming runner, reclaims tunnel inlets II12 connection and receives tank 5, and outlet II is by reclaiming acid wriggling Pump 7 connects recovery acid tank tank 4, receives the acid through diffusion dialysis device separation and recovery.Described pipeline can be silicone rubber tube Or latex tubing, the present embodiment selects silicone rubber tube to use as pipeline.
As in figure 2 it is shown, described electric deposition device 2 includes electrolysis bath 20, electrolysis bath 20 is internal is provided with minus plate 13, anode Plate 14 and upper end cover 19, minus plate 13 and positive plate 14 connect positive pole and the negative pole of power supply 15, the electrolysis bath import of electrolysis bath 20 21 and electrolyzer outlet 22 be connected to intermediate buffer tank 3 and the inside of electro-deposition residual liquid pond tank 23 by pipeline respectively.Middle slow Be respectively arranged with immersible pump I24 and immersible pump II25 in rushing tank 3 and electro-deposition residual liquid pond tank 23, and respectively by valve I26 and Valve II27 controls pipeline and opens, and forms the closed circuit of whole system.
The device of the present embodiment is on the diffusion dialysis device 1 of above-mentioned existing plate and frame and the basis of electric deposition device 2 On, the outlet I 9 of the acid pickle runner of this diffusion dialysis device 1 is connected with intermediate buffer tank 3, the electrolysis of electric deposition device 2 In groove 20, import 21 is connected with intermediate buffer tank 3, disposes buffering immersible pump I24 to delay thus by centre in intermediate buffer tank 3 Rush tank 3 and plate and frame diffusion dialysis device 1 and electric deposition device 2 are jointly formed what a metal ion acid pickle processed Integrating device.
When utilizing the above-mentioned acid pickle integrated treating device assembled to carry out the process operation of metal ion acid pickle, the most past Receive and tank 5 irrigates 2L tap water to the 2/3 of tank body capacity;In spent acid flow container 6, irrigate 2L consist of 0.15mol/L CuSO4 With 1.2mol/L H2SO4Metal ion acid pickle, account for the 2/3 of tank body;Receive at diffusion dialysis with reclaiming acid tank tank 4 The recovery acid obtained after reason;The acid residual liquid after diffusion dialysis processes is received with intermediate buffer tank 3;Rinse with acid pickle respectively The acid pickle runner of plate and frame diffusion dialysis device and with the recovery runner of fresh water flush plate and frame diffusion dialysis device to get rid of Bubble in runner, is then turned on reclaiming acid peristaltic pump 7 and diffusion dialysis residual liquid peristaltic pump 8, regulates a flow velocity as diffusion Dialysis flow velocity, and keep reclaiming acid peristaltic pump and diffusion dialysis residual liquid peristaltic pump in whole integrated processing procedure all the time with this stream Speed is run.The flow velocity Q regulating diffusion dialysis in the present embodiment is 0.6L/h.Reach stable at diffusion dialysis plant running 90min After, regulating pH to 3 in intermediate buffer tank 3, power-on 15 runs electric deposition device 2, and in the present embodiment, voltage can set respectively Being set to 3-9V, holding plate frame diffusion dialysis device 1 runs together with electric deposition device 2 afterwards.
In the integrated process operating process of above-mentioned metal ion acid pickle, pending consists of 0.12mol/L CuSO4With 1.2mol/L H2SO4Metal ion acid pickle entered in integrated treating device of the present invention by silicone rubber tube The acid pickle runner of plate and frame diffusion dialysis device 1, carry out abundant mass transfer exchange with the reception liquid receiving tank 5, then pass through Silicone rubber tube is also finally reached intermediate buffer tank 3, wherein during mass transfer exchanges, containing metal through diffusion dialysis peristaltic pump 8 Sulphuric acid in ion acid pickle reaches to reclaim runner through anion exchange membrane, is then wriggled by silicone rubber tube recovered acid Pump 7 eventually arrives at recovery acid tank, can return production recycling with commercial acid after mixing.Diffusion in intermediate buffer tank 3 is oozed After analysis residual liquid regulation pH is 3, is pumped in electric deposition device 2 electrolysis bath 20 by immersible pump 24, flood electricity at diffusion dialysis residual liquid After precipitation equipment yin, yang pole plate, power-on 15 runs electric deposition device 2, keeps diffusion dialysis device 1 and electro-deposition dress afterwards Put 2 to run together.When the concentration of metal ions in electric deposition device 2 is less than finite concentration, it is 1% herein, Open valve Electric deposition device water outlet is pumped in Waste Water Treatment by II27.Therefore, the present invention is to utilize the diffusion in integrated treating device Acid in the first waste acid recovery liquid of electrodialysis apparatus 1, reduces the concentration of acid in acid pickle simultaneously, then with electric deposition device 2 waste acid recovery Heavy metal in liquid, final outflow water is qualified discharge after water treatment system.By above-mentioned process operating process, gained partial results Arrange such as table 1.
Table 1 integrated treatment copper-containing waste acid liquid experimental result
As can be seen from Table 1: compared to single diffusion dialysis device, this integrating device has not only reclaimed acid, and returns Receive copper;Along with the increase of Q, acid recovering rate and recovery acid concentration diminish, and copper recovery and current efficiency increase;Along with voltage Increase, acid recovering rate and to reclaim acid concentration change little, and copper recovery and current efficiency increase;Integrating device is come Say, when selecting each operating parameter, the impact of each side should be considered.
Liquid waste processing integrating device of the present invention is utilized to carry out in the said process that metal ion acid pickle processes operation, While reclaiming acid, also reduce the acid concentration in waste liquid, then using waste liquid the connecing as electric deposition device after acid separates By liquid, reclaim metal therein.By being used in combination two kinds of devices, both compensate for conventional unheeded diffusion dialysis residual liquid Process problem, considerably reduces again the acid concentration of cupric resin desorption liquid, has expanded the scope of application of electrodeposition process, it is achieved acid With the effective recycling of heavy metal, thus realize the purpose of metal ion acid pickle resource.
Embodiment 2
The integrated retracting device containing metal acid pickle of the present embodiment, including diffusion dialysis device 1 and electric deposition device 2 Composition, diffusion dialysis device 1 and electric deposition device 2 passes through intermediate buffer tank 3 and is connected, it is achieved that our required both having Effect and feature.
As it is shown in figure 1, diffusion dialysis device 1 is plate and frame, described diffusion dialysis device 1 is by some leafing proton exchanges The membrane stack 16 of composition, and it is fixed on the front clamp plate 17 of membrane stack 16 both sides and rear clamping plate 18 forms.Described membrane stack 16 by The gripper shoe that sets gradually, sealing gasket, ion exchange membrane, sealing gasket, runner filter, sealing gasket, ion exchange membrane, sealing gasket and Gripper shoe is once overrided to form.Ion exchange membrane is 5-50 layer, selects different ions according to different demands with acid strength The number of plies of exchange membrane;Ion exchange membrane, for different disposal ion, selects different types of ion exchange membrane, and the present embodiment processes Nickel-bearing Waste acid solution, this place uses the NDADF1 type anion exchange membrane that Nan great Environmental Protection Technology Co., Ltd provides, uses 5 tunics to enter Row processes, and total effective film area of this device is about 10cm2
Diffusion dialysis device 1 is provided with two runners, and a runner is acid pickle runner, the import I11 of acid pickle runner Being connected to inside spent acid flow container by pipeline, outlet I9 is by pipeline and is connected to middle slow through diffusion dialysis residual liquid peristaltic pump 8 Rushing tank 3 internal, another runner, for reclaiming runner, reclaims tunnel inlets II12 connection and receives tank 5, and outlet II is by reclaiming acid wriggling Pump 7 connects recovery acid tank tank 4, receives the acid through diffusion dialysis device separation and recovery.Described pipeline can be silicone rubber tube Or latex tubing, the present embodiment selects latex tubing to use as pipeline.
As in figure 2 it is shown, described electric deposition device 2 includes electrolysis bath 20, electrolysis bath 20 is internal is provided with minus plate 13, anode Plate 14 and upper end cover 19, minus plate 13 and positive plate 14 connect positive pole and the negative pole of power supply 15, the electrolysis bath import of electrolysis bath 20 21 and electrolyzer outlet 22 be connected to intermediate buffer tank 3 and the inside of electro-deposition residual liquid pond tank 23 by pipeline respectively.Middle slow Be respectively arranged with immersible pump I24 and immersible pump II25 in rushing tank 3 and electro-deposition residual liquid pond tank 23, and respectively by valve I26 and Valve II27 controls pipeline and opens, and forms the closed circuit of whole system.
When utilizing the above-mentioned acid pickle integrated treating device assembled to carry out the process operation of metal ion acid pickle, the most past Receive and tank 5 irrigates 1L tap water to the 10% of tank body capacity;In spent acid flow container 6, irrigate 1L consist of 0.1mol/L Nickel-bearing Waste The metal ion acid pickle of acid solution and 0.5mol/L hydrochloric acid, accounts for the 10% of tank body;Receive with recovery acid tank tank 4 and ooze through diffusion The recovery acid that analysis obtains after processing;The acid residual liquid after diffusion dialysis processes is received with intermediate buffer tank 3;Use acid pickle respectively Rinse plate and frame diffusion dialysis device acid pickle runner and with the recovery runner of fresh water flush plate and frame diffusion dialysis device with Get rid of the bubble in runner, be then turned on reclaiming acid peristaltic pump 7 and diffusion dialysis residual liquid peristaltic pump 8, regulate a flow velocity conduct Diffusion dialysis flow velocity, and keep reclaiming acid peristaltic pump and diffusion dialysis residual liquid peristaltic pump in whole integrated processing procedure all the time with This flow velocity runs.The flow velocity Q regulating diffusion dialysis in the present embodiment is 0.3L/h.Reach at diffusion dialysis plant running 60min After Wen Ding, regulating pH to 2 in intermediate buffer tank 3, power-on 15 runs electric deposition device 2, and in the present embodiment, voltage is set to 9V, holding plate frame diffusion dialysis device 1 runs together with electric deposition device 2 afterwards.
Embodiment 3
The integrated retracting device containing metal acid pickle of the present embodiment, including diffusion dialysis device 1 and electric deposition device 2 Composition, diffusion dialysis device 1 and electric deposition device 2 passes through intermediate buffer tank 3 and is connected, it is achieved that our required both having Effect and feature.
As it is shown in figure 1, diffusion dialysis device 1 is plate and frame, described diffusion dialysis device 1 is by some leafing proton exchanges The membrane stack 16 of composition, and it is fixed on the front clamp plate 17 of membrane stack 16 both sides and rear clamping plate 18 forms.Described membrane stack 16 by The gripper shoe that sets gradually, sealing gasket, ion exchange membrane, sealing gasket, runner filter, sealing gasket, ion exchange membrane, sealing gasket and Gripper shoe is once overrided to form.Ion exchange membrane is 5-50 layer, selects different ions according to different demands with acid strength The number of plies of exchange membrane;Ion exchange membrane, for different disposal ion, selects different types of ion exchange membrane, and the present embodiment processes Nickel-bearing Waste acid solution, this place uses the NDADF1 type anion exchange membrane that Nan great Environmental Protection Technology Co., Ltd provides, uses 50 tunics Processing, total effective film area of this device is about 80cm2
Diffusion dialysis device 1 is provided with two runners, and a runner is acid pickle runner, the import I11 of acid pickle runner Being connected to inside spent acid flow container by pipeline, outlet I9 is by pipeline and is connected to middle slow through diffusion dialysis residual liquid peristaltic pump 8 Rushing tank 3 internal, another runner, for reclaiming runner, reclaims tunnel inlets II12 connection and receives tank 5, and outlet II is by reclaiming acid wriggling Pump 7 connects recovery acid tank tank 4, receives the acid through diffusion dialysis device separation and recovery.Described pipeline can be silicone rubber tube Or latex tubing, the present embodiment selects latex tubing to use as pipeline.
As in figure 2 it is shown, described electric deposition device 2 includes electrolysis bath 20, electrolysis bath 20 is internal is provided with minus plate 13, anode Plate 14 and upper end cover 19, minus plate 13 and positive plate 14 connect positive pole and the negative pole of power supply 15, the electrolysis bath import of electrolysis bath 20 21 and electrolyzer outlet 22 be connected to intermediate buffer tank 3 and the inside of electro-deposition residual liquid pond tank 23 by pipeline respectively.Middle slow Be respectively arranged with immersible pump I24 and immersible pump II25 in rushing tank 3 and electro-deposition residual liquid pond tank 23, and respectively by valve I26 and Valve II27 controls pipeline and opens, and forms the closed circuit of whole system.
When utilizing the above-mentioned acid pickle integrated treating device assembled to carry out the process operation of metal ion acid pickle, the most past Receive and tank 5 irrigates 2L tap water to the 90% of tank body capacity;In spent acid flow container 6 irrigate 2L consist of 10mol/L containing zinc give up The metal ion acid pickle of acid solution and 10mol/L nitric acid, accounts for the 90% of tank body;Receive with recovery acid tank tank 4 and ooze through diffusion The recovery acid that analysis obtains after processing;The acid residual liquid after diffusion dialysis processes is received with intermediate buffer tank 3;Use acid pickle respectively Rinse plate and frame diffusion dialysis device acid pickle runner and with the recovery runner of fresh water flush plate and frame diffusion dialysis device with Get rid of the bubble in runner, be then turned on reclaiming acid peristaltic pump 7 and diffusion dialysis residual liquid peristaltic pump 8, regulate a flow velocity conduct Diffusion dialysis flow velocity, and keep reclaiming acid peristaltic pump and diffusion dialysis residual liquid peristaltic pump in whole integrated processing procedure all the time with This flow velocity runs.The flow velocity Q regulating diffusion dialysis in the present embodiment is 0.6L/h.Reach at diffusion dialysis plant running 120min After Wen Ding, regulating pH to 7 in intermediate buffer tank 3, power-on 15 runs electric deposition device 2, and in the present embodiment, voltage is set to 6V, holding plate frame diffusion dialysis device 1 runs together with electric deposition device 2 afterwards.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, and difference is, includes sulphuric acid and hydrochloric acid mixed solution containing acid waste liquid, The sour mixed liquor needing metal ion to be processed to be aluminium ion, iron ion.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 2, and difference is, includes sulphuric acid, hydrochloric acid and nitric acid containing acid waste liquid Mixed liquor, need metal ion to be processed be copper ion, nickel ion, zinc ion, cadmium ion, chromium ion, lead ion, aluminium ion, The mixture that iron ion, tin ion, mercury ion, silver ion, gold ion are any more than two.
Embodiment 6
Utilizing the method that device processes metal ion acid pickle, step is as follows:
Step 1: irrigate tap water in tank 5 toward receiving, to the 10-90% accounting for tank body volume;
Step 2: in spent acid flow container 6 irrigate acid concentration be 0.5-10mol/L, concentration of metal ions be 0.1-10mol/L Metal ion acid pickle, to the 10-90% accounting for tank body volume;Heavy metal ion in metal ion acid pickle be copper from Son, nickel ion, zinc ion, cadmium ion, chromium ion, lead ion, aluminium ion, iron ion, tin ion, mercury ion, silver ion, gold from Son, or the mixture of any more than two of above-mentioned ion.Acid is hydrochloric acid, sulphuric acid, nitric acid, or any more than two of above-mentioned acid Mixture.
Step 3: receive the acid through diffusion dialysis device 1 separation and recovery with reclaiming acid tank tank 4;
Step 4: receive the diffusion dialysis residual liquid after diffusion dialysis device 1 with intermediate buffer tank 3;
Step 5: after diffusion dialysis, rinses the acid pickle runner of diffusion dialysis device 1 respectively, rushes with tap water with acid pickle That washes diffusion dialysis device reclaims runner to get rid of the bubble in two runners, treats that diffusion dialysis device 1 runs 60-120min and arrives Reach after stablizing, open diffusion dialysis residual liquid peristaltic pump 8, and keep diffusion dialysis residual liquid peristaltic pump 8 in whole Combined Treatment mistake Journey is run with constant flow rate all the time;
Step 6: after opening import I 11 isolated operation diffusion dialysis device 1, then spreads in regulation intermediate buffer tank 3 and oozes Analysis residual liquid pH is 2-7, the valve I26 being then turned in intermediate buffer tank 3, makes diffusion dialysis residual liquid flow into electrolysis bath 20, then opens Open power supply 15 and run electric deposition device 2, keep diffusion dialysis device 1 to run together with electric deposition device 2 afterwards, carry out containing metal The integration recycling of ion acid pickle.
Below being schematically described the invention and embodiment thereof, this description does not has restricted, not In the case of deviating from the spirit or essential characteristics of the present invention, it is possible to realize the present invention in other specific forms.Institute in accompanying drawing Show is also one of embodiment of the invention, and actual structure is not limited thereto, any attached in claim Figure labelling should not limit involved claim.

Claims (10)

1. the integrated retracting device containing metal acid pickle, it is characterised in that: include diffusion dialysis device (1) and electric deposition device (2) composition, diffusion dialysis device (1) is connected by intermediate buffer tank (3) with electric deposition device (2).
Integrated retracting device containing metal acid pickle the most according to claim 1, it is characterised in that: described diffusion is oozed The membrane stack (16) that analysis apparatus (1) is made up of some leafing proton exchanges, and it is fixed on the front clamp plate of membrane stack (16) both sides (17) form with rear clamping plate (18).
Integrated retracting device containing metal acid pickle the most according to claim 2, it is characterised in that: described membrane stack (16) by the gripper shoe set gradually, sealing gasket, ion exchange membrane, sealing gasket, runner filter, sealing gasket, ion exchange membrane, close Packing and gripper shoe are once overrided to form.
Integrated retracting device containing metal acid pickle the most according to claim 1, it is characterised in that: diffusion dialysis device (1) being provided with two runners, a runner is acid pickle runner, and the import I (11) of acid pickle runner is connected to give up by pipeline Inside acid solution tank, outlet I (9) is connected to intermediate buffer tank (3) inside by pipeline and through diffusion dialysis residual liquid peristaltic pump (8); Another runner, for reclaiming runner, reclaims tunnel inlets II (12) and connects reception tank (5), and outlet II is by reclaiming acid peristaltic pump (7) Connect and reclaim acid tank tank (4), receive the acid separated and recovered through diffusion dialysis device (1).
Integrated retracting device containing metal acid pickle the most according to claim 1, it is characterised in that: described electro-deposition Device (2) includes electrolysis bath (20), and electrolysis bath (20) is internal is provided with minus plate (13), positive plate (14) and upper end cover (19), cloudy Pole plate (13) and positive plate (14) connect positive pole and the negative pole of power supply (15), the electrolysis bath import (21) of electrolysis bath (20) and electrolysis Groove outlet (22) is connected to intermediate buffer tank (3) and the inside in electro-deposition residual liquid pond tank (23) by pipeline respectively.
Integrated retracting device containing metal acid pickle the most according to claim 5, it is characterised in that: intermediate buffer tank (3) immersible pump I (24) and immersible pump II (25) and it is respectively arranged with in electro-deposition residual liquid pond tank (23), and respectively by valve I (26) control pipeline open with valve II (27), form the closed circuit of whole system.
7. according to the integrated retracting device containing metal acid pickle described in claim 4 or 5 or 6, it is characterised in that: described Pipeline is silicone rubber tube or latex tubing.
8. utilizing the method that device described in claim 1 processes metal ion acid pickle, step is as follows:
Step 1: toward receiving perfusion tap water in tank (5), to the 10-90% accounting for tank body volume;
Step 2: past spent acid flow container (6) middle perfusion acid concentration is 0.5-10mol/L, concentration of metal ions is 0.1-10mol/L's Metal ion acid pickle, to the 10-90% accounting for tank body volume;
Step 3: receive the acid separated and recovered through diffusion dialysis device (1) with reclaiming acid tank tank (4);
Step 4: receive the diffusion dialysis residual liquid after diffusion dialysis device (1) with intermediate buffer tank (3);
Step 5: after diffusion dialysis, rinses the acid pickle runner of diffusion dialysis device (1) respectively, rinses with tap water with acid pickle The recovery runner of diffusion dialysis device, to get rid of the bubble in two runners, treats that diffusion dialysis device (1) runs 60-120min and arrives Reach after stablizing, open diffusion dialysis residual liquid peristaltic pump (8), and keep diffusion dialysis residual liquid peristaltic pump (8) to combine place whole All the time run with constant flow rate during reason;
Step 6: after opening import I (11) isolated operation diffusion dialysis device (1), then regulates diffusion in intermediate buffer tank (3) Dialysis residual liquid pH is 2-7, the valve I (26) being then turned in intermediate buffer tank (3), makes diffusion dialysis residual liquid flow into electrolysis bath (20), it is then turned on power supply (15) and runs electric deposition device (2), keep diffusion dialysis device (1) and electric deposition device (2) afterwards Run together, carry out the integration recycling of metal ion acid pickle.
The method of process metal ion acid pickle the most according to claim 8, it is characterised in that: metal ion spent acid Heavy metal ion in liquid is copper ion, nickel ion, zinc ion, cadmium ion, chromium ion, lead ion, aluminium ion, iron ion, stannum Ion, mercury ion, silver ion, gold ion, or the mixture of any more than two of above-mentioned ion.
The method of process metal ion acid pickle the most according to claim 8, it is characterised in that: acid is hydrochloric acid, sulfur Acid, nitric acid, or the mixture of any more than two of above-mentioned acid.
CN201610659331.5A 2016-08-11 2016-08-11 Integrated retracting device containing metal acid pickle and method Pending CN106277479A (en)

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CN113149248A (en) * 2021-01-19 2021-07-23 中基(海南)科技有限公司 Green electroplating wastewater recycling treatment process
CN116065033A (en) * 2023-01-03 2023-05-05 广东邦普循环科技有限公司 Method for treating nickel salt and acid by membrane method in hydrometallurgy and battery anode material

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CN105712545A (en) * 2016-01-27 2016-06-29 苏州得润环保科技有限公司 Copper-contained wastewater recycling system
CN205874104U (en) * 2016-08-11 2017-01-11 南京大学 Containing metal spent acid's integrated recovery unit

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CN101343039A (en) * 2008-08-20 2009-01-14 北京科技大学 Method for recycling pure acid from metallic ion containing waste acid and regenerating alkali
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CN110724963A (en) * 2019-10-24 2020-01-24 中国科学院过程工程研究所 Method for recovering acid and metal elements in metal surface pickling waste liquid
CN113149248A (en) * 2021-01-19 2021-07-23 中基(海南)科技有限公司 Green electroplating wastewater recycling treatment process
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Application publication date: 20170104