CN205874104U - Containing metal spent acid's integrated recovery unit - Google Patents
Containing metal spent acid's integrated recovery unit Download PDFInfo
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- CN205874104U CN205874104U CN201620865659.8U CN201620865659U CN205874104U CN 205874104 U CN205874104 U CN 205874104U CN 201620865659 U CN201620865659 U CN 201620865659U CN 205874104 U CN205874104 U CN 205874104U
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- 239000002253 acid Substances 0.000 title claims abstract description 199
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000011084 recovery Methods 0.000 title abstract description 39
- 238000009792 diffusion process Methods 0.000 claims abstract description 130
- 238000000502 dialysis Methods 0.000 claims abstract description 124
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 230000008021 deposition Effects 0.000 claims abstract description 42
- 238000004070 electrodeposition Methods 0.000 claims abstract description 32
- 235000021110 pickles Nutrition 0.000 claims description 81
- 238000005868 electrolysis reaction Methods 0.000 claims description 29
- 230000002572 peristaltic effect Effects 0.000 claims description 25
- 239000003014 ion exchange membrane Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 21
- 238000007789 sealing Methods 0.000 claims description 19
- 230000008676 import Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229920002379 silicone rubber Polymers 0.000 claims description 10
- 239000004945 silicone rubber Substances 0.000 claims description 10
- 239000004816 latex Substances 0.000 claims description 8
- 229920000126 latex Polymers 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 49
- 239000002699 waste material Substances 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 61
- 230000008569 process Effects 0.000 description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- -1 plating Inorganic materials 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The utility model discloses a containing metal spent acid's integrated recovery unit belongs to the waste recycling field. The utility model discloses utilize the diffusion dialysis device will be including the separation of the acid among the metal ion spent acid and metal ion, the acidizing fluid behind the separation metal ion can regard as the recovered acid to repeat cyclic utilization, and the metal ion waste liquid that contains after the separation is sour is recycled the reduction of electric deposition apparatus and is retrieved the metal, and final electro -deposition raffinate emits into effluent disposal system. The utility model discloses unite two kinds of devices, both solved metal ion recovery processing problem in the diffusion dialysis raffinate of in the past being ignored, reduced the acid concentration that contains metal ion spent acid again by a wide margin, created the application condition that electric deposition apparatus retrieved metal ion in the diffusion dialysis raffinate, utilize the complementary characteristics of diffusion dialysis and electro -deposition unit device, realized containing the metal ion 1 of sour and metal among the metal ion spent acid.
Description
Technical field
This utility model relates to field of waste recycle, more particularly, it relates to the integration recovery containing metal acid pickle
Device.
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, this utility model provides the integrated retracting device containing metal acid pickle, and it can be separately recovered containing metal spent acid
Acid and metal in liquid, 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, the utility model has the advantage of:
(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) method of a kind of diffusion dialysis of the present utility model and electro-deposition Combined Treatment metal ion acid pickle and dress
Putting, reclaim acid and can be back to after mixing with commercial acid produce, reclaiming metal can ooze through diffusion directly as by-product sale
Analysis and the final remaining electrodialysis residual liquid of electro-deposition Combined Treatment, its acidity is low, metal concentration is low, can use cost-effective
Qualified discharge after chemical precipitation 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, this utility model is described in detail.
Embodiment 1
This utility model for utilizing diffusion dialysis device to process containing metal acid pickle to reclaim acid, but produced contain high
Concentration metal ion diffusion dialysis residual liquid fails to realize resource reclaim, and causes nothing owing to the acid pickle acid concentration containing metal is the highest
Method utilizes electric deposition device to reclaim the problems such as metal, the invention provides a kind of diffusion dialysis with electro-deposition Combined Treatment containing metal
The method and apparatus of ion acid pickle, can solve the defect existed when above-mentioned processing unit is used alone, it is possible to be separately recovered
Containing acid and metal in metal 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.
Claims (7)
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.
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