Pumping oxygen electrode and molten salt electrolysis system

Abstract

The utility model belongs to the field of molten salt electrolysis, and particularly relates to an oxygen pumping electrode and a molten salt electrolysis system. The oxygen pumping electrode is provided with the oxygen pumping assembly and the connecting assembly, the porous conductive material of the oxygen pumping assembly is loaded with the catalyst so as to improve the catalytic capacity, the porous conductive material can be made of non-noble metal materials, and the connecting assembly is provided with the screws and the clamping plates, so that fixation and sealing are kept, and meanwhile disassembly is convenient. A conductive sheet and a binding post are arranged for connecting the conductive material and an external power supply.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the field of fused salt electrolysis, and particularly relates to a pump oxygen electrode and a fused salt electrolysis system. BACKGROUND

[0002] The information disclosed in this Background section is for the purpose of generally presenting the context of the application. The information disclosed in this Background section is not to be taken as an admission that it is prior art to the present application, nor necessarily essential to the practice of the application.

[0003] Traditional metallurgical industry extracts and prepares metals from corresponding minerals (mainly oxide minerals) through carbon thermal reduction or metal thermal reduction. The biggest disadvantage of this high-temperature metallurgical process is that a large amount of greenhouse gas CO2 is generated, and a large amount of reducing agent needs to be used, which faces the challenge of reducing agent shortage. Electrolysis of metal oxides in molten salt to prepare metal and alloy powder is considered to be a more efficient and environmentally friendly metallurgical method. This process was discovered by Professor Fray, Farthing and Chen of Cambridge University in the UK in 1997 when they were studying how to remove the oxide film on the surface of Ti, so it is also called FFC Cambridge process. In the FFC Cambridge process, solid oxides are made into cathodes, and metal oxides are electrolytically reduced under conditions of a temperature lower than the melting point of the metal and a decomposition voltage of the molten salt. Oxygen ions enter the molten salt and migrate to the anode to be discharged, and metals or alloys are left in the cathode.

[0004] Because of the oxidation reaction of oxygen ions at the anode in the process of molten salt electrolysis, the graphite anode used in the traditional electrolysis process such as the FFC Cambridge process will react with oxygen ions, and the final anode product is CO or CO2. On the one hand, the graphite electrode is dissolved by reaction, and on the other hand, pollution gas is generated. Metal anodes represented by noble metals such as platinum, gold and silver have good electrical conductivity and thermal shock resistance, and can effectively catalyze the reduction of oxygen ions to oxygen, but are easily corroded in the molten salt system.

[0005] The use of dense solid electrolyte separates the molten salt from the anode conductive material, so that the anode conductive material is not in direct contact with the molten salt system. Oxygen ions dissolved in the molten salt pass through the solid electrolyte to the side of the anode conductive material, and complete the gain and loss of electrons in the oxidation reaction, avoiding the corrosion of the anode conductive material by the molten salt system. The electrode that realizes the above functions is a pump oxygen electrode. However, the existing pump oxygen electrode still has the following defects: In order to ensure the oxidation efficiency of oxygen ions, noble metal materials with excellent catalytic ability need to be used for the anode conductive material, resulting in rising costs; an anode conductive material and an external power source need to be connected by a lead that penetrates through the electrode, which is costly and not conducive to disassembly and replacement; the solid electrolyte and the connecting pipe are mostly fixedly connected, and when the solid electrolyte needs to be replaced due to breakage, the replacement steps are cumbersome. SUMMARY

[0006] In order to solve the problems in the prior art, the utility model discloses a pump oxygen electrode and a fused salt electrolysis system. The utility model discloses pump oxygen electrode sets up pump oxygen subassembly and connecting subassembly, and the porous conductive material of pump oxygen subassembly is loaded with catalyst to improve the catalytic ability, so that the porous conductive material can be selected from non-precious metal materials, the screw and the clamping plate of connecting subassembly are arranged to facilitate dismounting while keeping fixed and sealed, and the conductive sheet and the terminal post are arranged to be used for connecting the conductive material and the external power supply.

[0007] In order to achieve the above object, the utility model is through the following technical scheme to realize:

[0008] Firstly, the utility model provides a kind of pump oxygen electrode, including pump oxygen subassembly and connecting subassembly;

[0009] The connecting subassembly includes connecting pipe with oxygen passage, screw and clamping plate arranged outside the connecting pipe, one end of the connecting pipe is closed end and is provided with terminal post, and the outer side wall of the other end is provided with conductive sheet communicated with the terminal post, the sidewall of the connecting pipe is provided with screw hole, and the screw is connected with the connecting pipe by screw hole and is slidably connected with the clamping plate;

[0010] The pump oxygen subassembly includes solid electrolyte tube with one end closed and porous conductive material connected to the inner wall of the solid electrolyte tube, and the porous conductive material is loaded with catalyst;

[0011] The open end of the pump oxygen subassembly is fixedly connected with the open end of the connecting subassembly by the clamping plate, and the porous conductive material is connected with the conductive sheet.

[0012] Connecting subassembly is used for fixedly connecting pump oxygen subassembly composed of solid electrolyte tube and porous conductive material, and provides outflow channel for generated oxygen to prevent oxygen from overflowing and polluting fused salt and protective gas. Clamping plate and screw are arranged on connecting subassembly to fix pump oxygen subassembly, and adjusting screw drives clamping plate to move, so that pump oxygen subassembly can be clamped and fixed to the outer wall of connecting pipe, or pump oxygen subassembly can be dismounted and replaced when pump oxygen subassembly is damaged, to realize sealing, fixing and dismounting. Traditional pump oxygen electrode needs to preset wire connected with conductive material, and wire needs to be replaced when conductive material needs to be replaced, to increase use cost. The sidewall of the connecting pipe of the utility model is provided with conductive sheet and terminal post, and the conductive sheet is connected with power supply through terminal post after being contacted with porous conductive material, so that porous conductive material can be connected with power supply, and porous conductive material can be separated from conductive sheet when dismounting is needed, so that conductive sheet does not need to be replaced with porous conductive material.

[0013] The porous conductive material in pump oxygen subassembly improves catalytic ability by loading catalyst, so that non-precious metal material can be selected for porous conductive material, to reduce the cost of pump oxygen electrode.

[0014] Optionally, the oxygen channel is arranged through the closed end face or the side wall of the connecting pipe, and the oxygen channel is provided with one or more.

[0015] The position and number of the oxygen channel can be adjusted according to the installation environment of the pump oxygen electrode and the reaction needs.

[0016] Optionally, the terminal post is connected with the conductive sheet through a conductive wire.

[0017] The terminal post is connected with the conductive sheet through a conductive wire. When the pump oxygen electrode is used for molten salt electrolysis, the lead of the power supply is connected with the terminal post, and then the current is conducted to the porous conductive material through the conductive wire and the conductive sheet, so as to realize electrolysis. The conductive wire can be attached to the outer wall of the connecting pipe, or can be arranged inside the side wall of the connecting pipe, or can be arranged on the inner wall through the side wall, so as to realize the connection function.

[0018] Further optionally, the conductive wire is arranged inside the side wall and the closed end of the connecting pipe.

[0019] The conductive wire arranged inside can prevent damage by external force or oxidation by oxygen, and ensure the stability of the electrolysis process.

[0020] Optionally, the conductive sheet is arranged in a ring shape or in multiple arc shapes.

[0021] Optionally, the screw, the screw hole and the clamping plate are correspondingly arranged in multiple.

[0022] Further optionally, the screw, the screw hole and the clamping plate are correspondingly arranged in multiple with equal included angles.

[0023] Optionally, the connecting pipe is a corundum pipe or a high-aluminum pipe, the clamping plate is a corundum clamping plate or a high-aluminum clamping plate, and the screw is a corundum screw or a high-aluminum screw.

[0024] Optionally, the porous conductive material is a silver mesh, a platinum mesh, a nickel foam or a copper foam, the conductive sheet is a copper sheet, a silver sheet or a platinum sheet, the conductive wire is a copper wire or a platinum wire, and the terminal post is a copper post or a platinum post.

[0025] The components for conducting electricity can be selected from non-precious metals or precious metals according to the factors such as the conductivity, the cost and the structural strength. The catalyst is loaded on the pores and the surface of the porous conductive material, and an existing oxygen evolution catalyst can be selected.

[0026] In a second aspect, the utility model provides a kind of fused salt electrolytic system, including power supply, metal oxide, the pump oxygen electrode as described in first aspect, fused salt and crucible, the negative pole of the power supply is connected with the metal oxide by wire, the positive pole of the power supply is connected with the binding post of the pump oxygen electrode by wire, the fused salt is placed in the inside of the crucible, the metal oxide is placed in the inside of the fused salt, the solid electrolyte tube of the pump oxygen electrode extends into the fused salt.

[0027] The oxide of target metal is made into cathode sheet for electrolysis, connecting electrode lead is used as cathode, pump oxygen electrode is used as anode, and they are placed in fused salt electrolytic system as cathode and anode respectively, electrolysis voltage is applied by direct current power supply, and the metal oxide of cathode is reduced to target metal, and the oxygen generated by anode is led out by connecting pipe and collected.

[0028] The above one or more technical solutions of the utility model have the following beneficial effects:

[0029] The clamping plate and screw on the connecting assembly of pump oxygen electrode are used for sealing and fixing pump oxygen assembly, sealing, fixing and dismounting can be realized by adjusting screw to change the connection state of clamping plate and pump oxygen assembly, the fixed connection and sealing function of pump oxygen assembly can be maintained, and the dismounting of pump oxygen assembly can also be realized.The conductive sheet is connected with power supply by binding post after being contacted with porous conductive material, and when it is necessary to replace and dismount, the porous conductive material can be separated from the conductive sheet, and the conductive sheet does not need to be replaced with the porous conductive material.The design of connecting assembly reduces the maintenance cost of pump oxygen electrode and improves the use efficiency of pump oxygen electrode.

[0030] The porous conductive material in pump oxygen assembly improves catalytic capacity by loading catalyst, so that the porous conductive material can be selected from non-noble metal materials, and the cost of pump oxygen electrode is reduced. BRIEF DESCRIPTION OF DRAWINGS

[0031] The drawings attached to the specification constitute part of the utility model and serve to provide further understanding of the utility model, and the illustrative embodiments of the utility model and the description thereof serve to explain the utility model, and do not constitute improper limitation on the utility model.

[0032] Figure 1 It is the cross-sectional structure schematic diagram of pump oxygen electrode in embodiment 1;

[0033] Figure 2 It is the structure schematic diagram of fused salt electrolytic system in embodiment 2;

[0034] In the drawing, 1 is connecting pipe, 2 is screw, 3 is clamping plate, 4 is binding post, 5 is oxygen passage, 6 is conductive sheet, 7 is solid electrolyte tube, 8 is porous conductive material, 100 is pump oxygen electrode, 200 is power supply, 300 is metal oxide, 400 is fused salt, and 500 is crucible. Detailed Implementation

[0035] To enable those skilled in the art to better understand the technical solution of this utility model, the technical solution of this utility model will be described in detail below with reference to specific embodiments and comparative examples.

[0036] Example 1

[0037] like Figure 1 As shown, the oxygen pumping electrode 100 includes an oxygen pumping assembly and a connecting assembly. The connecting assembly includes a connecting pipe 1 with an oxygen channel 5, four screws 2, and four clamps 3 disposed on the outside of the connecting pipe 1. One end of the connecting pipe 1 is closed and has a terminal 4. The outer wall of the other end has an annular conductive sheet 6 connected to the terminal 4 via a conductive wire (not shown). The conductive wire is disposed inside the side wall and the closed end of the connecting pipe 1. Four screw holes are opened in the side wall of the connecting pipe 1. Each screw 2 is threaded into the connecting pipe 1 through the screw hole and slidably connected to a clamp 3. The screws 2, clamps 3, and screw holes are correspondingly arranged and distributed at equal 90° angles. The oxygen channel 5 is disposed through the side wall of the connecting pipe 1. The oxygen pumping assembly includes a solid electrolyte tube 7 closed at one end and a porous conductive material 8 connected to the inner wall of the solid electrolyte tube 7. The porous conductive material 8 is loaded with a catalyst (not shown). The open end of the oxygen pumping assembly is fixedly connected to the open end of the connecting assembly through the clamps 3, and the porous conductive material 8 is connected to the conductive sheet 6. Connecting tube 1 is a corundum tube, clamp 3 is a corundum clamp, and screw 2 is a corundum screw. Porous conductive material 8 is nickel foam, conductive sheet 6 is a copper sheet, conductive wire is a copper wire, and terminal 4 is a copper post.

[0038] During assembly of the oxygen pumping electrode 100, the porous conductive material 8 is brought into contact with the conductive sheet, the clamping plate 3 is slidably connected to the screw 2, and the screw 2 is threadedly connected to the connecting pipe 1 through the screw hole. The screw 2 is rotated inwards into the connecting pipe 1 to ensure tight contact between the clamping plate 3 and the solid electrolyte tube 7. The clamping plate 3 and the connecting pipe 1 clamp the oxygen pumping assembly, thus fixing the assembly and ensuring circuit connection. When the oxygen pumping assembly is damaged and needs replacement, the screw 2 is rotated outwards from the connecting pipe to disengage the clamping plate 3 from the solid electrolyte tube 7, allowing the oxygen pumping assembly to be disassembled.

[0039] Example 2

[0040] like Figure 2 As shown, the molten salt electrolysis system includes a power supply 200, a metal oxide 300, an oxygen pumping electrode 100 of Example 1, molten salt 400, and a crucible 500. The negative terminal of the power supply 200 is connected to the metal oxide 300 via a wire, and the positive terminal of the power supply 200 is connected to the terminal 4 of the oxygen pumping electrode 100 via a wire. The molten salt 400 is placed inside the crucible 500, the metal oxide 300 is placed inside the molten salt 400, and the solid electrolyte tube 7 of the oxygen pumping electrode 100 extends into the molten salt 400.

[0041] In the case of power supply, the cathode large metal oxide 300 gets electrons, the metal oxide 200 is reduced to metal, and the oxygen ions enter the molten salt 400 under the action of the electric field, are pumped to the porous conductive material 8 through the solid electrolyte tube 7 outside the oxygen pumping electrode 100, and are reacted to form oxygen and are precipitated. As the oxygen in the metal oxide 200 continuously enters the molten salt 400 and is precipitated at the side of the oxygen pumping electrode 100, finally, the target metal is left at the cathode side, and oxygen is precipitated at the side of the oxygen pumping electrode 100 at the anode side. The specific electrode reactions are as follows:

[0042] Anode reaction: 2O2 - - 4e→O2

[0043] Cathode reaction: Me x O y + 2ye→xMe+0.5yO2 -

[0044] The molten salt 400 becomes a carrier of oxygen ions, and the oxygen ions are moved directionally by an applied voltage. In the case of stable existence of the oxygen pumping electrode 100, a high voltage between the electrodes will not cause electrolysis of the molten salt 400. By controlling the electrode potential, it can be ensured that the metal oxide 300 rather than the chloride or other compounds participates in the decomposition reaction, and the metal or alloy is directly prepared from the metal oxide 300, which greatly reduces the special requirements for raw materials and processes by using the traditional electrolysis method, and meets the requirements of high efficiency, low carbon and green metallurgy.

[0045] Example 3

[0046] The oxygen pumping electrode 100 comprises a pumping assembly and a connecting assembly. The connecting assembly comprises a connecting pipe 1 provided with an oxygen channel 5, two screws 2 and two clamping plates 3 arranged outside the connecting pipe 1. One end of the connecting pipe 1 is a closed end and is provided with a terminal post 4, and the outer side wall of the other end is provided with two arc-shaped conductive sheets 6 in communication with the terminal post 4 through a conductive wire, and the conductive wire is arranged inside the side wall and the closed end of the connecting pipe 1. Four screw holes are formed in the side wall of the connecting pipe 1, each screw 2 is connected with the connecting pipe 1 through the screw hole and is slidably connected with one clamping plate 3. The screw 2, the clamping plate 3 and the screw hole are correspondingly arranged and are distributed at an angle of 180°. The oxygen channel 5 is arranged through the side wall of the connecting pipe 1. The pumping assembly comprises a solid electrolyte tube 7 with one end closed and a porous conductive material 8 connected and arranged on the inner wall of the solid electrolyte tube 7, and the porous conductive material 8 is loaded with a catalyst. The open end of the pumping assembly is fixedly connected with the open end of the connecting assembly through the clamping plate 3, and the porous conductive material 8 is connected with the conductive sheet 6. The connecting pipe 1 is a high-aluminum pipe, the clamping plate 3 is a high-aluminum clamping plate, and the screw 2 is a high-aluminum screw. The porous conductive material 8 is a platinum mesh, the conductive sheet 6 is a platinum sheet, the conductive wire is a platinum wire, and the terminal post 4 is a platinum post.

[0047] Example 4

[0048] The pump oxygen electrode 100 comprises a pump oxygen assembly and a connecting assembly. The connecting assembly comprises a connecting pipe 1 provided with one oxygen channel 5, six screws 2 and six clamping plates 3 arranged outside the connecting pipe 1. One end of the connecting pipe 1 is a closed end and provided with a terminal post 4, and the outer wall of the other end is provided with an annular conductive sheet 6 in communication with the terminal post 4 through a conductive wire arranged on the inner wall of the connecting pipe 1 and the inner side of the closed end. Six screw holes are formed in the side wall of the connecting pipe 1, each screw 2 is connected with the connecting pipe 1 through the screw hole and is slidingly connected with a clamping plate 3. The screw 2, the clamping plate 3 and the screw hole are correspondingly arranged and distributed at an angle of 60°. The oxygen channel 5 is arranged through the closed end surface of the connecting pipe 1. The pump oxygen assembly comprises a solid electrolyte pipe 7 with one end closed and a porous conductive material 8 connected to the inner wall of the solid electrolyte pipe 7, and the porous conductive material 8 is loaded with a catalyst. The open end of the pump oxygen assembly is fixedly connected with the open end of the connecting assembly through the clamping plate 3, and the porous conductive material 8 is connected with the conductive sheet 6. The connecting pipe 1 is a corundum pipe, the clamping plate 3 is a corundum clamping plate, and the screw 2 is a corundum screw. The porous conductive material 8 is a foamed nickel, the conductive sheet 6 is a copper sheet, the conductive wire is a copper wire, and the terminal post 4 is a copper post.

[0049] Embodiment 5

[0050] The pump oxygen electrode 100 comprises a pump oxygen assembly and a connecting assembly. The connecting assembly comprises a connecting pipe 1 provided with one oxygen channel 5, six screws 2 and six clamping plates 3 arranged outside the connecting pipe 1. One end of the connecting pipe 1 is a closed end and provided with a terminal post 4, and the outer wall of the other end is provided with an annular conductive sheet 6 in communication with the terminal post 4 through a conductive wire arranged on the inner wall of the connecting pipe 1 and the inner side of the closed end. Six screw holes are formed in the side wall of the connecting pipe 1, each screw 2 is connected with the connecting pipe 1 through the screw hole and is slidingly connected with a clamping plate 3. The screw 2, the clamping plate 3 and the screw hole are correspondingly arranged and distributed at an angle of 60°. The oxygen channel 5 is arranged through the closed end surface of the connecting pipe 1. The pump oxygen assembly comprises a solid electrolyte pipe 7 with one end closed and a porous conductive material 8 connected to the inner wall of the solid electrolyte pipe 7, and the porous conductive material 8 is loaded with a catalyst. The open end of the pump oxygen assembly is fixedly connected with the open end of the connecting assembly through the clamping plate 3, and the porous conductive material 8 is connected with the conductive sheet 6.

[0051] The above only describes preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can be variously changed and modified. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A pump oxygen electrode characterized in that, The application relates to a pump-oxygen assembly and a connecting assembly. The connecting assembly comprises a connecting pipe provided with an oxygen channel, a screw and a clamping plate arranged outside the connecting pipe, one end of the connecting pipe is a closed end and is provided with a terminal post, the outer wall of the other end is provided with a conductive sheet in communication with the terminal post, a screw hole is formed in the side wall of the connecting pipe, the screw is threadedly connected with the connecting pipe through the screw hole and is slidably connected with the clamping plate. The pump-oxygen assembly comprises a solid electrolyte pipe with a closed end and porous conductive material arranged on the inner wall of the solid electrolyte pipe, and the porous conductive material is loaded with a catalyst. The open end of the pump-oxygen assembly is fixedly connected with the open end of the connecting assembly through the clamping plate, and the porous conductive material is connected with the conductive sheet.

2. The pump oxygen electrode of claim 1, wherein The oxygen channel is arranged through the closed end surface or the side wall of the connecting pipe, and the oxygen channel is provided with one or more.

3. The pump oxygen electrode of claim 1, wherein The terminal post is connected with the conductive sheet through a conductive wire.

4. The pump oxygen electrode of claim 3, wherein The conductive wire is arranged inside the side wall and the closed end of the connecting pipe.

5. The pump oxygen electrode of claim 1, wherein The conductive sheet is arranged in the form of a ring or multiple arcs.

6. The pump oxygen electrode of claim 1, wherein The screw, the screw hole and the clamping plate are correspondingly arranged in multiple.

7. The pump oxygen electrode of claim 1, wherein The connecting pipe is a corundum pipe or a high-aluminum pipe, the clamping plate is a corundum clamping plate or a high-aluminum clamping plate, and the screw is a corundum screw or a high-aluminum screw.

8. The pump oxygen electrode of claim 4, wherein, The porous conductive material is a silver mesh, a platinum mesh, foamed nickel or foamed copper, the conductive sheet is a copper sheet, a silver sheet or a platinum sheet, the conductive wire is a copper wire or a platinum wire, and the terminal post is a copper post or a platinum post.

9. A molten salt electrolysis system characterized in that, The application relates to a pump-oxygen electrode, a molten salt and a crucible, a metal oxide is arranged in the molten salt, and a solid electrolyte pipe of the pump-oxygen electrode is arranged in the molten salt.

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