CN110042426A - A kind of closed electrodeposition pipe and gallium electrodeposition system - Google Patents
A kind of closed electrodeposition pipe and gallium electrodeposition system Download PDFInfo
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- CN110042426A CN110042426A CN201910491154.8A CN201910491154A CN110042426A CN 110042426 A CN110042426 A CN 110042426A CN 201910491154 A CN201910491154 A CN 201910491154A CN 110042426 A CN110042426 A CN 110042426A
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- electrodeposition
- gallium
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- closed
- separating tank
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of closed electrodeposition pipe and gallium electrodeposition system, the closed electrodeposition pipe are vertically arranged；The closed electrodeposition pipe is equipped with electrodeposition solution inlet and electrodeposition taphole, and the electrodeposition solution inlet is lower than the electrodeposition taphole；Anode and cathode is additionally provided on the closed electrodeposition pipe.Compared with prior art, the present invention uses closed electrodeposition pipe, takes the pressure liquid in-out mode of vertical direction " bottom in and top out ", the internal circulating load containing Gallium solution is bigger, and it is higher to eliminate concentration polarization of the different parts containing Gallium solution, current efficiency in closed electrodeposition pipe.And electrolytic deposition process whole process all carries out under air-tight state, and the gas generated in electrolytic deposition process can be made to flow through exhaust pipe discharge with liquid, draws electrodeposition scene, open circuit conditions caused by avoiding electrolytic deposition process due to gas, site environment close friend in time.
Description
Technical field
The present invention relates to field of hydrometallurgy, more particularly to a kind of closed electrodeposition pipe and gallium electrodeposition system.
Background technique
Gallium is pale blue non-ferrous metal, becomes silvery white liquid at 29.76 DEG C.It is a kind of important semiconductor material, extensively
Applied to fields such as communication, integrated circuit, the energy, medical and health.Since concentration of the gallium in the earth's crust is very low, distribution is not concentrated,
It generally requires and is recycled and produced from richness Gallium solution obtained in other main Metal Productions, most commonly from aluminium oxide
Gallium is extracted and recycled in production solution.
Electrolytic deposition (referred to as " electrodeposition "), gallium ion are carried out to solution from generally requiring rich in recycling gallium in Gallium solution
The process for being electrolytic reduced to Metallic Gallium carries out in a cell.Application No. is 201810820545.5 to propose a kind of gold
Belong to gallium cyclic electrolysis system.Please shown in referring also to Fig. 1 and Fig. 2, Fig. 1 is the structure of prior art gallium cyclic electrolysis system
Schematic diagram, Fig. 2 are the structural schematic diagram of electrolytic cell in prior art gallium cyclic electrolysis system.It is specific as follows: a kind of metal
Gallium cyclic electrolysis system, includes storage element 10a, electrolytic cell 30a and heat exchanger 90a, the storage element 10a include cooling
Slot 11a, head tank 12a and dashpot 13a；The cooling bath 11a, head tank 12a and dashpot 13a and electrolytic cell 30a are successively
It is connected, forms circulation loop；Meanwhile the heat exchanger is connected to electrolytic cell 30a, head tank 12a respectively by pipeline and pump B,
Contain Gallium solution to cooling.The electrolytic cell 30a is rectangular configuration, and one end of the electrolytic cell 30a connection cooling bath 11a is on the lower
Position is provided with discharge port, and one end upper position of the electrolytic cell 30a connection dashpot 13a is provided with feed inlet 31a.Institute
State the inside of electrolytic cell 30a and perpendicular to the bottom plate of the electrolytic cell 30a be provided with multiple groups with parallel electricity is flowed to containing Gallium solution
Plate 32a is solved, the electrolytic zinc-coated steel sheet 32a is fixed on the electrolytic cell 30a's by the corresponding connection sheet 33a of multiple groups and group co-clip 34a
On bottom plate；The connection sheet 33a is connect with cathode and anode connection sheet 35a.When work, by yin, yang connection sheet 35a connection power supply
Positive and negative anodes occur electrochemical reaction on the surface electrolytic zinc-coated steel sheet 32a under impressed current effect containing Gallium solution, generate gallium.
The electrolytic cell of the above-mentioned gallium cyclic electrolysis system of the prior art uses the liquid in-out mode of horizontal direction, contains gallium
Flowing to for solution is single, causes its internal circulating load smaller, and it is serious to easily lead to concentration polarization of the electrolytic cell different parts containing Gallium solution, nothing
Method realizes high current electrodeposition, causes current efficiency low；Simultaneously as causing electricity containing residual organic matter matter possible in Gallium solution
There is gas output during product, which be easy to cause electrolytic deposition process breaking, in addition, gas directly diffuses to operation from electrolytic cell
Space keeps operating environment air quality poor, causes serious security risk to staff and process equipment；And cell bottom
The gallium needs of portion's deposition are collected by way of being manually discharged, cumbersome, and gallium is be easy to cause to lose.
Summary of the invention
Based on this, the present invention provides a kind of closed electrodeposition pipe and gallium electrodeposition system, can be in electrolytic deposition under closed environment
Gallium, current efficiency with higher.
Closed electrodeposition pipe of the present invention is vertically arranged；The closed electrodeposition pipe is equipped with electrodeposition solution inlet and electrodeposition is molten
Liquid outlet, and the electrodeposition solution inlet is lower than the electrodeposition taphole；Anode and yin are additionally provided on the closed electrodeposition pipe
Pole.
Compared with prior art, the present invention uses closed electrodeposition pipe, and the pressure of vertical direction " bottom in and top out " is taken to pass in and out
Liquid mode, compared with the horizontal direction liquid in-out mode of conventional electrolysis slot, the internal circulating load containing Gallium solution is bigger, and eliminates closed
Concentration polarization of the different parts containing Gallium solution in electrodeposition pipe, current efficiency with higher.And electrolytic deposition process whole process is all closed
It is carried out under state, the gas generated in electrolytic deposition process can be made to flow through exhaust pipe discharge with liquid, draw electrodeposition scene in time,
Open circuit conditions caused by electrolytic deposition process is avoided due to gas, site environment are friendly.
Further, the closed electrodeposition pipe includes: vertically arranged tube body；Lower cover, the lower cover are arranged in institute
It states at the nozzle below tube body, the electrodeposition solution inlet is formed in the lower cover；And upper end cover, the upper end cover setting
At the nozzle above the tube body, the electrodeposition taphole is formed in the upper end cover.
The pressure liquid in-out mode for taking vertical direction " bottom in and top out ", the internal circulating load containing Gallium solution is maximum, is eliminating
In closed electrodeposition pipe while concentration polarization of the different parts containing Gallium solution, make closed electrodeposition pipe that there is high current efficiency.
Further, the anode is anode tube, and the lower end of the anode tube, which is worn, to be fixed in the lower cover；It is described
The tube body part of anode tube is arranged in the tube body along the central axis of the tube body；The cathode is the tube body, institute
State the central axis upright setting of tube body.
The anode tube and cathode cylinder run through the closed electrodeposition pipe, expand significantly and electrodeposition occurs containing Gallium solution
The contact area of reaction improves electrolysis effectiveness；And compared with conventional electrolytic deposition process, high current electrodeposition may be implemented, it is maximum reachable
To 1600A, current efficiency is higher.
The present invention also provides a kind of gallium electrodeposition systems, including reserve tank, separating tank and the closed electrodeposition pipe；
The reserve tank, separating tank are sequentially connected, and the top of the separating tank is arranged in the closed electrodeposition pipe；
Enter in closed electrodeposition pipe containing Gallium solution from the electrodeposition solution inlet of closed electrodeposition pipe, is issued in impressed current effect
Raw electrochemical reaction generates gallium；It is discharged again from the electrodeposition taphole containing Gallium solution, gallium is from electrodeposition solution inlet
Discharge.
Compared with prior art, the present invention uses closed electrodeposition pipe, and the pressure of vertical direction " bottom in and top out " is taken to pass in and out
Liquid mode, compared with the horizontal direction liquid in-out mode of conventional electrolysis slot, the internal circulating load containing Gallium solution is bigger, and eliminates closed
Concentration polarization of the different parts containing Gallium solution in electrodeposition pipe.And electrolytic deposition process whole process all carries out under air-tight state, can make electrodeposition
The gas generated in the process flows through exhaust pipe discharge with liquid, draws electrodeposition scene in time, avoids electrolytic deposition process because of gas
Body and caused by open circuit conditions, site environment is friendly.
Further, the separating tank is closed cell；The top of the separating tank is equipped with separating tank inlet and separating tank
Liquid outlet；The bottom of the separating tank is equipped with separating tank and arranges gallium mouth；The separating tank liquid outlet is molten with the closed electrodeposition pipe
The connection of liquid entrance.
Separating tank of the invention mainly plays buffering and gallium is separated with containing Gallium solution.On the one hand, make to be pumped into point
There are a buffering and uniformly mixed space containing Gallium solution from slot, to improve electrolytic deposition process efficiency in subsequent closed electrodeposition pipe；
On the other hand, rationally control solution flow velocity, the gallium for making generation under the effect of gravity, are freely fallen into separating tank, realize electricity
Solve the physical separation of liquid and gallium.
It further, further include exhaust pipe；The exhaust pipe is arranged on the closed electrodeposition pipe and the separating tank；Institute
The gas of closed electrodeposition pipe electrolytic deposition process generation is stated by being discharged in exhaust pipe.
The exhaust pipe is vented automatically by exhaust valve, the gas generated in electrolytic deposition process is discharged.It can prevent close
It closes gas in electrodeposition pipe and separating tank to be enriched with, influences electric effect；The subsequent waste gas treatment device that can be set receives the gas
Collection and processing.
Further, the reserve tank is equipped with reserve tank inlet and electrodeposition liquid outlet；The reserve tank inlet is logical
A pipeline is crossed to be connected to the electrodeposition taphole of the closed electrodeposition pipe；The electrodeposition liquid outlet is separated by a pipeline with described
Slot inlet connection, so that the reserve tank, separating tank and closed electrodeposition pipe be made to form closed loop.
Reserve tank of the invention mainly plays a part of to recycle containing gallium ion in Gallium solution, and original is fresh containing Gallium solution
After electrochemical reaction occurs in into closed electrodeposition pipe, the gallium ion and unreacted in electrolyte are thorough.In order to improve closed electricity
Product manages the electrodeposition efficiency of interior gallium ion, will contain Gallium solution by the taphole at a pipeline from closed electrodeposition tube top end and lead back storage
In slot, and it is pumped into separating tank and closed electrodeposition pipe again, so that the further electrolytic deposition of the thorough gallium ion of unreacted.
It further, further include heat exchanger, the heat exchanger includes first fluid channel and second fluid channel；Described
The import of one fluid channel is connect with the cooling liquid outlet of the reserve tank, the outlet and the storage in the first fluid channel
The connection of slot inlet, the first fluid and the reserve tank form a sealing and circulating circuit；The second fluid channel is surround
The outer wall in the first fluid channel, and be passed through coolant liquid to the second fluid channel, and controlled by automatic regulating valve cold
But the flow velocity and flow of liquid, to adjust the temperature of solution in the first fluid channel indirectly.
Electrolyte inevitably heats up in electrolytic deposition process, and the temperature of electrolyte can be effectively controlled by heat exchanger, with
Guarantee electrolytic deposition process continues efficiently to carry out.
It further, further include gallium separator；The gallium separator is that a bottom is funnelform container；The gallium separation
Entrance at the top of device is connect with separating tank row's gallium mouth；The gallium separator funnel-form bottom end offers gallium collection port；The gallium point
Filtrate port is offered from device side wall.
It further, further include filtrate receiver；The entrance of the filtrate receiver is connect with the filtrate port of gallium separator, the filtrate
The outlet of slot is connect by filtrate pump and circulation pipe with reserve tank inlet, and the solution pump in filtrate receiver is back to reserve tank
In.
The gallium that closed electrodeposition pipe generates finally is deposited on through entering in separating tank and gallium separator under gravity
Gallium separator funnel-form bottom end can realize the collection of gallium by manual nest or automatic discharging device, simple to operate,
Avoid the loss of gallium caused by personnel's lock out operation.Contain part gallium ion in the electrolyte that filtrate receiver is collected, still in order into one
Step improves the rate of recovery of gallium ion, will be in the liquid blowback reserve tank in filtrate receiver using filtrate pump, further circulation and electrodeposition.
Compared with the existing technology, closed electrodeposition pipe of the present invention and gallium electrodeposition system have the advantages that (1) is molten containing gallium
Liquid in closed electrodeposition pipe, takes the pressure liquid in-out mode of vertical direction " bottom in and top out ", with conventional electrolysis by circulating pump
The horizontal direction liquid in-out mode of slot is compared, and the internal circulating load containing Gallium solution is bigger, and eliminates different parts in closed electrodeposition pipe
Concentration polarization containing Gallium solution；Compared with conventional electrolytic deposition process, high current electrodeposition may be implemented, maximum can reach 1600A, electric current
It is more efficient.(2) closed electrodeposition pipe is used, electrolytic deposition process whole process is carried out all under air-tight state, can make to produce in electrolytic deposition process
Raw gas flows through exhaust pipe discharge with liquid, draws electrolytic deposition process scene in time, avoids electrolytic deposition process due to gas
Caused by open circuit conditions, site environment is friendly.(3) it is temporarily stored in gallium separator after gallium output, passes through manual or automatic row
Expect that device realizes the collection of gallium, it is simple to operate, avoid the loss of gallium caused by personnel's lock out operation.(4) entire gallium
Electrodeposition system full automatic working sets solution temperature using PLC control platform, adjusts supplement cooling water and guarantees that heat exchanger is assisted automatically
It runs；Reflect working condition in real time using instrument such as flowmeter and pressure gauges, guarantees that electrolytic deposition process is safe, controllable.And it powers
The full PLC control of system, automatically gives input current, and feedback current density adds up the electrodeposition time, shows power consumption and voltage etc., and
Fault alarm when can be achieved abnormal.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of prior art gallium cyclic electrolysis system.
Fig. 2 is the structural schematic diagram of electrolytic cell in prior art gallium cyclic electrolysis system.
Fig. 3 is the structural schematic diagram of gallium electrodeposition system of the present invention.
Fig. 4 is the structural schematic diagram of reserve tank in gallium electrodeposition system of the present invention.
Fig. 5 is the structural schematic diagram of closed separating tank in gallium electrodeposition system of the present invention.
Fig. 6 is the structural schematic diagram of closed electrodeposition pipe in gallium electrodeposition system of the present invention.
In Fig. 3~6, mark as follows:
Reserve tank 10, separating tank 20, closed electrodeposition pipe 30, exhaust pipe 40, gallium separator 50, filtrate receiver 60, control device
70, power supply unit 80, heat exchanger 90；
Reserve tank inlet 11, electrodeposition liquid outlet 12, cooling liquid outlet 13, accumulator relief mouth 14, reserve tank sewage draining exit
15, reserve tank fluid infusion 16；
Separating tank inlet 21, partition 23, separating tank row gallium mouth 24, separating tank exhaust outlet 25, divides separating tank liquid outlet 22
From slot leakage fluid dram 26；
Lower cover 31, electrodeposition solution inlet 32, upper end cover 33, electrodeposition taphole 34, cathode 35, anode 36, cathode are led
Electric block 37, anode conducting block 38；
Circulating pump B1, filtrate pump B2, heat exchanger circulating pump B3；
Liquid supplementation pipe L1, sewage pipe L2, drain pipe L3, circulation pipe L5, filtrate pipe L5；
Radar levelmeter R, temperature detector T, flowmeter F, pressure gauge P, automatic regulating valve V.
Specific embodiment
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", "upper", "lower",
The orientation or positional relationship of the instructions such as "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside" is
It is based on the orientation or positional relationship shown in the drawings, is merely for convenience of description of the present invention and simplification of the description, rather than instruction or dark
Show that signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as pair
Limitation of the invention.In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or more.
Referring to Fig. 3, Fig. 3 is the structural schematic diagram of gallium electrodeposition system of the present invention, gallium electrodeposition system of the invention includes storage
Deposit slot 10, separating tank 20, closed electrodeposition pipe 30, exhaust pipe 40, gallium separator 50, filtrate receiver 60, control device 70, power supply unit
80 and heat exchanger 90.The reserve tank 10, separating tank 20 are sequentially connected, and the closed electrodeposition pipe 30 is arranged in the separating tank 20
Top, and the solution inlet of the closed electrodeposition pipe 30 is connect with the liquid outlet of the separating tank 20；The exhaust pipe 40 divides
It is located on separating tank 20 and closed electrodeposition pipe 30.The separating tank 20, gallium separator 50, filtrate receiver 60 are sequentially connected.The control
Device 70 processed is electrically connected with reserve tank 10, separating tank 20, closed electrodeposition pipe 30, exhaust pipe 40, and controls reserve tank 10, separating tank
20, the operation operation of closed electrodeposition pipe 30, exhaust pipe 40, and feed back their working condition of display.The power supply unit 80 with
The control device 70 is electrically connected, and provides power supply for the control device 70.The heat exchanger 90 is connect with the reserve tank 10,
A circulation loop is constituted, the temperature to solution in reserve tank 10 described in circulating cooling.
Specifically, referring to figure 4., Fig. 4 is the structural schematic diagram of reserve tank in gallium electrodeposition system of the present invention.The reserve tank
10 have the container at 5~10 ° of inclinations angle for bottom surface, and reserve tank inlet 11, electrodeposition liquid outlet are equipped on the reserve tank 10
12, cooling liquid outlet 13, accumulator relief mouth 14 and reserve tank sewage draining exit 15.The reserve tank inlet 11 and accumulator relief
The top of the reserve tank 10 is arranged in mouth 15；The electrodeposition liquid outlet 12 and cooling liquid outlet 13 are arranged in the reserve tank 10
Lower end；The lower end of 10 bottom surface of reserve tank is arranged in the reserve tank sewage draining exit 15, and is circumscribed with a sewage pipe L2, uses
With the soiling solution being periodically discharged in reserve tank 10.Reserve tank fluid infusion 16, the fluid infusion are additionally provided at the top of the reserve tank 10
Mouthfuls 16 supplemented by a liquid supplementation pipe L1 into reserve tank 10 it is fresh containing Gallium solution；
It is additionally provided with radar levelmeter R on the reserve tank 10, to monitor the liquid level in reserve tank 10；Meanwhile it also setting up
There are temperature detector T, such as thermal resistance, to detect the temperature of liquid in reserve tank 10.
Referring to Fig. 5, Fig. 5 is the structural schematic diagram of closed separating tank in gallium electrodeposition system of the present invention.The separating tank 20
For closed cell, whole in 10 °~20 ° inclinations, optimal is 15 ° of inclinations.Separating tank import 21, separation are equipped on the separating tank
Slot liquid outlet 22, partition 23, separating tank row gallium mouth 24, separating tank exhaust outlet 25 and separating tank leakage fluid dram 26.The separating tank into
Liquid mouth 21 is arranged in above the side wall of the separating tank 20 at top plate, and passes through a pipeline and circulating pump B1 and the storage
The electrodeposition liquid outlet 12 of slot 10 is connected to, and is equipped with flowmeter F on the pipeline.The separating tank liquid outlet 22 and separating tank exhaust
The top of the separating tank 20 is arranged in mouth 25.The setting of partition 23 goes out in the separating tank inlet 21 with the separating tank
Between liquid mouth 22, to slow down the flow velocity containing Gallium solution for entering separating tank 20 by separating tank inlet 21.The separating tank row
The lower end of 20 bottom of separating tank is arranged in gallium mouth 24；The side of the separating tank 20 is arranged in the separating tank leakage fluid dram 26
Below wall at bottom plate, and it is circumscribed with a drain pipe L3, convenient for the solution being periodically discharged in separating tank 20.
Pressure gauge P is installed on the separating tank 20, to detect the pressure in separating tank 20.
Referring to Fig. 6, Fig. 6 is the structural schematic diagram of closed electrodeposition pipe in gallium electrodeposition system of the present invention, the closed electrodeposition
Pipe 30 is a vertically arranged tube body；As a preference, the closed electrodeposition pipe 30 is the vertically disposed tube body of an axis.
The closed electrodeposition pipe 30 includes lower cover 31, upper end cover 33, cathode 35, anode 36, cathode conducting block 37, anode
Conducting block 38 and electrodeposition pipe exhaust outlet (not shown).The lower cover 31 is arranged at the nozzle below the tube body, and described
Electrodeposition solution inlet 32 is formed in the lower cover 31, and the separating tank of the electrodeposition solution inlet 32 and the separating tank 20 goes out
Liquid mouth 22 connects, and enters closed electrodeposition pipe 30 containing Gallium solution to make.The pipe above the tube body is arranged in the upper end cover 33
Mouthful place, the electrodeposition taphole 34 is formed in the upper end cover 33, the electrodeposition taphole 34 by circulation pipe L4 and
The reserve tank inlet 11 of reserve tank 10 is connected to, and is flow back into reserve tank 10 containing Gallium solution by closed electrodeposition pipe 30 to make.Institute
It states cathode conducting block 37 and anode conducting block 28 is arranged on the outer cylinder of the closed electrodeposition pipe 20；And the cathode 35 with it is described
Cathode conducting block 37 connects, and the anode 36 is connect with the anode conducting block 38.The electrodeposition solution inlet 32 simultaneously be also
Electrodeposition pipe arranges gallium mouth.
Preferably, the cathode 35 is the tube body, the central axis upright of the tube body is arranged.The anode 36 is
Anode tube, the lower end of the anode tube 36, which is worn, to be fixed in the lower cover 31；The body portion of the anode tube 36 is along institute
The central axis for stating tube body is arranged in the tube body；
The exhaust pipe 40 be a pipeline, entrance respectively with the separating tank exhaust outlet 25 of separating tank 20, closed electricity
The electrodeposition pipe exhaust outlet (not shown) connection of product pipe 30, the exhaust pipe 40 is equipped with exhaust valve, to be automatically drained out electrodeposition mistake
The gas and a small amount of heat generated in journey.On the one hand, gas in slot 20 and closed electrodeposition pipe 30 can be prevented separation to be enriched with, influenced
Electricity effect；On the other hand, subsequent waste gas treatment device to can be set the gas is collected and is handled.
The gallium separator 50 is that a bottom is funnelform container.The entrance (not shown) at 50 top of gallium separator
It is connect with the separating tank of separating tank 20 row's gallium mouth 24；Its funnel-form bottom end offers gallium collection port (not shown), for periodically arranging
It is deposited on the gallium of gallium separator 50 out；Its side wall offers filtrate port (not shown).
The filtrate receiver 60 is open type groove body, and entrance connect with the filtrate port (not shown) of gallium separator 50, goes out
Mouth is connected to by filtrate pump B2 and circulation pipe L4 with reserve tank inlet 11, and the solution pump in filtrate receiver 60 is back to reserve tank
In 10.
The control device 70 be preferably PLC control platform, with circulating pump B1, filtrate pump B2, heat exchanger circulating pump B3,
Pressure gauge P, flowmeter F, thermal resistance T, radar levelmeter R electrical connection, control the operation of each device and show each device
Working condition.
The power supply unit 80 uses artificial PLC, gives control device 70, reserve tank 10, separating tank 20, closed electrodeposition pipe
30, exhaust pipe 40, heat exchanger 90 power, with circulating pump B1, filtrate pump B2, heat exchanger circulating pump B3, pressure gauge P, flowmeter F,
The electrical connection such as thermal resistance T, radar levelmeter R is entire gallium electrodeposition system power supply.
The heat exchanger 90 is the equipment that the partial heat of hot fluid is passed to cold fluid, mainly logical including first fluid
Road and second fluid channel.Wherein the entrance in first fluid channel passes through the cold of a pipeline and heat exchanger circulating pump B3 and reserve tank
But liquid outlet 13 is connected to, and the outlet in first fluid channel is connected by the reserve tank inlet 11 at 10 top of a pipeline and reserve tank
It is logical, to form a sealing and circulating circuit.The second fluid channel around the first fluid channel outer wall, and to described
Second fluid channel is passed through coolant liquid, and the flow velocity and flow of coolant liquid are controlled by automatic regulating valve V, to adjust institute indirectly
State the temperature of solution in first fluid channel.
The working principle of gallium electrodeposition system of the present invention is as follows:
Firstly, entering in reserve tank 10 containing Gallium solution through liquid supplementation pipe L1, to the liquid in radar levelmeter R feedback reserve tank 10
After position reaches setting height, circulating pump B1 is opened, by being pumped into separating tank 20 in reserve tank 10 containing Gallium solution.
Secondly, controlling pipeline flow and pressure, such as control flow in 1~5m by frequency modulation flowmeter F3Between/h, pipe
When road pressure is less than 0.2MPa, in separating tank 20 containing Gallium solution under the driving of hydraulic pressure, through separating tank liquid outlet 22
Enter closed electrodeposition pipe 30 with electrodeposition solution inlet 32；After containing Gallium solution full of after closed electrodeposition pipe 30, then through circulation pipe L4 by
The electrodeposition taphole 31 of closed 30 upper end of electrodeposition pipe is back in reserve tank 10, forms closed cycle.
Then, constant current is inputed at the interface of control device 70, and feeds back display voltage and current density, such as inputed to
When constant current 800A, feedback display voltage 25V, current density 800A.Make containing the gallium element in Gallium solution in the electric current inputted
Under, electrochemical reaction occurs in closed electrodeposition pipe 30 and generates liquid metal gallium (fusing point is 29.76 DEG C), gallium deposits to
The bottom of closed electrodeposition pipe 30, and (while being also that electrodeposition pipe arranges gallium by the electrodeposition solution inlet 32 of closed 30 lower end of electrodeposition pipe
Mouthful) be discharged into separating tank 20.
After in closed electrodeposition pipe 30 electrolytic deposition reaction about for 24 hours after, open separating tank row gallium mouth 24 valve, gallium and
Electrolyte is drained into together in gallium separator 50.Since the density of gallium is much larger than the density of electrolyte, therefore gallium is deposited on
50 funnel-form bottom end of gallium separator, electrolyte then flows into filtrate receiver 60 from the filtrate port of gallium separator 50, then through filtrate pump
B2 is flow back into reserve tank 10；Gallium is then separated from the discharge of row's gallium mouth (not shown) of gallium separator 50, and under entrance
Washing, purification process together.It is open state that exhaust pipe 40 is kept in entire electrolytic deposition process, so that the gas that electrolytic deposition process generates
Body drains into designated position in time.
Exhaust pipe 40 is checked in gallium electrodeposition system operation, and guarantees that electric current and voltage are normal.Normal course of operation
Middle solution temperature is gradually increasing, and opens solution temperature setting less than 60 DEG C；When solution temperature reaches 60 DEG C, control device 70 is certainly
It is dynamic to open heat exchanger 90 and heat exchanger circulating pump B3, to carry out cooling processing to containing Gallium solution；The feedback of control device 70 is aobvious simultaneously
The temperature for showing solution in 90 first fluid channel of heat exchanger, by adjusting the flow and flow rate of coolant liquid in second fluid channel,
To adjust the temperature of solution in first fluid channel indirectly, so that the temperature is stablized in the zone of reasonableness of setting.
It is demonstrated experimentally that the room temperature containing 10~80g/L Ga, 2~8g/L Al, 100~250g/L NaOH is passed through containing Gallium solution
After crossing above-mentioned gallium electrodeposition system processing, gallium recovery rate is greater than 99.9%.Then using hydrochloric acid carrying out washing treatment after, the rate of recovery of gallium
It can achieve 99.99% or more.
Compared with the existing technology, closed electrodeposition pipe of the present invention and gallium electrodeposition system have the advantages that (1) is molten containing gallium
Liquid in closed electrodeposition pipe, takes the pressure liquid in-out mode of vertical direction " bottom in and top out ", with conventional electrolysis by circulating pump
The horizontal direction liquid in-out mode of slot is compared, and the internal circulating load containing Gallium solution is bigger, and eliminates different parts in closed electrodeposition pipe
Concentration polarization containing Gallium solution；Compared with conventional electrolytic deposition process, high current electrodeposition may be implemented, maximum can reach 1600A, electric current
It is more efficient.(2) closed electrodeposition pipe is used, electrolytic deposition process whole process is carried out all under air-tight state, can make to produce in electrolytic deposition process
Raw gas flows through exhaust pipe discharge with liquid, draws electrolytic deposition process scene in time, avoids electrolytic deposition process due to gas
Caused by open circuit conditions, site environment is friendly.(3) it is temporarily stored in gallium separator after gallium output, passes through manual or automatic row
Expect that device realizes the collection of gallium, it is simple to operate, avoid the loss of gallium caused by personnel's lock out operation.(4) entire gallium
Electrodeposition system full automatic working sets solution temperature using PLC control platform, adjusts supplement cooling water and guarantees that heat exchanger is assisted automatically
It runs；Reflect working condition in real time using instrument such as flowmeter and pressure gauges, guarantees that electrolytic deposition process is safe, controllable.And it powers
The full PLC control of system, automatically gives input current, and feedback current density adds up the electrodeposition time, shows power consumption and voltage etc., and
Fault alarm when can be achieved abnormal.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (10)
1. a kind of closed electrodeposition pipe, it is characterised in that: the closed electrodeposition pipe is vertically arranged；The closed electrodeposition pipe is equipped with electricity
Product solution inlet and electrodeposition taphole, and the electrodeposition solution inlet is lower than the electrodeposition taphole；The closed electrodeposition
Anode and cathode is additionally provided on pipe.
2. closed electrodeposition pipe according to claim 1, it is characterised in that: the closed electrodeposition pipe includes:
Vertically arranged tube body；
Lower cover, the lower cover are arranged at the nozzle below the tube body, the electrodeposition solution inlet be formed in it is described under
In end cap；With
Upper end cover, the upper end cover are arranged at the nozzle above the tube body, and the electrodeposition taphole is formed on described
In end cap.
3. closed electrodeposition pipe according to claim 2, it is characterised in that:
The anode is anode tube, and the lower end of the anode tube, which is worn, to be fixed in the lower cover；The tube body of the anode tube
Part is arranged in the tube body along the central axis of the tube body；
The cathode is the tube body, and the central axis upright of the tube body is arranged.
4. a kind of gallium electrodeposition system, it is characterised in that:
Including reserve tank, separating tank and the closed electrodeposition pipe as described in claims 1 to 3 is any；
The reserve tank, separating tank are sequentially connected, and the top of the separating tank is arranged in the closed electrodeposition pipe；
Enter in closed electrodeposition pipe containing Gallium solution from the electrodeposition solution inlet of closed electrodeposition pipe, electricity occurs under impressed current effect
Chemical reaction generates gallium；It is discharged again from the electrodeposition taphole containing Gallium solution, gallium is discharged from electrodeposition solution inlet.
5. gallium electrodeposition system according to claim 4, it is characterised in that: the separating tank is closed cell；The separating tank
Top is equipped with separating tank inlet and separating tank liquid outlet；The bottom of the separating tank is equipped with separating tank and arranges gallium mouth；The separation
Slot liquid outlet is connect with the solution inlet of the closed electrodeposition pipe.
6. gallium electrodeposition system according to claim 5, it is characterised in that: further include exhaust pipe；The exhaust pipe is arranged in institute
It states on closed electrodeposition pipe and the separating tank；The gas that the closed electrodeposition pipe electrolytic deposition process generates in exhaust pipe by being discharged.
7. gallium electrodeposition system according to claim 6, it is characterised in that: the reserve tank is equipped with reserve tank inlet and electricity
Product liquid outlet；The reserve tank inlet is connected to by a pipeline with the electrodeposition taphole of the closed electrodeposition pipe；The electricity
Product liquid outlet is connected to by a pipeline with the separating tank inlet, to make the reserve tank, separating tank and closed electrodeposition pipe
Form closed loop.
8. gallium electrodeposition system according to claim 7, it is characterised in that: further include heat exchanger, the heat exchanger includes first
Fluid channel and second fluid channel；The import in the first fluid channel is connect with the cooling liquid outlet of the reserve tank, institute
The outlet for stating first fluid channel is connect with the reserve tank inlet, and the first fluid and reserve tank formation one are closed
Circulation loop；The second fluid channel surround the outer wall in the first fluid channel, and is passed through to the second fluid channel
Coolant liquid, and by the flow velocity and flow of automatic regulating valve control coolant liquid, to adjusted in the first fluid channel indirectly
The temperature of solution.
9. gallium electrodeposition system according to claim 8, it is characterised in that: further include gallium separator；The gallium separator is one
Bottom is funnelform container；Entrance at the top of the gallium separator is connect with separating tank row's gallium mouth；The gallium separator funnel
Shape bottom end offers gallium collection port；The gallium separator sidewall offers filtrate port.
10. gallium electrodeposition system according to claim 9, it is characterised in that: further include filtrate receiver；The entrance of the filtrate receiver with
The filtrate port of gallium separator connects, and the outlet of the filtrate receiver is connect by filtrate pump and circulation pipe with reserve tank inlet, with
Solution pump in filtrate receiver is back in reserve tank.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491154.8A CN110042426A (en) | 2019-06-06 | 2019-06-06 | A kind of closed electrodeposition pipe and gallium electrodeposition system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491154.8A CN110042426A (en) | 2019-06-06 | 2019-06-06 | A kind of closed electrodeposition pipe and gallium electrodeposition system |
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| CN110042426A true CN110042426A (en) | 2019-07-23 |
Family
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| CN201910491154.8A Pending CN110042426A (en) | 2019-06-06 | 2019-06-06 | A kind of closed electrodeposition pipe and gallium electrodeposition system |
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Citations (5)
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| WO2009117354A2 (en) * | 2008-03-19 | 2009-09-24 | Eltron Research & Development, Inc. | Electrowinning apparatus and process |
| CN205974696U (en) * | 2016-07-11 | 2017-02-22 | 陕西瑞凯环保科技有限公司 | Torrent electrodeposition small test device |
| CN108842171A (en) * | 2018-09-13 | 2018-11-20 | 陕西瑞凯环保科技有限公司 | A kind of method and apparatus that turbulent flow electrodeposition prepares metal-powder |
| CN109208032A (en) * | 2018-09-28 | 2019-01-15 | 浙江科菲科技股份有限公司 | A method of gallium is recycled from electrodeposition in alkaline solution containing gallium |
| CN109295479A (en) * | 2018-10-12 | 2019-02-01 | 浙江田成环境科技有限公司 | The rotating flow electrowinning plant of heavy metal in a kind of recycling slag |
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2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009117354A2 (en) * | 2008-03-19 | 2009-09-24 | Eltron Research & Development, Inc. | Electrowinning apparatus and process |
| CN205974696U (en) * | 2016-07-11 | 2017-02-22 | 陕西瑞凯环保科技有限公司 | Torrent electrodeposition small test device |
| CN108842171A (en) * | 2018-09-13 | 2018-11-20 | 陕西瑞凯环保科技有限公司 | A kind of method and apparatus that turbulent flow electrodeposition prepares metal-powder |
| CN109208032A (en) * | 2018-09-28 | 2019-01-15 | 浙江科菲科技股份有限公司 | A method of gallium is recycled from electrodeposition in alkaline solution containing gallium |
| CN109295479A (en) * | 2018-10-12 | 2019-02-01 | 浙江田成环境科技有限公司 | The rotating flow electrowinning plant of heavy metal in a kind of recycling slag |
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