CN212404222U

CN212404222U - Hydrogenation spent catalyst recovery device

Info

Publication number: CN212404222U
Application number: CN202021881099.8U
Authority: CN
Inventors: 周冲; 张溪; 浦晓峰
Original assignee: Wuxi Apt Equipment Technology Co ltd
Current assignee: Wuxi Apt Equipment Technology Co ltd
Priority date: 2020-09-02
Filing date: 2020-09-02
Publication date: 2021-01-26
Anticipated expiration: 2030-09-02

Abstract

The utility model relates to a hydrogenation waste catalyst recovery device, in the device, a desorption feeding system, a cylindrical mixer, a primary roasting rotary kiln and a feeding port of a primary leaching groove are communicated; the first leaching tank, the first filtering device, the vanadium or tungsten precipitation stirring tank, the second filtering device, the molybdenum precipitation stirring tank, the third filtering device, the dilute molybdic acid adsorption tank, the deamination tower and the first evaporative crystallization device are communicated in sequence, and materials are treated in sequence. The utility model discloses a low process cost, green, effective cyclic utilization useful component in the useless catalyst of hydrogenation, greatly reduced system operation acid consumption, consume alkali volume.

Description

Hydrogenation spent catalyst recovery device

Technical Field

The utility model relates to a useless catalyst comprehensive utilization system especially relates to a useless catalyst recovery unit of hydrogenation, and the device is suitable for and draws useful metal from the useless catalyst of hydrogenation, especially effectively retrieves cobalt metal, molybdenum metal and aluminium metal in the hydrogenation catalyst.

Background

Spent catalysts are recognized environmental pollutants that must be converted to harmless substances before entering the environment. The residual oil hydrogenation waste catalyst contains rare metals such as molybdenum, vanadium and the like, and has high economic value. However, separation is difficult due to the chemical commonality of molybdenum and vanadium.

At present, domestic and foreign companies generally adopt a combined process of oxidizing roasting-wet treatment, wherein more than 90% of the processes adopt the oxidizing roasting-ammonia leaching process, such as the utility model patent with the application number of CN200810228402.1 or the utility model patent with the application number of CN201110100657.1, and the method is used, and the main purpose of oxidizing roasting is to mix MoS₂Conversion to MoO₃，MoO₃Is easy to dissolve in ammonia water, the calcine is leached by the ammonia water to prepare ammonium molybdate, and the ammonium molybdate is used for preparing other molybdenum compounds. However, the purity of molybdenum and vanadium obtained by the existing separation process is not high, and the molybdenum and vanadium with high purity can be obtained only by multiple separation processes, so the cost is high.

The utility model with application number CN201711091099.0 and name of a waste catalyst comprehensive utilization system also provides a waste catalyst comprehensive utilization system, and the main disadvantages of this patent are: sodium hydroxide is used for sodium salt roasting, so that alkali cannot be recycled, alkali consumption is large, only nickel-aluminum mixed powder is simply separated finally, acid leaching is needed in later period utilization, acid consumption and alkali consumption are large, and cost is high.

The waste hydrogenation catalyst contains rare metals such as molybdenum, vanadium and the like, and also contains other components, and the waste hydrogenation catalyst also has economic value. The method has profound significance for China with low per capita resource ownership rate. Therefore, a novel comprehensive utilization system of the waste catalyst is developed, and the system has certain significance for recycling the hydrogenation waste catalyst.

SUMMERY OF THE UTILITY MODEL

To the not enough of prior art, the utility model discloses a useless catalyst recovery unit of hydrogenation.

The utility model discloses the technical scheme who adopts as follows:

the recycling device for the hydrogenation waste catalyst is characterized in that: a discharge port of the thermal desorption feeding system is communicated with a feed port of the cylindrical mixer; the discharge port of the cylindrical mixer is communicated with the feed port of the cylinder of the primary roasting rotary kiln; the discharge port of the cylinder of the primary roasting rotary kiln is communicated with the feed port of the primary leaching groove; the liquid phase outlet of the first leaching tank is communicated with the feed inlet of the impurity removal stirring tank; a discharge hole of the impurity removal stirring tank is communicated with a feed hole of the first filtering equipment; a liquid-phase filtrate outlet of the first filtering device is communicated with a feeding port of the vanadium or tungsten precipitation stirring tank; a discharge port of the vanadium or tungsten precipitation stirring tank is communicated with a feed port of the second filtering device; a liquid-phase filtrate outlet of the second filtering device is communicated with a feed inlet of the molybdenum precipitation stirring tank; a discharge port of the molybdenum precipitation stirring tank is communicated with a feed port of the third filtering device; a liquid-phase filtrate outlet of the third filtering device is communicated with a feed inlet of the dilute molybdic acid adsorption tank; a discharge hole of the dilute molybdic acid adsorption tank is communicated with a feed inlet of the deamination tower; the discharge port of the deamination tower is communicated with the feeding port of the first evaporative crystallization device.

The further technical scheme is as follows: the thermal desorption feeding system comprises a conveying and extracting pipe, a heat conducting oil furnace and a condensing tank; the conveying and extracting pipe is a spiral material conveying mechanism with a steel interlayer on the outer wall; the heat conduction oil outlet of the heat conduction oil furnace is communicated with the interlayer inlet of the steel interlayer, and the interlayer outlet of the steel interlayer is communicated with the oil return port of the heat conduction oil furnace; and a gas output port of the conveying and extracting pipe is communicated with a condensation inlet of the condensation tank.

The further technical scheme is as follows: the device also comprises a secondary treatment system; the secondary treatment system comprises a secondary roasting rotary kiln, a second leaching tank, an aluminum precipitation tank, a fourth filtering device and a second evaporative crystallization device; the solid-phase sediment outlet of the first leaching tank and/or the solid-phase sediment outlet of the first filtering device is communicated with a feeding port of the secondary roasting rotary kiln; the discharge hole of the secondary roasting rotary kiln is communicated with the feed inlet of the secondary leaching tank; the liquid phase outlet of the second leaching tank is communicated with the feeding port of the aluminum precipitation tank; a discharge hole of the aluminum precipitation tank is communicated with a feed hole of the fourth filtering device; a liquid-phase filtrate outlet of the fourth filtering device is communicated with a feeding port of the second evaporative crystallization device; the discharge hole of the second evaporative crystallization device is communicated with the recycled alkali feeding hole of the cylindrical mixer and/or communicated with the feeding hole of the secondary roasting rotary kiln; and a condensed water outlet of the second evaporative crystallization device is communicated with a water replenishing port of the second leaching tank.

The further technical scheme is as follows: the condensed water outlet of the first evaporative crystallization device is communicated with the water replenishing port of the first leaching tank.

The utility model has the advantages as follows:

the utility model discloses a cost that the device is constituteed is lower, and the whole process green of device operation can effective cyclic utilization useful composition in the hydrogenation spent catalyst to add the leaching groove in the device, used the water logging technology to replace traditional pickling technology, retrieve alkali cyclic utilization, greatly reduced system operation acid consumption, consume alkali volume.

Based on the above reason, the utility model discloses can extensively promote in fields such as cyclic utilization of chemical waste, have very strong practicality.

Drawings

FIG. 1 is a schematic view showing the structure of an example of an apparatus for recovering a spent hydrogenation catalyst.

FIG. 2 is a schematic flow diagram of an embodiment of a process for the recovery of spent hydroprocessing catalyst.

In the figure: 1. a thermal desorption feed system; 2. a cylindrical mixer; 3. primary roasting in a rotary kiln; 4. a primary leaching tank; 5. an impurity removal stirring tank; 6. a first filtering device; 7. a vanadium or tungsten precipitation stirring tank; 8. a second filtering device; 9. a molybdenum precipitation stirring tank; 10. a third filtering device; 11. a dilute molybdic acid adsorption tank; 12. a deamination tower; 13. a first evaporative crystallization device; 14. secondary roasting in a rotary kiln; 15. a second leaching tank; 16. an aluminum deposition tank; 17. a fourth filtration device; 18. and a second evaporative crystallization device.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.

FIG. 1 is a schematic view showing the structure of an example of an apparatus for recovering a spent hydrogenation catalyst. As shown in fig. 1, the present embodiment provides an apparatus for recovering spent hydrogenation catalyst, including:

and the thermal desorption feeding system 1 is used for performing thermal desorption on the hydrogenation waste catalyst. Thermal desorption feed system 1 is including carrying extraction tube, heat conduction oil furnace and condensing equipment.

The conveying and extracting pipe is a spiral material conveying mechanism with a steel interlayer on the outer wall.

The heat conduction oil furnace is a device which directly inserts an electric heater into heat conduction oil to heat the heat conduction oil, carries out liquid phase circulation through a high-temperature oil pump to convey the heated heat conduction oil to a heat utilization device, and then returns the heated heat conduction oil to the electric heating oil furnace for heating through an oil outlet of the heat utilization device. The heat conducting oil outlet of the heat conducting oil furnace is communicated with the interlayer inlet of the steel interlayer, and the interlayer outlet of the steel interlayer is communicated with the oil return port of the heat conducting oil furnace. And (4) the heat-conducting oil enters the steel interlayer, and the waste hydrogenation catalyst in the conveying and extracting pipe is subjected to thermal desorption to obtain the waste deoiling catalyst material.

The condensing device comprises a condensing tank, and a circulating water spraying and washing device is arranged in the condensing tank. The gas output port of the conveying and extracting pipe is communicated with the condensation inlet of the condensation tank. And the condensing device carries out circulating water spraying and washing on the high-temperature desorption gas obtained by thermal desorption.

The cylindrical mixer 2 comprises a feeding port and a recycled alkali feeding port. The cylinder mixer 2 is used for mixing materials input by the two ports of the feed inlet and the recycled alkali input port. And a feeding port of the cylindrical mixer 2 is communicated with a discharging port of the thermal desorption feeding system 1. Obtaining deoiled waste catalyst material and recovered alkali mixed material in a cylindrical mixer 2.

The primary roasting rotary kiln 3 is a device for roasting a material. The primary roasting rotary kiln 3 includes a cylinder and a combustion device. The discharge port of the cylindrical mixer 2 is communicated with the feed port of the cylinder of the primary roasting rotary kiln 3. The combustion device is positioned at the discharge hole of the cylinder of the primary roasting rotary kiln 3. The primary roasting rotary kiln 3 is used for carrying out primary roasting on the deoiling waste catalyst material and the recovered alkali mixed material.

The leaching tank is a facility for implementing the leaching process, and water can be added into the leaching tank to extract substances which are easy to dissolve in water in the material, and other liquid can be added into the leaching tank to leach. The leaching tank comprises a liquid phase outlet for discharging liquid and a solid phase sludge outlet for discharging solid phase sludge. The discharge port of the cylinder of the primary roasting rotary kiln 3 is communicated with the feed port of the primary leaching tank 4. The liquid phase outlet of the primary leaching tank 4 is communicated with the material inlet of the impurity removal stirring tank 5, and the solid phase sediment outlet of the primary leaching tank 4 is communicated with the material inlet of the secondary roasting rotary kiln 14.

The impurity removal stirring tank 5 is a vertical stainless steel stirring tank, and stirring blades rotate in a fixed direction under the driving of a power unit; in the rotating process, the material is driven to rotate axially and radially. The materials in the stirrer simultaneously have axial motion and circular motion, so that several stirring modes such as shearing stirring, diffusion stirring and the like simultaneously exist. Can be effective to carry out quick stirring, mixing to the material. In the impurity removal stirring tank 5, ammonium sulfate and magnesium sulfate are added into the mixed solution which is separated from the primary leaching tank 4 and discharged from the liquid phase outlet, and a small amount of impurities such as aluminum, phosphorus and the like are removed. The mixed solution can be a solution containing sodium molybdate and sodium vanadate, and can also be a solution containing sodium tungstate and sodium molybdate.

The filtering equipment is a plate-and-frame filter press which generally comprises a head plate, a tail plate, a filter plate, a hydraulic cylinder, a main beam, a transmission and pulling device and the like. The hydraulic cylinder piston pushes the head plate to enable the filter plates to tightly press the adjacent filter plates to form a filter chamber; the slurry is sent into a filter chamber by a slurry pump, water is discharged through a liquid outlet through filter cloth, and the solid slurry forms a filter cake in the filter chamber. After the filter chamber is filled with the slurry, the slurry is continuously pressurized and filtered by a high-pressure pump, so that solid and liquid are separated in the filter chamber. The filtering equipment comprises a liquid-phase filtrate outlet and a solid-phase sediment outlet. The discharge hole of the impurity removal stirring tank 5 is communicated with the feeding hole of the first filtering equipment 6. The material discharged from the discharge opening of the impurity removal stirring tank 5 is filtered in a first filtering device 6.

A liquid-phase filtrate outlet of the first filtering device 6 is communicated with a feeding port of the vanadium or tungsten precipitation stirring tank 7, and a solid-phase sediment outlet of the first filtering device 6 is communicated with a feeding port of the secondary roasting rotary kiln 14.

The vanadium or tungsten precipitation stirring tank 7 is a vertical stainless steel stirring tank, and the principle and the work are similar to those of the impurity removal stirring tank 5.

And a discharge port of the vanadium or tungsten precipitation stirring tank 7 is communicated with a feed port of the second filtering equipment 8. The second filtering device 8 filters the liquid discharged from the discharge hole of the vanadium or tungsten precipitation stirring tank 7. The solid-phase filtrate obtained from the solid-phase sediment outlet of the second filtering device 8 is the product ammonium metavanadate or calcium tungstate. And a liquid-phase filtrate outlet of the second filtering device 8 is communicated with a feeding port of the molybdenum precipitation stirring tank 9.

The molybdenum precipitation stirring tank 9 is a vertical stainless steel stirring tank, and the principle and the work are similar to those of the impurity removal stirring tank 5.

The discharge hole of the molybdenum precipitation stirring tank 9 is communicated with the feed inlet of the third filtering device 10. The third filtering device 10 filters the liquid discharged from the discharge hole of the molybdenum precipitation stirring tank 9. The solid-phase filtrate obtained from the solid-phase sediment outlet of the third filtering device 10 is the product molybdic acid, the liquid-phase filtrate outlet of the third filtering device 10 is communicated with the feed inlet of the dilute molybdic acid adsorption tank 11, and the dilute molybdic acid without precipitation is discharged into the dilute molybdic acid adsorption tank 11.

The shell of the dilute molybdic acid adsorption tank 11 is made of steel-lined low-calcium and magnesium rubber, the flower plate at the lower part of the tower is made of steel low-calcium and magnesium rubber, a filter cap is arranged on the flower plate, and molybdic acid adsorption resin is filled on the flower plate. The middle part of the tower is provided with a distribution pipe which is made of steel lining low-calcium magnesium rubber, and the upper part of the distribution pipe is also provided with a filter cap. In operation, the filtrate enters from the top of the column, flows through the resin bed, and then flows out from the lower part of the column, wherein molybdic acid ions are adsorbed by the resin, so that molybdic acid is enriched. And the dilute molybdic acid adsorption tank 11 is used for carrying out resin adsorption on the molybdenum precipitation filtrate separated by the third filtering device 10.

Further, after the adsorption of the resin in the dilute molybdic acid adsorption tank 11 is saturated, a sodium hydroxide solution can be added for soaking and regeneration, and the soaked molybdate-containing eluent returns to the molybdenum precipitation stirring tank 9 to precipitate molybdic acid again for recovery.

Deamination tower 12 is operated in series with double towers to increase the recovery concentration of ammonia. And an ammonia nitrogen sulfuric acid absorption tower is arranged behind the stripping tower, so that the ammonia nitrogen waste gas stripped by blowing is treated by the sulfuric acid absorption tower and is discharged after reaching the standard. Firstly, ammonia nitrogen in the wastewater is blown out through aeration in a blow-off tower, ammonia nitrogen waste gas enters a purification tower from a lower gas inlet, the space of a gas inlet section is quickly filled under the power action of a ventilator, and then the ammonia nitrogen waste gas uniformly rises to a first-stage filler absorption section through a flow equalizing section. On the surface of the packing, ammonia gas in the gas phase reacts chemically with water or sulfuric acid in the liquid phase to produce ammonium sulfate, which flows into the lower sump. The incompletely absorbed ammonia gas continuously rises to enter a first-stage spraying section. The absorption liquid is sprayed out from the uniformly distributed nozzles at high speed in the spraying section to form countless fine fog drops, the fog drops are fully mixed and contacted with the gas to continuously carry out chemical reaction, and then the ammonia gas rises to the secondary filling section and the spraying section to carry out the absorption process similar to the primary absorption process. The second stage and the first stage have different nozzle densities, different liquid spraying pressures and different concentration ranges of the absorbed acid gas. The process of contacting the spraying section and the filling section is also the process of heat transfer and mass transfer. The process is ensured to be sufficient and stable by controlling the flow rate and the residence time of the tower. The uppermost part of the tower body is a demisting section, absorption liquid fog drops in the gas are removed, and the treated clean air is exhausted into the atmosphere from an exhaust pipe at the upper end of the purification tower. The discharge port of the dilute molybdic acid adsorption tank 11 is communicated with the feed port of the deamination tower 12. The deamination tower 12 is used for adding sulfuric acid into the filtrate after resin adsorption in the dilute molybdic acid adsorption tank 11 to generate and recover an ammonium sulfate solution.

The evaporative crystallization device comprises an evaporation part and a condensed water crystallization part, wherein the evaporation part discharges a solvent from a solution to increase the concentration of the solution, and then the supersaturated solution is cooled through the circulation of the condensed water to separate out solute crystals. The discharge hole of the deammoniation tower 12 is communicated with the feeding hole of the first evaporative crystallization device 13. In the first evaporative crystallization device 13, a solid phase crystallization product, namely the byproduct sodium sulfate, is obtained. The condensed water outlet of the primary evaporative crystallization device 13 is communicated with the water replenishing port of the primary leaching tank 4 and is used as the leaching solution of the primary leaching tank 4.

A secondary treatment system is also included. The secondary treatment system comprises a secondary roasting rotary kiln 14, a secondary leaching tank 15, an aluminum precipitation tank 16, a fourth filtering device 17 and a second evaporative crystallization device 18.

And the secondary roasting rotary kiln 14 is used for carrying out secondary roasting on the tailings after the leaching process of the primary leaching tank 4 is finished and/or the impurity-removed slag after the impurities are removed by the primary filtering equipment 6. The solid-phase sediment outlet of the primary leaching tank 4 is communicated with the feeding port of the secondary roasting rotary kiln 14. The solid-phase sediment outlet of the first filtering device 6 is communicated with the feeding port of the secondary roasting rotary kiln 14. The discharge hole of the secondary roasting rotary kiln 14 is communicated with the feed hole of the secondary leaching tank 15.

The aluminum precipitation tank 16 is a vertical stainless steel stirring tank, and the principle and the work are similar to the impurity removal stirring tank 5. The aluminum precipitation tank 16 is used for precipitating aluminum element. The liquid phase outlet of the secondary leaching tank 15 is communicated with the feed inlet of the aluminum precipitation tank 16. The solid-phase sediment of the aluminum precipitation tank 16 is the crude cobalt product.

The discharge hole of the aluminum precipitation tank 16 is communicated with the feed hole of the fourth filtering device 17. The fourth filter device 17 filters the material discharged from the aluminum precipitation tank 16.

The liquid-phase filtrate outlet of the fourth filtering device 17 is communicated with the feed inlet of the second evaporative crystallization device 18. The solid-phase filtrate obtained from the solid-phase sediment outlet of the fourth filtering device 17 is the product aluminum hydroxide. The solid phase crystallization product of the second evaporative crystallization device 18 is the recovered alkali. The discharge hole of the second evaporative crystallization device 18 is communicated with the recycled alkali feeding hole of the cylindrical mixer 2. The discharge port of second evaporative crystallization device 18 may also be connected to secondary roasting rotary kiln 14 for adding alkali during secondary roasting.

FIG. 2 is a schematic flow diagram of an embodiment of a process for the recovery of spent hydroprocessing catalyst. As shown in fig. 2, the method for recovering hydrogenation catalyst by using the device of the present invention comprises the following steps:

and S1, deoiling the hydrogenated waste catalyst in a thermal desorption mode to obtain the deoiled waste catalyst. The hydrogenation waste catalyst is subjected to deoiling treatment of indirect thermal desorption through a thermal desorption feeding system 1, the heating temperature is 2808350 ℃, and a deoiled waste catalyst and a condensed oil-water mixture are obtained;

and S2, mixing the deoiled waste catalyst and alkali, and roasting for the first time. Mixing the deoiling waste catalyst and the recovered alkali in a mixer 2, then sending into a primary roasting rotary kiln 3 for roasting, and roasting at the high temperature of 95081100 ℃ for about 2 hours to obtain clinker; the main reaction equation of the primary roasting stage is as follows:

MoS₂+3.5O₂＝MoO₃+2SO₂；

MoS₃+4.5O₂＝MoO₃+3SO₂；

MoO₃+Na₂CO₃＝Na₂MoO₄+CO₂；

2V₂O₄+O₂＝2V₂O₅；

V₂O₅+Na₂CO₃＝2NaVO₃+CO₂；

SO₂+Na₂CO₃＝Na₂SO₃+CO₂；

WS₂+3.5O₂＝WO₃+2SO₂；

WO₃+Na₂CO₃＝Na₂WO₄+CO₂；

SiO₂+Na₂CO₃＝Na₂SiO₃+CO₂；

s3, performing primary leaching on the clinker obtained in the step S2 to obtain a leaching solution, filtering the leaching solution, and separating the solution and tailings; the solution is a mixed solution of sodium vanadate and sodium molybdate, or a mixed solution of sodium tungstate and sodium molybdate. Specifically, the measured clinker is added into a primary leaching tank 4, the temperature is raised through steam indirect heating, a mixed solution of sodium vanadate and sodium molybdate is fully dissolved and then filtered, and the solution and tailings are separated; or fully dissolving the mixed solution of sodium tungstate and sodium molybdate, and filtering to separate the solution and the tailings. The solution will be processed in the next recovery process. The tailings enter a secondary roasting rotary kiln 14 for further recovery of metals such as cobalt and aluminum.

And S4, removing impurities from the mixed solution obtained in the step S3, and filtering and separating. The solution enters an impurity removal stirring tank 5, substances such as ammonium sulfate, magnesium sulfate and the like are added into the solution in the impurity removal stirring tank 5, a small amount of impurities such as aluminum, phosphorus and the like contained in the solution are removed, then the solution is filtered in a first filtering device 6, and filter mud obtained at a solid-phase sediment outlet after the solution is filtered by the first filtering device 6 is sent to a secondary treatment system; and the purified liquid obtained at the liquid-phase filtrate outlet after the filtration of the first filtering device 6 flows into a vanadium or tungsten precipitation stirring tank 7.

If the leaching solution in the step S3 is a mixed solution of sodium vanadate and sodium molybdate, which contains a small amount of impurities such as aluminum and phosphorus, and needs to be removed, ammonium sulfate and magnesium sulfate are added to remove the impurities, and the main reaction equation is as follows:

(NH₄)₂SO₄+2MgSO₄+2Na₃PO₄+6H₂O＝2MgNH₄PO₄·6H₂O↓+3Na₂SO₄；

the filtered phosphorus mud is sent to a secondary roasting system,

if the leaching solution in the step S3 is a mixed solution of sodium tungstate and sodium molybdate, adding magnesium chloride into the mixed solution to remove impurities, wherein the main reaction equation is as follows:

2Na2HPO₄+MgCl₂+＝MgHPO₄↓+2NaCl；

Na₂SiO₃+MgCl₂＝MgSiO₃+2NaCl；

the filtered silicon-phosphorus waste residue is sent to a secondary roasting system,

and S5, carrying out vanadium precipitation or tungsten precipitation treatment on the solution obtained in the step S4, and filtering. Specifically, the method comprises the following steps:

if the solution containing sodium vanadate and sodium molybdate is obtained in the primary leaching tank 4 in the step S3, adding ammonium sulfate into the vanadium or tungsten precipitation stirring tank 7, adjusting the pH value to 7.589.0 to separate out ammonium metavanadate, and performing a reaction equation:

2NaVO₃+(NH₄)2SO₄＝2NH₄VO₃↓+Na₂SO₄；

then the filtrate flows into a second filtering device 8 from a discharge hole of a vanadium or tungsten precipitation stirring tank 7, and is filtered to obtain a product ammonium metavanadate,

if the solution containing sodium tungstate and sodium molybdate is obtained in the primary leaching tank 4 in the step S3, adding calcium hydroxide into the vanadium or tungsten precipitation stirring tank 7, adjusting the pH value to 7.589.0 to separate out calcium tungstate, and performing the reaction equation:

Na₂WO₄+Ca(OH)₂＝CaWO₄↓+2NaOH；

then the filtrate flows into a second filtering device 8 from a discharge hole of a vanadium or tungsten precipitation stirring tank 7, and is filtered to obtain a product calcium tungstate,

the filtrate filtered by the second filtering device 8 flows into a molybdenum precipitation stirring tank 9.

And S6, carrying out molybdenum precipitation treatment on the solution obtained in the step S5, and filtering.

Adding a proper amount of sulfuric acid into the filtrate in a molybdenum precipitation stirring tank 9, adjusting the pH to 2, and reacting sodium molybdate and the sulfuric acid to generate molybdic acid precipitate, wherein the reaction equation is as follows:

Na₂MoO₄+H₂SO₄＝H₂MoO₄↓+Na₂SO₄；

and filtering in a third filtering device 10 to obtain molybdic acid product;

the third filtering device 10 flows into a dilute molybdic acid adsorption tank 11 as a recovery solution after filtering;

s7, recovering molybdate radicals remained in the solution obtained in the step S6; the solution after recovering the molybdate radical is adjusted to alkaline pH value. The filtrate filtered by the third filtering device 10 is put in a dilute molybdic acid adsorption tank 11, the residual molybdic acid radicals are adsorbed by resin, sodium hydroxide solution is added for soaking after the adsorption of the resin is saturated, and the soaked eluent containing the molybdic acid radicals returns to the molybdenum precipitation process of the step S6; after the solution after resin adsorption is added with sodium hydroxide to adjust the pH to be alkaline, the alkaline solution flows into a deamination tower 12.

S8, adding sulfuric acid into the deamination tower 12, and allowing the alkaline solution to pass through the deamination tower 12 to form a solution containing ammonium sulfate; the solution containing sodium sulfate in deamination tower 12 enters first evaporative crystallization device 13.

Further, if the leaching solution obtained in step S3 is a mixed solution of sodium vanadate and sodium molybdate, the ammonium sulfate solution obtained in step S8 is used for the vanadium precipitation treatment in step S5.

S9, carrying out an evaporation crystallization step on the solution obtained in the step S8. Recovering a byproduct sodium sulfate solid in the first evaporative crystallization device 103; the condensed water is recycled and flows into the primary leaching tank 4 to be utilized by the leaching production process.

Further, for the secondary treatment system, the method may further include a secondary treatment step, where the secondary treatment step specifically includes:

and S10, mixing the tailings obtained in the step S3 and/or the impurity-removed slag obtained in the step S4 with alkali, and then carrying out secondary roasting. Mixing alkali with tailings obtained after the solid-phase sediment outlet of the first leaching tank 4 and impurity-removed slag obtained after impurity removal at the solid-phase sediment outlet of the first filtering device 6, then roasting in a secondary roasting rotary kiln 14, oxidizing and roasting for more than 2 hours at 8008950 ℃, so that aluminum oxide in the tailings reacts with recovered alkali (mainly sodium carbonate as a component of the recovered alkali) in a high-temperature roasting activation process to generate soluble sodium aluminate, wherein the reaction equation is as follows:

Na₂CO₃+Al₂O₃＝2NaAlO₂+CO₂；

and is sent into a secondary leaching tank 15 from a discharge port of a secondary roasting rotary kiln 14.

S11, secondary leaching the clinker obtained in the step S10.

In a secondary leaching tank 15, the sodium aluminate enters the roasted clinker, water-insoluble cobalt and aluminum are leached out by water, soluble sodium aluminate, sodium vanadate and sodium molybdate are dissolved in water, crude cobalt is obtained by filtering, and the filtrate is pumped to a feeding port of an aluminum precipitation tank 16;

and S12, carrying out aluminum precipitation treatment on the solution obtained in the step S11, and filtering. Step S12 is specifically a carbon dioxide aluminum precipitation process, in which carbon dioxide is introduced into the aluminum precipitation tank 16, and in the solution containing sodium aluminate, carbon dioxide and sodium aluminate generate an aluminum hydroxide precipitate, and the reaction equation is:

2NaAlO₂+CO₂+3H₂O＝2Al(OH)₃↓+Na₂CO₃；

then filtering in a fourth filtering device 17 to obtain an aluminum hydroxide product;

s13, carrying out an evaporation crystallization step on the solution obtained in the step S12, and using the obtained alkali for the primary roasting in the step S2 and/or the secondary roasting in the step S10.

And (3) evaporating and crystallizing residual liquid discharged from a liquid phase outlet of the fourth filtering device 17 in the second evaporation and crystallization device 18 to recover alkali, wherein the residual liquid filtered by the fourth filtering device 17 contains a large amount of sodium carbonate and a certain amount of sodium vanadate and sodium molybdate, the recovered alkali containing the sodium vanadate and the sodium molybdate is completely recovered through the second evaporation and crystallization device 18, and the obtained recovered alkali is used for the primary roasting of the step S2 and/or the secondary roasting of the step S10. The condensed water discharged from the secondary evaporative crystallization device 18 is returned to the secondary leaching tank 15 for the secondary leaching production process of step S11.

The utility model discloses the thermal desorption feed system, blendor, rotary kiln, leaching groove, agitator tank, filtration equipment, adsorption tank, deamination tower, evaporation crystallization device, heavy devices such as aluminium jar and equipment itself that involve in are the common device and equipment in the field, the utility model discloses do not make the change to the structure and the function of itself of these devices and equipment, in the above, have simply narrated structure and the principle of these prior art, can directly build or directly purchase according to the corresponding equipment among the prior art and use the product sold in the market and can build the spent catalyst recovery unit of hydrogenation disclosed.

The above description is for the purpose of explanation and not limitation of the invention, which is defined in the claims, and any modifications may be made without departing from the basic structure of the invention.

Claims

1. The recycling device for the hydrogenation waste catalyst is characterized in that: a discharge port of the thermal desorption feeding system (1) is communicated with a feed port of the cylindrical mixer (2); the discharge hole of the cylindrical mixer (2) is communicated with the feeding hole of the cylinder of the primary roasting rotary kiln (3); the discharge hole of the cylinder of the primary roasting rotary kiln (3) is communicated with the feed hole of the primary leaching tank (4); the liquid phase outlet of the primary leaching tank (4) is communicated with the feed inlet of the impurity removal stirring tank (5); a discharge hole of the impurity removal stirring tank (5) is communicated with a feed hole of the first filtering equipment (6); a liquid-phase filtrate outlet of the first filtering device (6) is communicated with a feed inlet of the vanadium or tungsten precipitation stirring tank (7); a discharge hole of the vanadium or tungsten precipitation stirring tank (7) is communicated with a feed hole of the second filtering equipment (8); a liquid-phase filtrate outlet of the second filtering device (8) is communicated with a feed inlet of the molybdenum precipitation stirring tank (9); a discharge port of the molybdenum precipitation stirring tank (9) is communicated with a feed port of the third filtering equipment (10); a liquid-phase filtrate outlet of the third filtering device (10) is communicated with a feeding port of the dilute molybdic acid adsorption tank (11); a discharge hole of the dilute molybdic acid adsorption tank (11) is communicated with a feed inlet of the deamination tower (12); the discharge hole of the deamination tower (12) is communicated with the feed inlet of the first evaporative crystallization device (13).

2. The spent hydrogenation catalyst recovery apparatus according to claim 1, wherein: the thermal desorption feeding system (1) comprises a conveying and extracting pipe (101), a heat conducting oil furnace (102) and a condensing tank (103); the conveying and extracting pipe (101) is a spiral material conveying mechanism with a steel interlayer on the outer wall; a heat conduction oil outlet of the heat conduction oil furnace (102) is communicated with an interlayer inlet of the steel interlayer, and an interlayer outlet of the steel interlayer is communicated with an oil return port of the heat conduction oil furnace (102); and a gas output port of the conveying and extracting pipe (101) is communicated with a condensation inlet of a condensation tank (103).

3. The spent hydrogenation catalyst recovery apparatus according to claim 1, wherein: the device also comprises a secondary treatment system; the secondary treatment system comprises a secondary roasting rotary kiln (14), a secondary leaching tank (15), an aluminum precipitation tank (16), a fourth filtering device (17) and a second evaporative crystallization device (18); a solid-phase sediment outlet of the first leaching tank (4) and/or a solid-phase sediment outlet of the first filtering device (6) is communicated with a feeding port of the secondary roasting rotary kiln (14); the discharge hole of the secondary roasting rotary kiln (14) is communicated with the feed inlet of the secondary leaching tank (15); the liquid phase outlet of the secondary leaching tank (15) is communicated with the feeding port of the aluminum precipitation tank (16); a discharge hole of the aluminum precipitation tank (16) is communicated with a feed hole of the fourth filtering equipment (17); a liquid-phase filtrate outlet of the fourth filtering device (17) is communicated with a feeding port of the second evaporative crystallization device (18); a discharge hole of the second evaporative crystallization device (18) is communicated with a recycled alkali feeding hole of the cylindrical mixer (2) and/or is communicated with a feeding hole of the secondary roasting rotary kiln (14); the condensed water outlet of the second evaporative crystallization device (18) is communicated with the water replenishing port of the second leaching tank (15).

4. The spent hydrogenation catalyst recovery apparatus according to claim 1, wherein: the condensed water outlet of the first evaporative crystallization device (13) is communicated with the water replenishing port of the first leaching tank (4).