CN212404221U - System for metal resource recycle in abandonment SCR denitration catalyst - Google Patents

Abstract

The utility model discloses a system of metal resource recycle in abandonment SCR denitration catalyst, including being used for getting rid of the pretreatment systems of surperficial impurity with abandonment SCR denitration catalyst, pretreatment systems's exit linkage to ball-milling system, the exit linkage of ball-milling system is to calcining the system, and the exit linkage of calcining the system is used for realizing drawing the fused salt hot dipping and the electrodeposition system of retrieving to metal V, Mo and W, and the fused salt hot dipping and the residual exit linkage of electrodeposition system are used for realizing drawing the fused salt electrolysis system of retrieving to metal Ti. The utility model discloses can realize that metal element's in the abandonment SCR denitration catalyst simple substance attitude separation draws recycle.

Description

System for metal resource recycle in abandonment SCR denitration catalyst

Technical Field

The utility model relates to a solid waste handles the field, concretely relates to system of metal resources recycle in abandonment SCR denitration catalyst.

Background

The emission of a large amount of nitrogen oxides in a coal-fired power plant can cause pollution problems such as acid rain, photochemical smog and dust haze, and serious threats are caused to the quality of the atmospheric environment and the health of human beings. Therefore, controlling the emission of nitrogen oxides has been an important issue of great concern to governments of various countries.

Due to the advantages of high denitration efficiency, mature technology and the like, the SCR method is the most widely applied flue gas denitration post-treatment technology of the current domestic and foreign coal-fired power plants. In the whole SCR denitration system, the denitration catalyst is the core of the SCR denitration system, and the cost of the denitration catalyst accounts for 30-40% of the total investment of the denitration device. The main component of the carrier in the denitration catalyst is TiO₂The active ingredient is mainly V₂O₅、WO₃And MoO₃And the like. In the actual operation process of the SCR system, along with the increase of the operation time, the denitration catalyst inevitably has the problems of activity reduction, service life shortening and the like, so that the denitration efficiency is reduced. Although part of the denitration catalyst can be regeneratedThe waste is treated and reused, but after being regenerated for a plurality of times (3 times), the original structure of the waste is seriously damaged and cannot be normally used, and finally the waste is generated.

V is contained in the waste SCR denitration catalyst₂O₅、WO₃Or MoO₃And the toxic metal oxides belong to dangerous solid wastes, and the landfill treatment of the toxic metal oxides not only occupies a large amount of land resources, but also brings potential pollution risks to the environment. Titanium, vanadium, tungsten, molybdenum, and the like are important metal resources required for the development of human economic society, and vanadium, tungsten, and molybdenum are called rare metals because of their low abundance in the earth's crust. Therefore, the method has great environmental benefit and extremely high economic value for effectively recycling the metal resources in the waste denitration catalyst.

At present, the methods for recycling metal resources in the waste SCR denitration catalyst mainly comprise sodium (calcium) roasting-water leaching, wet acid leaching, alkali leaching and the like, so that a large amount of chemical agents are consumed, most of recovered products are metal oxides, and the economic added value of the products is low. The technology for carrying out elemental state separation, extraction and recovery on main metal elements Ti, V, W and Mo in the waste SCR denitration catalyst is not reported.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide a metal resource recycle's system in abandonment SCR denitration catalyst to overcome the problem that exists among the prior art, the utility model discloses can realize that metal element's in the abandonment SCR denitration catalyst simple substance attitude separation draws recycle.

In order to achieve the above purpose, the utility model adopts the following technical scheme:

the utility model provides a system of metal resource recycle in abandonment SCR denitration catalyst, includes the pretreatment systems who is used for getting rid of surperficial impurity with abandonment SCR denitration catalyst, and pretreatment systems's exit linkage is to ball-milling system, and the exit linkage of ball-milling system is to calcining the system, and calcining the exit linkage of system is used for realizing extracting the fused salt hot dipping and the electrodeposition system of retrieving to metal V, Mo and W, and fused salt hot dipping and the residual export of electrodeposition system are connected to the fused salt electrolysis system that is used for realizing extracting the retrieving to metal Ti.

Further, the pretreatment system comprises a high-pressure air gun for purging the waste SCR denitration catalyst, a water washing device for washing the purged catalyst, and a drying device for drying the washed catalyst.

Further, the calcining system comprises a heating device adopting a ring heating mode and a thermocouple which is arranged at the same horizontal position with the calcining material.

Further, the molten salt hot dipping and electro-deposition system comprises an electrolysis device, the electrolysis device comprises an electrolysis cell, the electrolysis cell is arranged in a reactor, the reactor is arranged in a high-temperature electric furnace, a gas inlet on the reactor is connected to a gas distribution system for providing inert gas through a gas drying device, and a gas outlet on the reactor is respectively connected to a vacuum pump and a tail gas recovery system.

Furthermore, the reactor is also connected with a control system, and the control system comprises a temperature control system for controlling the heating temperature and the heating rate of the high-temperature electric furnace and a reaction control system for controlling the parameters of the reaction process.

Compared with the prior art, the utility model discloses following profitable technological effect has:

the utility model discloses system's device is simple, and process flow is short, convenient operation. (1) Firstly, realizing the conversion of components in the waste SCR denitration catalyst through the thermochemical reaction between metal oxide components and alkali metal oxide in the waste SCR denitration catalyst so as to increase the solubility of part of the components in molten salt; (2) by utilizing different solubility of different components in molten salt in products after thermochemical reaction, V, Mo and W elements are separated from Ti elements through molten salt soaking; (3) by utilizing the difference of electrodeposition potentials among V, Mo and W elements in ionic states after molten salt soaking and dissolving, metals V, Mo and W can be respectively obtained by applying different reaction potentials or reaction voltages in sequence, so that the separation and recovery of the V, Mo and W elements in the waste SCR denitration catalyst are realized; (4) and the residual substance which is in a solid state after being soaked in the molten salt is used as a reaction cathode, and the metal Ti is prepared by adopting a molten salt electrolysis solid-state reduction method, so that the separation, extraction and recovery of the metal element Ti in the waste SCR denitration catalyst are realized.

The utility model has no consumption and discharge of acid and alkali reagents, and the recovery process has the characteristics and advantages of green and low pollution; the metal resources V, Mo, W and Ti in the waste SCR catalyst can be separated, extracted and recovered in a metal simple substance form with high efficiency, the product purity is high, and the economic added value of the recovered product is high.

Drawings

Fig. 1 is the utility model discloses to metal resource separates in abandonment SCR denitration catalyst and draws recycle's process flow diagram.

Fig. 2 is the utility model discloses to metal resource separates in the abandonment SCR denitration catalyst and draws recycle's system schematic diagram.

Fig. 3 is the utility model discloses to metal resource among the abandonment SCR denitration catalyst separate extract recycle in-process fused salt hot dipping and electrodeposition system's schematic diagram.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings and specific embodiments:

referring to fig. 1, a system for recycling metal resources in a waste SCR denitration catalyst mainly includes a pretreatment system, a ball milling system, a calcination system, a molten salt hot dipping and electrodeposition system, and a molten salt electrolysis system; the pretreatment system is connected with the ball milling system, the ball milled product enters the calcining system, and the calcined product is wrapped and then sent to the molten salt hot dipping and electro-deposition system, so that the extraction and recovery of metals V, Mo and W are realized; and (4) enabling the residues after molten salt hot dipping to enter a molten salt electrolysis system to realize extraction and recovery of metal Ti.

The pretreatment system is mainly used for treating the waste catalyst in a mechanical mode, and comprises a high-pressure air gun purging process and a water washing process, and further comprises a drying device for drying the washed waste catalyst. The pretreated waste catalyst is sent to a ball milling system, and a ball milling tank and ball milling beads adopted by the ball milling system are made of agate materials, so that the pollution of other metal elements to the waste catalyst is reduced. The ball milling can adopt a dry milling mode or a wet milling mode, and the liquid adopted in the wet milling process is ethanol and other solvents which are volatile and do not react with the raw materials. The calcination system adopts a degree temperature control method to realize standard program control of the temperature rise process and the temperature rise rate. The inner part is provided with an annular resistance wire, so that the calcined material is uniformly heated; and placing a thermocouple at the same horizontal position of the calcined material to realize accurate monitoring of the heated temperature and accurate control of the heating rate, wherein the adopted calcination temperature is 650-850 ℃. The waste SCR catalyst after calcination needs to be wrapped by a high-temperature-resistant material with certain porosity before entering a molten salt hot dipping and molten salt electro-deposition system, so that on one hand, sufficient contact reaction between the waste SCR catalyst and the molten salt is guaranteed, on the other hand, components which do not perform thermochemical reaction with the molten salt are guaranteed to be retained in the high-temperature-resistant material, and the molten salt is convenient to move out subsequently. The molten salt hot dipping and the electro-deposition system can respectively realize a molten salt hot dipping process and a molten salt electro-deposition process. The device consists of a high-temperature electric furnace, a reactor, an electrolytic cell, a thermocouple and the like. Wherein the high-temperature electric furnace can heat the reactor; the reactor is arranged in the high-temperature electric furnace and is made of high-temperature-resistant metal materials, ceramic materials or graphite, and the top of the reactor is provided with an anode port, a cathode port, an observation port, an air inlet, an air outlet and a circulating cooling water inlet and outlet; the anode port and the cathode port can be respectively used for placing corresponding anode and cathode materials. The observation port can observe the internal state of the reactor in real time; the circulating cooling water can cool the top of the reactor, preventing potential safety risks caused by high temperatures at the top of the reactor. The thermocouple is arranged between the high-temperature electric furnace and the reactor, and can monitor the reaction temperature of the electrolysis system in real time. The reaction electrolytic cell is arranged in the reactor and is made of ceramic materials or graphite, and the anode materials and the cathode materials adopted by the reaction electrolytic cell are inserted into the electrolytic cell through the anode port and the cathode port of the reactor, so that the depth of the reaction electrolytic cell being immersed in electrolyte and the distance between the anode and the cathode are fixed. The molten salt hot dipping and electro-deposition system is connected with the temperature control device and the reaction control device; the temperature control system can control the temperature rise temperature and the temperature rise rate of the high-temperature electric furnace in real time; the reaction control system main body is a reaction power supply, mainly uses a direct current stabilized voltage power supply, and is connected with the reaction anode and the reaction cathode through leads, and the reaction control system can control reaction current, reaction voltage, reaction time, reaction electric quantity and the like to realize control of reaction rate and deoxidation degree. The molten salt hot dipping and electro-deposition system is connected with a gas distribution system which mainly conveys inert gases such as Ar gas and the like to the interior of the molten salt hot dipping and molten salt electro-deposition system so as to prevent the oxidation of the reactor and an electrolysis product under the high-temperature condition. And a gas drying device is arranged between the gas distribution system and the molten salt hot dipping and electro-deposition system to dry the gas entering the molten salt hot dipping and electro-deposition system. The molten salt electrolysis system is similar to the molten salt hot dipping and electrodeposition system in terms of the composition of the device, but is different from the operation and recovery principle of the recovered metal. Molten salt hot dipping and electrodeposition systems are mainly aimed at extracting V, Mo, W. The method comprises two steps of molten salt hot dipping and electrodeposition, and must be carried out in one system. The general process comprises the steps of soaking materials in a molten salt hot dipping and electro-deposition system, dissolving soluble substances (containing V, Mo and W substances) into the molten salt hot dipping and electro-deposition system, then carrying out electro-deposition operation in the molten salt hot dipping and electro-deposition system, and respectively carrying out electro-deposition recovery on the dissolved V, Mo and W substances (the same system, two steps in sequence); and insoluble substances exist in the form of solid residues after hot dipping, and are removed from the molten salt hot dipping and electrodeposition system, and then the molten salt electrolysis operation is carried out on the insoluble substances in the molten salt electrolysis system, so that the recovery of Ti is realized.

When in use, the method specifically comprises the following steps:

the main component is V₂O₅/MoO₃/WO₃/TiO₂The waste SCR denitration catalyst is placed in a pretreatment system, and impurities on the surface of the catalyst are removed. Then the mixture is sent to a ball milling system together with alkali metal oxide (one of lithium oxide, potassium oxide, sodium oxide, calcium oxide and magnesium oxide) and mixed with alkali metal oxide in a certain proportion, so that all components are uniformly mixed. And placing the reaction substances subjected to ball milling in a calcining system, and calcining for a certain time at a proper reaction temperature. Then, a net bag made of high-temperature resistant materials with certain porosity is adopted to carry out calcination on the calcined substanceAnd (6) packaging.

And (3) conveying the coated reaction substance into a molten salt hot dipping and electro-deposition system, after thermochemical reaction for a certain time, transferring metal elements V, Mo and W into a reaction electrolyte in an ionic state, and removing a compound corresponding to the metal element Ti out of the molten salt hot dipping and electro-deposition system, wherein the compound still exists in the coating material. Because the metal elements V, Mo and W in the ion state in the reaction electrolyte have different reduction potentials, the high-temperature-resistant conductive material is taken as a reaction cathode, the soluble or insoluble material is taken as a reaction anode, and different reaction potentials or reaction voltages E are applied in sequence₁、E₂、E₃The metal elements V, Mo and W can be respectively recovered by electrodeposition.

A compound corresponding to a metal element Ti is used as a reaction cathode, and a soluble or insoluble material is used as a reaction anode. The reaction cathode and the reaction anode are placed in a molten salt electrolysis system, proper reaction voltage is applied between the cathode and the anode, and proper reaction time is selected for electrolysis, so that an electrolysis product Ti can be obtained at the cathode.

The present invention will be described in further detail with reference to the following embodiments:

example 1

And (3) pretreating the waste SCR denitration catalyst by adopting a high-pressure air gun and water washing mode to remove impurities on the surface. After drying treatment, 5g of the waste SCR denitration catalyst and calcium oxide are weighed according to the molar ratio of 1:1 and placed in a ball milling tank to be ball milled for 24 hours under the condition that the rotating speed is 300 rpm. And placing the mixed substances subjected to ball milling in a calcining device, raising the temperature to 850 ℃, and carrying out calcining treatment for 6 hours. And (3) wrapping the calcined reaction substance by using a metal net bag made of a high-temperature resistant material, and integrally fixing the metal net bag on an operating rod made of a high-temperature resistant material.

With 500g CaCl₂Is used as a reaction electrolyte and is placed in an alumina crucible to form a reaction electrolytic cell. The reaction electrolytic cell is arranged in a graphite crucible, the graphite crucible can prevent the hearth from being damaged by leakage liquid, and a certain amount of oxygen can be consumed to control the atmosphere in the reactor. For CaCl at 300 DEG C₂Drying treatment is carried out for 48 h. Followed byUnder the condition of argon and the protection of cooling water, at 5 ℃ for min^-1The ramp rate of (a) slowly raises the temperature to 850 c while the molten salt is in a molten state.

And (3) placing the metal net bag coated with the reaction substance in a molten salt hot dipping and molten salt electrodeposition device, and removing the metal net bag out of the molten salt after reacting for 4 hours. Because the metal compounds corresponding to the metal elements vanadium, molybdenum and tungsten in the reaction substance after calcination treatment have high solubility in the molten salt, the corresponding compounds are dissolved and transferred to the CaCl serving as a reaction electrolyte in an ionic state₂And the solubility of the compound corresponding to the metal titanium is low, and the compound is retained in the metal net bag in a solid state. Thereby realizing the primary separation of the components.

Placing a graphite rod as an anode and stainless steel as a cathode in a reaction electrolyte CaCl₂In the process, under the condition of 850 ℃, 1.6V electrolytic voltage is applied between a cathode and an anode, after 10 hours of reaction, the current value is basically kept stable, no obvious metal is separated out, and a stainless steel cathode is slowly moved out of a reaction electrolyte CaCl₂Cooling in inert atmosphere, washing the deposited product on the surface of the stainless steel cathode by using deionized water to remove a small amount of electrolyte, and drying under vacuum condition to obtain the product with the main component of metal molybdenum.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂In the process, under the condition of 850 ℃, 1.65V electrolytic voltage is applied between a cathode and an anode, after 10 hours of reaction, the current value is basically kept stable, no obvious metal is separated out, and a stainless steel cathode is slowly moved out of a reaction electrolyte CaCl₂Cooling in inert atmosphere, washing the stainless steel cathode product with deionized water to remove a small amount of electrolyte, and drying under vacuum condition to obtain the product with main component of metal tungsten.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂In the process, under the condition of 850 ℃, 1.75V electrolytic voltage is applied between a cathode and an anode, after reaction for 10 hours, the current value is basically kept stable, no obvious metal is separated out, and a stainless steel cathode is slowly moved out of a reaction electrolyte CaCl₂Cooling under inert atmosphere, and applying deionized water to stainless steel cathode productCleaning to remove a small amount of electrolyte, and drying under vacuum condition to obtain the product with main component of vanadium metal.

1.5g of the residual reaction substance in the metal string bag was weighed and subjected to press molding of a cathode test piece (diameter 20mm) under a pressure of 10 MPa. The cathode coupon was wrapped with nickel foam and secured to a cathode current collector molybdenum rod with a molybdenum wire. With CaCl₂The method comprises the steps of taking graphite as a reaction anode, placing the reaction electrolyte, a reaction cathode and the reaction anode in a molten salt electrolysis device, applying 3.0V electrolysis voltage between the cathode and the anode at 850 ℃, after reacting for 10h, slowly extracting a cathode test piece, cooling under the inert atmosphere condition, washing a stainless steel cathode product by using deionized water to remove a small amount of electrolyte, and drying under the vacuum condition to obtain a product, wherein the main component of the product is metallic titanium.

Example 2

And (3) pretreating the waste SCR denitration catalyst by adopting a high-pressure air gun and water washing mode to remove impurities on the surface. After drying treatment, 5g of the waste SCR denitration catalyst and sodium oxide are weighed according to the molar ratio of 1:1 and placed in a ball milling tank to be ball milled for 24 hours under the condition that the rotating speed is 300 rpm. Placing the mixed material after ball milling in a heatable reaction device, raising the temperature to 650 ℃, and carrying out calcination treatment for 6 hours. And (3) wrapping the calcined reaction substance by using a metal net bag made of a high-temperature resistant material, and integrally fixing the metal net bag on an operating rod made of a high-temperature resistant material.

500g of CaCl₂And (3) taking NaCl mixed salt as a reaction electrolyte, and placing the NaCl mixed salt in an alumina crucible to form a reaction electrolytic cell. The reaction electrolytic cell is arranged in a graphite crucible, the graphite crucible can prevent the hearth from being damaged by leakage liquid, and a certain amount of oxygen can be consumed to control the atmosphere in the reactor. For CaCl at 300 DEG C₂NaCl was oven dried for 48 h. Then under the condition of argon and the protection of cooling water, at 5 ℃ for min^-1The ramp rate of (a) slowly raises the temperature to 750 c while the molten salt is in a molten state.

Placing the metal net bag coated with the reaction substance in a molten salt hot dipping and molten salt electrodeposition device, reacting for 8h, and then placing the metal net bagThe molten salt is removed. Because the metal compounds corresponding to the metal elements vanadium, molybdenum and tungsten in the reaction substance after calcination treatment have high solubility in the molten salt, the corresponding compounds are dissolved and transferred to the CaCl serving as a reaction electrolyte in an ionic state₂In NaCl, the solubility of the compound corresponding to the metal titanium is low, and the compound is retained in the metal net bag in a solid state. Thereby realizing the primary separation of the components.

Placing a graphite rod as an anode and stainless steel as a cathode in a reaction electrolyte CaCl₂In NaCl, applying 1.9V electrolytic voltage between the cathode and the anode at 750 ℃, after 12h of reaction, keeping the current value basically stable and no obvious metal precipitation, and slowly moving the stainless steel cathode out of the CaCl serving as a reaction electrolyte₂And NaCl, cooling in an inert atmosphere, washing the deposited product on the surface of the stainless steel cathode by using deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain a product with the main component of metal molybdenum.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂In NaCl, at 750 deg.c, applying 1.95V electrolytic voltage between the anode and the cathode, after reaction for 12 hr, maintaining the current value stable and no obvious metal precipitation, and slowly shifting the stainless steel cathode out of the CaCl as the reaction electrolyte₂And NaCl, cooling in an inert atmosphere, washing the stainless steel cathode product by using deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain the product with the main component of metal tungsten.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂In NaCl, applying 2.1V electrolytic voltage between the cathode and the anode at 750 ℃, after 12h of reaction, keeping the current value basically stable and no obvious metal precipitation, and slowly moving the stainless steel cathode out of the CaCl serving as a reaction electrolyte₂And NaCl, cooling in an inert atmosphere, washing the stainless steel cathode product by using deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain a product with the main component of vanadium metal.

1.5g of the residual reaction substance in the metal string bag was weighed and subjected to press molding of a cathode test piece (diameter 20mm) under a pressure of 10 MPa. With bubblesAnd the nickel foam wraps the cathode test piece and is fixed on the cathode current collector molybdenum rod by using a molybdenum wire. Graphite as reaction anode and CaCl₂NaCl is used as a reaction electrolyte, a reaction anode, a reaction cathode and the reaction electrolyte are placed in a molten salt electrolysis device, the reaction temperature is increased to 900 ℃, 3.0V electrolysis voltage is applied between the cathode and the anode, after reaction for 10 hours, a cathode test piece is slowly extracted, cooling is carried out under the inert atmosphere condition, deionized water is used for cleaning a stainless steel cathode product to remove a small amount of electrolyte, drying is carried out under the vacuum condition, and the main component of the obtained product is metallic titanium.

Example 3

And (3) pretreating the waste SCR denitration catalyst by adopting a high-pressure air gun and water washing mode to remove impurities on the surface. After drying treatment, 5g of the waste SCR denitration catalyst and lithium oxide are weighed according to the molar ratio of 1:1 and placed in a ball milling tank to be ball milled for 24 hours under the condition that the rotating speed is 300 rpm. And placing the mixed substances subjected to ball milling in a heatable reaction device, raising the temperature to 725 ℃, and carrying out calcination treatment for 6 hours. And (3) wrapping the calcined reaction substance by using a metal net bag made of a high-temperature resistant material, and integrally fixing the metal net bag on an operating rod made of a high-temperature resistant material.

500g of CaCl₂And (3) taking LiCl mixed salt as a reaction electrolyte, and placing the LiCl mixed salt in an alumina crucible to form a reaction electrolytic cell. The reaction electrolytic cell is arranged in a graphite crucible, the graphite crucible can prevent the hearth from being damaged by leakage liquid, and a certain amount of oxygen can be consumed to control the atmosphere in the reactor. For CaCl at 300 DEG C₂Drying treatment of LiCl for 48 h. Then under the condition of argon and the protection of cooling water, at 5 ℃ for min^-1The temperature rise rate of (a) slowly raised the temperature to 800 ℃, at which time the molten salt was in a molten state.

And (3) placing the metal net bag coated with the reaction substance in a molten salt hot dipping and molten salt electrodeposition device, and after reacting for 6 hours, removing the metal net bag out of the molten salt. Because the metal compounds corresponding to the metal elements vanadium, molybdenum and tungsten in the reaction substance after calcination treatment have high solubility in the molten salt, the corresponding compounds are dissolved and transferred to the CaCl serving as a reaction electrolyte in an ionic state₂in-LiClThe solubility of the compound corresponding to the metal titanium is low, and the compound is retained in the metal net bag in a solid state. Thereby realizing the primary separation of the components.

Placing a graphite rod as an anode and stainless steel as a cathode in a reaction electrolyte CaCl₂in-LiCl, under the condition of 800 ℃, applying 1.7V electrolytic voltage between a cathode and an anode, after 12 hours of reaction, keeping the current value basically stable and having no obvious metal precipitation, and slowly moving a stainless steel cathode out of a reaction electrolyte CaCl₂-LiCl, cooling in an inert atmosphere, washing the deposited product on the surface of the stainless steel cathode by using deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain the product with the main component of metal molybdenum.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂in-LiCl, under the condition of 800 ℃, applying 1.75V electrolytic voltage between a cathode and an anode, after 12 hours of reaction, keeping the current value basically stable and having no obvious metal precipitation, and slowly moving a stainless steel cathode out of a reaction electrolyte CaCl₂-LiCl, cooling in an inert atmosphere, washing the stainless steel cathode product with deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain the product with the main component of metal tungsten.

Replacing and using a new stainless steel cathode to be placed in the previous reaction electrolyte CaCl₂in-LiCl, under the condition of 800 ℃, applying 1.85V electrolytic voltage between a cathode and an anode, after 12 hours of reaction, keeping the current value basically stable and having no obvious metal precipitation, and slowly moving a stainless steel cathode out of a reaction electrolyte CaCl₂-LiCl, cooling in an inert atmosphere, washing the stainless steel cathode product with deionized water to remove a small amount of electrolyte, and drying under a vacuum condition to obtain the product with the main component of vanadium metal.

1.5g of the residual reaction substance in the metal string bag was weighed and subjected to press molding of a cathode test piece (diameter 20mm) under a pressure of 10 MPa. The cathode coupon was wrapped with nickel foam and secured to a cathode current collector molybdenum rod with a molybdenum wire. Graphite as reaction anode and CaCl₂LiCl is used as a reaction electrolyte, a reaction anode, a reaction cathode and the reaction electrolyte are placed in a molten salt electrolysis device, and the reaction is increasedAnd (2) applying 3.0V electrolytic voltage between the cathode and the anode at the temperature of 900 ℃, slowly extracting the cathode test piece after reacting for 10 hours, cooling under the inert atmosphere, cleaning a stainless steel cathode product by using deionized water to remove a small amount of electrolyte, and drying under the vacuum condition to obtain a product with the main component of metallic titanium.

Claims (5)

1. The utility model provides a system of metal resource recycle in abandonment SCR denitration catalyst, its characterized in that, including the pretreatment systems who is used for getting rid of the surperficial impurity with abandonment SCR denitration catalyst, the export of pretreatment systems is connected to the ball-milling system, and the export of ball-milling system is connected to the system of calcining, and the export of the system of calcining is connected to being used for realizing drawing the fused salt hot dipping and the electrodeposition system of retrieving to metal V, Mo and W, and the residual export of fused salt hot dipping and the electrodeposition system is connected to being used for realizing drawing the fused salt electrolysis system of retrieving to metal Ti.

2. The system for recycling metal resources in the waste SCR denitration catalyst according to claim 1, wherein the pretreatment system comprises a high pressure air gun for purging the waste SCR denitration catalyst, a water washing device for washing the purged catalyst, and a drying device for drying the washed catalyst.

3. The system for recycling metal resources in the waste SCR denitration catalyst according to claim 1, wherein the calcination system comprises a heating device adopting a ring heating mode, and a thermocouple placed at the same horizontal position with the calcination material.

4. The system for recycling metal resources in the waste SCR denitration catalyst according to claim 1, wherein the molten salt hot dipping and electro-deposition system comprises an electrolysis device, the electrolysis device comprises an electrolysis cell, the electrolysis cell is arranged in a reactor, the reactor is arranged in a high-temperature electric furnace, a gas inlet on the reactor is connected to a gas distribution system for providing inert gas through a gas drying device, and a gas outlet on the reactor is respectively connected to a vacuum pump and a tail gas recovery system.

5. The system for recycling metal resources in the waste SCR denitration catalyst according to claim 4, wherein the reactor is further connected with a control system, and the control system comprises a temperature control system for controlling the temperature rise temperature and the temperature rise rate of the high-temperature electric furnace and a reaction control system for controlling the parameters of the reaction process.

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