Electrochemical recovery system for waste hard alloy

Abstract

The utility model discloses a waste hard alloy electrochemical recovery system which comprises an electrolysis device, a hydrogen separation device and a hydrogen collection device, the electrolysis device is provided with a mixed gas outlet and an acid liquor inlet, the hydrogen separation device is provided with a mixed gas inlet, an acid liquor outlet and a first hydrogen outlet, and the hydrogen collection device is provided with a first hydrogen inlet; the mixed gas outlet is communicated with the mixed gas inlet, the acid liquid outlet is communicated with the acid liquid inlet, and the first hydrogen outlet is communicated with the first hydrogen inlet; the electrolysis device is used for carrying out acidic electrolysis on the waste hard alloy to obtain mixed gas, the mixed gas is discharged through the mixed gas outlet and enters the hydrogen separation device through the mixed gas inlet to be separated to obtain hydrogen and acid liquor, and the hydrogen is discharged through the first hydrogen outlet and collected by the hydrogen collection device; and the acid liquor is discharged from the acid liquor outlet and is recycled into the electrolysis device through the acid liquor inlet, so that environmental pollution and resource waste caused by direct discharge of mixed gas are avoided.

Description

TECHNICAL FIELD

[0001] The utility model relates to waste hard alloy recycling technical field more specifically, relate to a kind of waste hard alloy electrochemical recovery system. BACKGROUND

[0002] The electrochemical recovery of waste hard alloy is an efficient and environmentally friendly recycling method. In the electrolytic cell, waste hard alloy is used as the anode. By applying an external electric field and using suitable electrolyte (such as acidic electrolyte hydrochloric acid, sulfuric acid, etc.), different components in the alloy are separated during electrolysis. Specifically, the binder phase metal (such as cobalt) in the alloy loses electrons and dissolves into the electrolyte, forming corresponding ions; while the hard phase (such as tungsten carbide) is precipitated in the form of anode mud, which is further processed for the production of hard alloy.

[0003] In the prior art, when the electrochemical device performs electrolysis on waste hard alloy, hydrogen gas and acid byproduct mixed gas are produced. In the prior art, the byproduct mixed gas is transported to sodium hydroxide liquid to absorb the acid in the mixed gas, resulting in wastewater. Then the wastewater and hydrogen gas are directly discharged. The direct discharge of hydrogen gas causes resource waste, and the wastewater pollutes the environment.

[0004] Therefore, there is an urgent need to provide a waste hard alloy electrochemical recovery system that can collect gas and improve exhaust. UTILITY MODEL CONTENT

[0005] The utility model aims to overcome the above-mentioned defects in the prior art, and provides a waste hard alloy electrochemical recovery system, comprising:

[0006] An electrolytic device is provided with a mixed gas outlet and an acid liquid inlet;

[0007] A hydrogen gas separation device is provided with a mixed gas inlet, an acid liquid outlet and a first hydrogen gas outlet; and

[0008] A hydrogen gas collection device is provided with a first hydrogen gas inlet;

[0009] The mixed gas outlet is in communication with the mixed gas inlet, the acid liquid outlet is in communication with the acid liquid inlet, and the first hydrogen gas outlet is in communication with the first hydrogen gas inlet;

[0010] The electrolysis device is used for acid electrolysis of the waste hard alloy to obtain mixed gas, the mixed gas includes hydrogen and acid liquid gaseous byproducts, the mixed gas is discharged through the mixed gas outlet, enters the hydrogen separation device through the mixed gas inlet, and is separated to obtain the hydrogen and the acid liquid gaseous byproducts or the acid liquid, the hydrogen is discharged through the first hydrogen outlet and is collected by the hydrogen collection device, and the acid liquid gaseous byproducts or the acid liquid is discharged through the acid liquid outlet and is recycled into the electrolysis device through the acid liquid inlet.

[0011] The embodiment of the utility model is implemented, will have the following beneficial effect:

[0012] The utility model provides a kind of waste hard alloy electrochemical recovery system, comprising: electrolysis device, hydrogen separation device and hydrogen collection device, electrolysis device is equipped with mixed gas outlet and acid liquid inlet, hydrogen separation device is equipped with mixed gas inlet, acid liquid outlet and first hydrogen outlet, hydrogen collection device is equipped with first hydrogen inlet;Mixed gas outlet is communicated with mixed gas inlet, acid liquid outlet is communicated with acid liquid inlet, first hydrogen outlet is communicated with first hydrogen inlet;Electrolysis device is used for acid electrolysis waste hard alloy to obtain mixed gas, mixed gas is discharged through mixed gas outlet, enters hydrogen separation device through mixed gas inlet, and is separated to obtain hydrogen and acid liquid, hydrogen is discharged through first hydrogen outlet and is collected by hydrogen collection device, and acid liquid is discharged through acid liquid outlet and is recycled into electrolysis device through acid liquid inlet.The hydrogen and the acid liquid are separated by hydrogen separation device to the mixed gas, and the acid liquid can be returned to electrolysis device for reuse, to avoid environmental pollution and resource waste caused by direct discharge of mixed gas. ACCURATE DRAWINGS

[0013] In order to more clearly illustrate the technical scheme in the embodiments of the utility model or the prior art, the drawings needed to be used in the embodiment or the prior art description will be briefly introduced below, and obviously, the drawings in the following description are only some embodiments of the utility model, and for those skilled in the art, other drawings can be obtained without creative labor on the basis of these drawings.

[0014] Among them:

[0015] Figure 1 A kind of schematic diagram of waste hard alloy electrochemical recovery system provided by the utility model is provided;

[0016] Figure 2 Another schematic diagram of waste hard alloy electrochemical recovery system provided by the utility model is provided;

[0017] 1-electrolytic device, 11-mixed gas outlet, 12-acid liquid inlet, 13-solid outlet, 2-hydrogen separation device, 21-mixed gas inlet, 22-acid liquid outlet, 23-first hydrogen outlet, 3-hydrogen collection device, 31-first hydrogen inlet, 32-second hydrogen outlet, 4-dry deoxidizing device, 41-second hydrogen inlet, 42-solid inlet. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the utility model will be clearly and completely described below with reference to the drawings in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, rather than all the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the utility model.

[0019] Referring to Figure 1 The utility model discloses a kind of waste hard alloy electrochemical recovery systems, comprising: electrolytic device 1, hydrogen separation device 2 and hydrogen collection device 3, electrolytic device 1 is equipped with mixed gas outlet 11 and acid liquid inlet 12, hydrogen separation device 2 is equipped with mixed gas inlet 21, acid liquid outlet 22 and first hydrogen outlet 23;Hydrogen collection device 3 is equipped with first hydrogen inlet 31;Mixed gas outlet 11 is communicated with mixed gas inlet 21, acid liquid outlet 22 is communicated with acid liquid inlet 12, first hydrogen outlet 23 is communicated with first hydrogen inlet 31;

[0020] Electrolytic device 1 is used for acid electrolysis waste hard alloy to obtain mixed gas, and the mixed gas includes hydrogen and acid liquid gaseous byproduct, the mixed gas is discharged through mixed gas outlet 11, enters hydrogen separation device 2 by mixed gas inlet 21, and is separated to obtain hydrogen and acid liquid gaseous byproduct or acid liquid, hydrogen is discharged through first hydrogen outlet 23 and is collected by hydrogen collection device 3, and acid liquid gaseous byproduct or acid liquid is discharged through acid liquid outlet 22 and recirculated to electrolytic device 1 by acid liquid inlet 12.

[0021] It should be noted that waste hard alloy includes waste tungsten alloy, in the process that electrolyte solution in electrolytic cell electrolyzes waste tungsten alloy, under the action of electric field, metal components in alloy can occur oxidation reaction, and corresponding metal ions enter solution, while non-metal components (such as tungsten carbide) remain in electrolytic cell in the form of solid, and mixed gas of hydrogen and acid liquid gaseous byproduct is generated, and tungsten carbide and other solid substances are used to make hard alloy products.

[0022] In prior art, when mixed gas of hydrogen and acid liquid gaseous byproduct is treated, mixed gas is usually introduced into alkali to remove acid liquid gaseous byproduct, and then hydrogen is directly discharged, which causes resource waste and environmental pollution.

[0023] The embodiment sets the hydrogen separation device 2, the mixed gas of hydrogen and acid liquid gaseous byproducts enters the hydrogen separation device 2 for separation and purification, and hydrogen and acid liquid gaseous byproducts or acid liquid are obtained respectively, the acid liquid gaseous byproducts or acid liquid returns to the electrolysis device 1 for repeated use, the hydrogen enters the hydrogen collection device 3 for collection, and environmental pollution and resource waste caused by direct discharge of the mixed gas are avoided.

[0024] In a specific embodiment, the hydrogen separation device 2 comprises a spraying mechanism and a liquid accumulation groove, the liquid accumulation groove comprises an acid liquid outlet 22, the spraying device sprays a solvent, and the acid liquid is contained in the liquid accumulation groove after being soluble with the solvent.

[0025] Further, the solvent comprises water.

[0026] Further, the electrolysis device 1 comprises an electrolytic tank, and the electrolytic tank contains an electrolyte solution.

[0027] It should be noted that the acid liquid gaseous byproducts are soluble in water, and the hydrogen is not easy to dissolve in water, so the mixed gas is separated by water washing, the acid liquid byproducts are dissolved in water after the mixed gas passes through the spraying device, and then are contained in the liquid accumulation groove, the hydrogen is discharged from the first hydrogen outlet 23 for collection, and the acid liquid in the liquid accumulation groove can be further discharged from the acid liquid outlet 22 and recycled to the electrolysis device 1 through the acid liquid inlet 12 for reuse.

[0028] Further, the electrolysis device 1 contains an electrolyte solution, the electrolyte solution comprises dilute hydrochloric acid, the mixed gas comprises hydrogen chloride and hydrogen, the hydrogen chloride is dissolved in water to obtain hydrochloric acid, which is contained in the liquid accumulation groove and can be further discharged from the acid liquid outlet 22 and recycled to the electrolysis device 1 through the acid liquid inlet 12 for reuse, and the hydrogen is discharged from the first hydrogen outlet 23 for collection. Alternatively, the electrolyte solution can also comprise dilute sulfuric acid.

[0029] Alternatively, the hydrogen chloride and hydrogen mixed gas can also be separated by a low-temperature reboiling rectification system, the low-temperature reboiling rectification system comprises a rectification tower, a mixed gas inlet is arranged in the middle of the rectification tower, and a first hydrogen outlet 23 is arranged at the top of the rectification tower; the rectification tower is designed as an upper section packing and a lower section packing, a condenser is arranged above the rectification tower, the condenser is connected with a liquid nitrogen tank, a catalytic reactor is connected with the middle part of the rectification tower, a super-pure hydrogen chloride storage tank is connected with the lower part of the rectification tower, the super-pure hydrogen chloride storage tank is provided with an acid liquid outlet 22, and the super-pure hydrogen chloride storage tank is connected with a reboiling heater.

[0030] The mixed gas of hydrogen chloride and hydrogen enters the low-temperature reboiling rectification system from the mixed gas inlet, and the mixed gas entering the rectification tower flows upwards through the condenser, and the hydrogen chloride is liquefied into liquid state under the action of gravity and flows downwards into the ultra-pure hydrogen chloride storage tank provided with a reboiling heater at the bottom; the liquid state hydrogen chloride passes through the rectification tower filler and contacts the upward flowing hydrogen chloride and hydrogen gas mixed gas on the filler, the hydrogen chloride in the mixed gas is dissolved into the liquid state hydrogen chloride, and the non-condensed hydrogen gas is discharged from the first hydrogen gas outlet 23 at the top end of the rectification tower through the condenser, and the liquid state hydrogen chloride is discharged from the acid liquid outlet 22. Further, part of the hydrogen chloride in the ultra-pure hydrogen chloride storage tank is boiled again under the action of the reboiling heater, passes through the lower segment filler of the rectification tower, forms a countercurrent with the downward flowing liquid state hydrogen chloride, and strips the hydrogen gas not completely separated from the liquid state hydrogen chloride, and the hydrogen gas is mixed with the upward flowing gas and is finally discharged from the first hydrogen gas outlet 23 at the top end of the rectification tower.

[0031] In a specific embodiment, referring to Figure 2 , the waste hard alloy electrochemical recycling system further comprises a drying and deoxidizing device 4 connected with the electrolysis device 1 and the hydrogen gas collecting device 3 respectively.

[0032] Further, the electrolysis device 1 comprises a solid outlet 13, and the drying and deoxidizing device 4 comprises a solid inlet 42 in communication with the solid outlet 13. The solid substances such as tungsten carbide generated in the electrolysis device 1 enter the deoxidizing device for further treatment through the solid outlet 13 and the solid inlet 42 in sequence, for the production of hard alloy, and the purity of the tungsten carbide after the drying and deoxidizing treatment is improved, which helps to improve the physical and chemical properties of the tungsten carbide.

[0033] Further, the hydrogen gas collecting device 3 comprises a second hydrogen gas outlet 32, and the drying and deoxidizing device 4 comprises a second hydrogen gas inlet 41 in communication with the second hydrogen gas outlet 32.

[0034] The hydrogen gas can react with the oxide on the surface of the tungsten carbide in the drying and deoxidizing process to generate water and tungsten carbide, so as to remove the oxide impurities and improve the purity of the tungsten carbide, which helps to improve the physical and chemical properties of the tungsten carbide. In the embodiment, the mixed gas generated by the electrolysis device 1 is separated by the hydrogen gas separating device 2 to obtain acid liquid and hydrogen gas, the acid liquid is returned to the electrolysis device 1 for reuse, and the hydrogen gas enters the drying and deoxidizing device 4 for use, so as to improve the product recycling quality.

[0035] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the patent application scope. It should be noted that, for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. An electrochemical recycling system for waste cemented carbide, characterized in that, include: An electrolysis device, wherein the electrolysis device is provided with a mixed gas outlet and an acid inlet; A hydrogen separation device, wherein the hydrogen separation device is provided with a mixed gas inlet, an acid outlet and a first hydrogen outlet; as well as A hydrogen collection device, wherein the hydrogen collection device is provided with a first hydrogen inlet; The mixed gas outlet is connected to the mixed gas inlet, the acid liquid outlet is connected to the acid liquid inlet, and the first hydrogen gas outlet is connected to the first hydrogen gas inlet. The electrolysis device is used for acidic electrolysis of the waste cemented carbide to obtain a mixed gas, which includes hydrogen and gaseous acid byproducts. The mixed gas is discharged through the mixed gas outlet and enters the hydrogen separation device through the mixed gas inlet to separate the hydrogen and the gaseous acid byproducts or acid. The hydrogen is discharged through the first hydrogen outlet and collected by the hydrogen collection device. The gaseous acid byproducts or acid is discharged through the acid outlet and recycled back into the electrolysis device through the acid inlet.

2. The waste cemented carbide electrochemical recycling system according to claim 1, characterized in that, The hydrogen separation device includes a spraying mechanism and a liquid collection tank. The liquid collection tank includes the acid outlet. The spraying mechanism sprays solvent, and the acid and the solvent are mixed and contained in the liquid collection tank.

3. The waste cemented carbide electrochemical recycling system according to claim 2, characterized in that, The solvent includes water.

4. The waste cemented carbide electrochemical recycling system according to claim 3, characterized in that, The electrolysis device contains an electrolyte solution, which includes dilute hydrochloric acid. The mixed gas includes hydrogen chloride and hydrogen gas, and the hydrogen chloride is dissolved in water and contained in the liquid collection tank.

5. The waste cemented carbide electrochemical recycling system according to claim 1, characterized in that, It also includes a drying and deoxygenation device, which is connected to the electrolysis device and the hydrogen collection device respectively.

6. The waste cemented carbide electrochemical recycling system according to claim 5, characterized in that, The hydrogen collection device includes a second hydrogen outlet, and the drying and deoxygenation device includes a second hydrogen inlet. The second hydrogen outlet is connected to the second hydrogen inlet.

7. The waste cemented carbide electrochemical recycling system according to claim 5, characterized in that, The electrolysis device includes a solid outlet, and the drying and deoxidation device includes a solid inlet, with the solid outlet connected to the solid inlet.

8. The waste cemented carbide electrochemical recycling system according to claim 1, characterized in that, The electrolysis apparatus includes an electrolytic cell.

9. The waste cemented carbide electrochemical recycling system according to claim 1, characterized in that, The waste cemented carbide includes waste tungsten alloy.

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