A device for extracting molybdenum from molybdenum-containing waste catalyst

Abstract

The invention discloses a device for extracting molybdenum from molybdenum-containing waste catalyst, the device comprising a plurality of vertically arranged sublimation furnaces (4), external heaters (6), feeders, slag dischargers (11), or a plurality of horizontally arranged sublimation tubes (20), material pushers (21), external heaters (6), hoppers (17); and a matching blast device, condensation recovery device and control system; during operation, the molybdenum-containing waste catalyst moves from top to bottom, and the oxidation wind passes through the molybdenum-containing waste catalyst from bottom to top; or the molybdenum-containing waste catalyst moves from one end to the other end, and the oxidation wind passes through the molybdenum-containing waste catalyst in the opposite direction; the external heater (6) heats the molybdenum-containing waste catalyst to 800-1200 degrees Celsius, and the molybdenum is oxidized and sublimated under the action of the oxidation wind and recovered in the condensation recovery device, and the oxidation wind can be an oxygen-rich gas. Compared with the prior art, the structure of the invention is more scientific and reasonable, simple, and can be continuously operated in industrialization.

Description

Technical Field

[0001] The present invention relates to the field of solid waste treatment, and in particular to a device for extracting molybdenum from molybdenum-containing waste catalysts. Background Art

[0002] Molybdenum-containing catalysts are used in petroleum refining and coal-to-oil processes. Their service life is about three years, so a large number of molybdenum-containing catalysts are scrapped every year. At present, wet methods are used to recover molybdenum from waste catalysts. The basic principle is to first add alkali to the waste catalyst for roasting, so that the molybdenum in the form of sulfide (MoS2) in the waste catalyst is converted into molybdenum oxide (Mo2O3) and further (Na2CO3), etc., to generate soluble compounds (Na2MoO4), and then use water as a leaching agent to allow molybdenum to enter the solution. Finally, molybdenum is separated from other metals by acid adjustment, precipitation, extraction and other methods. The metals recovered by wet methods have high purity and recovery rate, but their disadvantages are long process flow, high water consumption, high acid and alkali consumption, and high environmental pressure.

[0003] CN110129573 A proposes a device for recovering molybdenum from waste catalysts by pyrometallurgical method, which cannot realize industrial continuous production and has high energy consumption. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies in the prior art and to provide a pyrometallurgical device which can significantly improve efficiency, has a short process flow, low costs, low environmental pressure and can achieve industrial continuous production.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A device for extracting molybdenum from molybdenum-containing waste catalyst, the device adopts one of the following two structures:

[0007] Type A, the device of the type A structure comprises at least one set of vertically arranged sublimation furnace, external heater, feeder with hopper, slag discharger, and blasting device, condensation recovery device, and control system; the sublimation furnace is a closed cylindrical structure mainly surrounded by furnace walls, the upper part of which is provided with a feed inlet and a high-temperature molybdenum-containing gas outlet, the outer periphery of the middle part is provided with an external heater, the external heater heats the molybdenum-containing waste catalyst in the sublimation furnace through the furnace wall in the middle part to oxidize the molybdenum to generate molybdenum oxide and sublime, the lower part is provided with an oxidation air inlet, and the slag discharger is provided at the bottom; the outlet of the feeder is connected with the feed inlet of the sublimation furnace, the high-temperature molybdenum-containing gas outlet is connected with the high-temperature molybdenum-containing gas inlet of the condensation recovery device through a pipeline, and the oxidation air inlet is connected with the blasting device; the external heater, feeder, slag discharger and blasting device are all electrically connected with the control system;

[0008] Type B, the device of the Type B structure comprises at least one group of horizontally arranged sublimation tubes, material pushers, external heaters, hoppers, and air blowers, condensation recovery devices, and control systems; a material pusher is arranged in the sublimation tube, and the material pusher moves the molybdenum-containing waste catalyst in the sublimation tube from one end to the other end; a feed port is arranged at one end of the sublimation tube, and a slag outlet is arranged at the other end; an external heater is arranged on the outer periphery of the middle part thereof, and the external heater heats the molybdenum-containing waste catalyst in the middle part thereof through the tube wall in the middle part thereof to oxidize the molybdenum to generate molybdenum oxide and sublime; a high-temperature molybdenum-containing gas outlet is arranged on the tube wall between the external heater and the feed port, and an oxidation air inlet is arranged on the tube wall between the external heater and the slag outlet; the outlet of the hopper is connected with the feed port of the sublimation tube, the high-temperature molybdenum-containing gas outlet is connected with the high-temperature molybdenum-containing gas inlet of the condensation recovery device through a pipeline, and the oxidation air inlet is connected with the air blower; the material pusher, the external heater, and the air blower are all electrically connected with the control system.

[0009] The horizontal cross section of the middle part of the sublimation furnace of the A-type structure device is circular or rectangular, the height from the feed port to the slag outlet is H, that is, the working height is H, the diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross section of the middle part of the sublimation furnace of the A-type structure device is D, H / D is greater than 3; or D < 1.5m at the same time;

[0010] The vertical cross-section of the middle part of the sublimation tube of the device of the B-type structure is circular or rectangular, and the length from the feed port to the slag outlet is L, that is, the working length is L. The diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross-section of the middle part of the sublimation tube of the device of the B-type structure is D, and L / D is greater than 3; or D<1.5m at the same time.

[0011] The device of the A-type structure also includes a material level meter; the material level meter is arranged on the top or the side of the upper part of the sublimation furnace and is electrically connected to the control system to measure the height of the molybdenum-containing waste catalyst in the sublimation furnace;

[0012] The feeder of the A-type structure device includes a hopper, a feed pipe and a screw propeller; the feed pipe is arranged horizontally, can be tilted downward along the feeding direction, and a screw propeller is arranged inside the feed pipe, one end of the feed pipe is connected to the outlet of the hopper, and the other end is connected to the feed port on the sublimation furnace; the feed pipe can be extended into the sublimation furnace to make the material distribution uniform;

[0013] At least one thermocouple is arranged in the sublimation furnace or on the furnace wall, or at least one thermocouple is arranged in the sublimation tube or on the tube wall, and the thermocouple is electrically connected to the control system.

[0014] The material level meter includes a high temperature resistant probe rod and a probe rod up and down reciprocating device; the probe rod up and down reciprocating device drives the high temperature resistant probe rod to move up and down at a frequency of once per second to once per hour, and when the high temperature resistant probe rod moves downward and touches the molybdenum-containing waste catalyst, it returns upward and transmits the material level signal to the control system;

[0015] The top of the sublimation furnace can be provided with a blind plate structure cover fastened by bolts, which is convenient for disassembly;

[0016] A sleeve is arranged outside the material transfer pipe to form a jacket structure, and the sleeve passes through the furnace wall to be connected with the inner cavity of the sublimation furnace, and at the same time, its outer surface is tightly connected with the furnace wall; the outlet of the material transfer pipe is the feed port of the sublimation furnace, and the annular opening between the outlet of the material transfer pipe and the end of the sleeve is the outlet of the high-temperature molybdenum-containing gas; when working, the high-temperature molybdenum-containing gas enters the condensation recovery device through the annular pipeline between the material transfer pipe and the sleeve, and at the same time, the molybdenum-containing waste catalyst in the material transfer pipe is dried and preheated.

[0017] The external heater adopts one of the following two structures:

[0018] Electric heating type: The electric heating type external heater includes an electric heating element and a refractory material, and the electric heating element and the refractory material constitute at least one level of independently controlled heating unit; the heating unit heats the furnace wall of the sublimation furnace or the tube wall of the sublimation tube at a temperature of 800 to 1200 degrees Celsius;

[0019] Open flame type: The open flame type external heater includes a burner, an annular heating chamber that surrounds the furnace wall at least one level or an annular heating chamber that surrounds the tube wall of the sublimation tube at least one level, the annular heating chamber is a closed annular cavity structure mainly surrounded by refractory materials and the outer surface of the furnace wall or the outer surface of the sublimation tube, and a fire inlet and a hot air outlet are arranged on it; the heating temperature of the furnace wall or the tube wall of the sublimation tube by the annular heating chamber is 800 degrees Celsius to 1200 degrees Celsius; the flame nozzle of the burner is connected to the fire inlet, and the electrical control part of the burner is electrically connected to the control system;

[0020] The device of type A structure or the device of type B structure also includes a raw material drying device and a condensed exhaust gas environmental protection treatment device; the discharge port of the raw material drying device is arranged above the feed port of the hopper; the hot air outlet can be connected to the raw material drying device to provide it with a drying heat source.

[0021] The electric heating type external heater includes a primary heating unit and a secondary heating unit; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation furnace, they are distributed up and down, and can heat the furnace wall of the sublimation furnace in sections independently, and the heating temperature of the furnace wall by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the furnace wall by the secondary heating unit is 300 degrees to 1050 degrees Celsius; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation tube, they are distributed left and right, and can heat the tube wall of the sublimation tube in sections independently, the heating unit close to the high-temperature molybdenum-containing gas outlet is the primary heating unit, the heating temperature of the tube wall of the sublimation tube by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the tube wall of the sublimation tube by the secondary heating unit is 300 degrees to 1050 degrees Celsius;

[0022] The open flame type external heater includes a primary annular heating chamber and a secondary annular heating chamber; the primary annular heating chamber and the secondary annular heating chamber surrounding the furnace wall are distributed up and down, and can heat the furnace wall of the sublimation furnace in sections independently, the heating temperature of the primary annular heating chamber to the furnace wall is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber to the furnace wall is 300 degrees to 1050 degrees Celsius; or the primary annular heating chamber and the secondary annular heating chamber surrounding the tube wall of the sublimation tube are distributed left and right, and can heat the tube wall of the sublimation tube in sections independently, the annular heating chamber near the high-temperature molybdenum-containing gas outlet is the primary annular heating chamber, the heating temperature of the primary annular heating chamber to the tube wall of the sublimation tube is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber to the tube wall of the sublimation tube is 300 degrees to 1050 degrees Celsius;

[0023] The primary annular heating chamber and the secondary annular heating chamber can also be connected in series, that is, the hot air outlet of the primary annular heating chamber is connected to the fire inlet of the secondary annular heating chamber;

[0024] The top surface of the molybdenum-containing waste catalyst accumulated in the sublimation furnace is the material top surface, and the height difference between the lowest point of the material top surface and the highest point of the heating part of the heating unit outside the furnace wall / the highest point of the inner cavity of the annular heating chamber is less than 1.5m.

[0025] The condensation recovery device includes at least one condensation unit, and a single condensation unit includes two condensation tubes, a small storage bin and a bin bottom discharger. The two condensation tubes are vertically arranged and the lower ends thereof are both connected to the small storage bin. The small storage bin is a closed chamber structure, and the outlet at the bottom thereof is provided with a bin bottom discharger. The upper end of one condensation tube is provided with a high-temperature molybdenum-containing gas inlet, and the upper end of the other condensation tube is provided with an exhaust gas outlet;

[0026] The device of the A-type structure or the device of the B-type structure also includes a raw material drying device and a condensed tail gas environmental protection treatment device; the discharge port of the raw material drying device is arranged above the feed port of the hopper.

[0027] The condenser is also equipped with a scraper; the scraper includes a connecting rod, a scraper and a scraper driver, the scraper is arranged in the condenser and connected to the connecting rod, and the connecting rod is connected to the scraper driver; under the action of the scraper driver, the scraper moves up and down in the condenser to scrape off the molybdenum-containing material adhering to the inner wall of the condenser;

[0028] The top of the condenser tube can also be provided with a condenser tube top cover of a blind plate structure fastened by bolts, so as to facilitate disassembly;

[0029] The condensation recovery device is composed of no less than 2 condensation units connected in series, or no less than 2 condensation units connected in parallel;

[0030] A jacket water cooling device or a jacket air cooling device can be provided on the periphery of the condenser tube; the hot air outlet of the jacket air cooling device can be connected to the raw material drying device to provide a drying heat source therefor.

[0031] A blast beam with air outlet holes and / or a central air hood with air outlet holes are arranged at the lower part of the sublimation furnace; the blast beam and / or the central air hood are connected with the blast device through a pipeline, and the pipeline passes through the oxidation air inlet.

[0032] The device of type A structure includes three or more vertical sublimation furnaces, external heaters, feeders and slag dischargers; or the device of type B structure includes three or more horizontal sublimation tubes, material pushers, external heaters and hoppers;

[0033] The cavity wind speed of the oxidation wind entering the sublimation furnace / sublimation tube through the oxidation wind inlet is less than 1 m / s; the oxidation wind is an oxygen-rich gas with an oxygen content greater than that of air.

[0034] Compared with the prior art, the structure of the invention is more scientific and reasonable, simple and feasible, has high recovery efficiency, and can realize industrial continuous operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic structural diagram of an A-type structure device embodiment of the present invention.

[0036] Figure 2 It is a schematic structural diagram of a device embodiment of a B-type structure of the present invention.

[0037] Figure 3 It is a schematic structural diagram of a condensation recovery device embodiment of the present invention.

[0038] In the figure: 1-level meter, 2-top cover, 3-high temperature resistant probe rod, 4-sublimation furnace, 5-furnace wall, 6-external heater, 7-primary annular heating chamber, 8-secondary annular heating chamber, 9-oxidation air inlet, 10-slag outlet, 11-slag discharger, 12-hot air outlet, 13-burner, 14-screw propeller, 15-sleeve, 16-material transfer pipe, 17-hopper, 18-high temperature molybdenum-containing gas outlet, 19-raw material drying device, 20-sublimation tube, 21-material propeller, 22-connecting rod, 23-condenser top cover, 24-scraper, 25-high temperature molybdenum-containing gas inlet, 26-condenser, 27-material storage bin, 28-bin bottom discharger, 29-blast beam, 30-air outlet, 31-material top surface. DETAILED DESCRIPTION

[0039] The present invention will be further described below in conjunction with embodiments:

[0040] Reference Figure 1-3 : A device for extracting molybdenum from molybdenum-containing waste catalyst, the device adopts one of the following two structures:

[0041] A type, the device of the A type structure comprises at least one set of vertically arranged sublimation furnace 4, external heater 6, feeder with hopper 17, slag discharger 11, and blasting device, condensation recovery device, and control system; the sublimation furnace 4 is a closed cylindrical structure mainly surrounded by furnace wall 5, and a feed port and a high-temperature molybdenum-containing gas outlet 18 are arranged on the upper part thereof, and an external heater 6 is arranged on the outer periphery of the middle part thereof, and the external heater 6 heats the molybdenum-containing waste catalyst in the sublimation furnace 4 through the furnace wall 5 in the middle part to oxidize the molybdenum to generate molybdenum oxide and sublime, and an oxidation air inlet 9 is arranged on the lower part thereof, and a slag discharger 11 is arranged at the slag outlet 10 at the bottom thereof; the outlet of the feeder is connected with the feed port of the sublimation furnace 4, the high-temperature molybdenum-containing gas outlet 18 is connected with the high-temperature molybdenum-containing gas inlet 25 of the condensation recovery device through a pipeline, and the oxidation air inlet 9 is connected with the blasting device; the external heater 6, feeder, slag discharger 11 and blasting device are all electrically connected with the control system;

[0042] Type B, the device of the type B structure comprises at least one group of horizontally arranged sublimation tubes 20, material pushers 21, external heaters 6, hoppers 17, and blasting devices, condensation recovery devices, and control systems; the sublimation tube 20 is provided with a material pusher 21, and the material pusher 21 moves the molybdenum-containing waste catalyst in the sublimation tube 20 from one end to the other end, the sublimation tube 20 is provided with a feed port at one end and a slag outlet 10 at the other end, the outer periphery of the middle part thereof is provided with an external heater 6, and the external heater 6 heats the molybdenum-containing waste catalyst in the middle part thereof through the tube wall in the middle part thereof to oxidize the molybdenum to generate molybdenum oxide and sublime, a high-temperature molybdenum-containing gas outlet 18 is provided on the tube wall between the external heater 6 and the feed port, and an oxidation air inlet 9 is provided on the tube wall between the external heater 6 and the slag outlet 10; the outlet of the hopper 17 is connected to the feed port of the sublimation tube 20, and the high-temperature molybdenum-containing gas outlet 18 is connected to the high-temperature molybdenum-containing gas inlet 25 of the condensation recovery device through a pipeline. The oxidation air inlet 9 is connected to the blowing device; the material pusher 21, the external heater 6, and the blowing device are all electrically connected to the control system.

[0043] Reference Figure 1-2 : The horizontal cross section of the middle part of the sublimation furnace 4 of the A-type structure device is circular or rectangular, the height from the feed port to the slag outlet 10 is H, that is, the working height is H, the diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross section of the middle part of the sublimation furnace 4 of the A-type structure device is D, H / D is greater than 3; or D <1.5m at the same time;

[0044] The vertical cross-section of the middle part of the sublimation tube 20 of the B-type structure device is circular or rectangular, and the length from the feed port to the slag outlet 10 is L, that is, the working length is L. The diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross-section of the middle part of the sublimation tube 20 of the B-type structure device is D, and L / D is greater than 3; or D<1.5m at the same time.

[0045] Reference Figure 1 : The device of the A-type structure also includes a material level meter 1; the material level meter 1 is arranged on the top or upper side of the sublimation furnace 4 and is electrically connected to the control system to measure the height of the molybdenum waste catalyst in the sublimation furnace 4;

[0046] The feeder of the A-type structure device includes a hopper 17, a feed pipe 16 and a screw propeller 14; the feed pipe 16 is arranged horizontally and can be tilted downward along the feeding direction, and the screw propeller 14 is arranged inside the feed pipe 16, one end of the feed pipe 16 is connected to the outlet of the hopper 17, and the other end is connected to the feed port on the sublimation furnace 4; the feed pipe 16 can extend into the sublimation furnace 4 to make the material distribution uniform;

[0047] At least one thermocouple is arranged in the sublimation furnace 4 or on the furnace wall 5, or at least one thermocouple is arranged in the sublimation tube 20 or on the tube wall, and the thermocouple is electrically connected to the control system.

[0048] Reference Figure 1 : The material level meter 1 includes a high temperature resistant probe rod 3 and a probe rod up and down shuttle; the probe rod up and down shuttle drives the high temperature resistant probe rod 3 to move up and down at a frequency of once per second to once per hour, and when the high temperature resistant probe rod 3 moves downward and touches the molybdenum-containing waste catalyst, it returns upward and transmits the material level signal to the control system;

[0049] The top of the sublimation furnace 4 can be provided with a top cover 2 of a blind plate structure fastened by bolts, which is convenient for disassembly;

[0050] A sleeve 15 is arranged outside the feed pipe 16 to form a jacket structure, and the sleeve 15 passes through the furnace wall 5 and is connected to the inner cavity of the sublimation furnace 4, while its outer surface is tightly connected to the furnace wall 5; the outlet of the feed pipe 16 is the feed inlet of the sublimation furnace 4, and the annular opening between the outlet of the feed pipe 16 and the end of the sleeve 15 is the high-temperature molybdenum-containing gas outlet 18; when working, the high-temperature molybdenum-containing gas enters the condensation recovery device through the annular pipeline between the feed pipe 16 and the sleeve 15, and the molybdenum-containing waste catalyst in the feed pipe 16 is dried and preheated.

[0051] Reference Figure 1-2 The external heater 6 adopts one of the following two structures:

[0052] Electric heating type: The electric heating type external heater 6 includes an electric heating element and a refractory material, and the electric heating element and the refractory material constitute at least one level of independently controlled heating unit; the heating unit heats the furnace wall 5 of the sublimation furnace 4 or the tube wall of the sublimation tube 20 to a temperature of 800 to 1200 degrees Celsius;

[0053] Open flame type: The open flame type external heater 6 includes a burner 13, an annular heating chamber that surrounds the furnace wall 5 at least one level or an annular heating chamber that surrounds the tube wall of the sublimation tube 20 at least one level, the annular heating chamber is a closed annular cavity structure mainly surrounded by refractory materials and the outer surface of the furnace wall 5 or the outer surface of the sublimation tube 20, and a fire inlet and a hot air outlet 12 are arranged on it; the heating temperature of the furnace wall 5 or the tube wall of the sublimation tube 20 by the annular heating chamber is 800 degrees Celsius to 1200 degrees Celsius; the flame nozzle of the burner 13 is connected to the fire inlet, and the electric control part of the burner 13 is electrically connected to the control system;

[0054] The device of type A structure or the device of type B structure also includes a raw material drying device 19 and a condensed exhaust gas environmental protection treatment device; the discharge port of the raw material drying device 19 is arranged above the feed port of the hopper 17; the hot air outlet 12 can be connected to the raw material drying device 19 to provide it with a drying heat source.

[0055] Reference Figure 1-2 : The electric heating type external heater 6 includes a primary heating unit and a secondary heating unit; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation furnace 4, they are distributed up and down, and can heat the furnace wall 5 of the sublimation furnace 4 in sections independently, and the heating temperature of the furnace wall 5 by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the furnace wall 5 by the secondary heating unit is 300 degrees to 1050 degrees Celsius; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation tube 20, they are distributed left and right, and can heat the tube wall of the sublimation tube 20 in sections independently, the heating unit close to the high-temperature molybdenum-containing gas outlet 18 is the primary heating unit, the heating temperature of the tube wall of the sublimation tube 20 by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the tube wall of the sublimation tube 20 by the secondary heating unit is 300 degrees to 1050 degrees Celsius;

[0056] The open flame type external heater 6 includes a primary annular heating chamber 7 and a secondary annular heating chamber 8; the primary annular heating chamber 7 and the secondary annular heating chamber 8 surrounding the furnace wall 5 are distributed up and down, and can heat the furnace wall 5 of the sublimation furnace 4 in sections independently, and the heating temperature of the primary annular heating chamber 7 to the furnace wall 5 is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber 8 to the furnace wall 5 is 300 degrees to 1050 degrees Celsius; or the primary annular heating chamber 7 and the secondary annular heating chamber 8 surrounding the tube wall of the sublimation tube 20 are distributed left and right, and can heat the tube wall of the sublimation tube 20 in sections independently, the annular heating chamber near the high-temperature molybdenum-containing gas outlet 18 is the primary annular heating chamber 7, the heating temperature of the primary annular heating chamber 7 to the tube wall of the sublimation tube 20 is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber 8 to the tube wall of the sublimation tube 20 is 300 degrees to 1050 degrees Celsius;

[0057] The primary annular heating chamber 7 and the secondary annular heating chamber 8 can also be connected in series, that is, the hot air outlet 12 of the primary annular heating chamber 7 is connected to the fire inlet of the secondary annular heating chamber 8;

[0058] The top surface of the molybdenum-containing waste catalyst accumulated in the sublimation furnace 4 is the material top surface 31, and the height difference between the lowest point of the material top surface 31 and the highest point of the heating part of the heating unit outside the furnace wall 5 / the highest point of the inner cavity of the annular heating chamber is less than 1.5m.

[0059] Reference Figure 3: The condensation recovery device includes at least one condensation unit, and a single condensation unit includes two condensation pipes 26, a small storage bin 27 and a bin bottom discharger 28. The two condensation pipes 26 are vertically arranged and their lower ends are connected to the small storage bin 27. The small storage bin 27 is a closed chamber structure, and the outlet at the bottom is provided with a bin bottom discharger 28. The upper end of one condensation pipe 26 is provided with a high-temperature molybdenum-containing gas inlet 25, and the upper end of the other condensation pipe 26 is provided with an exhaust gas outlet;

[0060] The device of the A-type structure or the device of the B-type structure further includes a raw material drying device 19 and a condensed tail gas environmental protection treatment device; the discharge port of the raw material drying device 19 is arranged above the feed port of the hopper 17.

[0061] Reference Figure 3 : The condenser 26 is also equipped with a scraper; the scraper includes a connecting rod 22, a scraper 24 and a scraper driver, the scraper 24 is arranged in the condenser 26 and connected to the connecting rod 22, and the connecting rod 22 is connected to the scraper driver; under the action of the scraper driver, the scraper 24 moves up and down in the condenser 26 to scrape off the molybdenum-containing material adhering to the inner wall of the condenser 26;

[0062] The top of the condenser tube 26 can also be provided with a condenser tube top cover 23 of a blind plate structure fastened by bolts, so as to facilitate disassembly;

[0063] The condensation recovery device is composed of no less than 2 condensation units connected in series, or no less than 2 condensation units connected in parallel;

[0064] A jacket water cooling device or a jacket air cooling device can be provided on the periphery of the condenser tube 26; the hot air outlet of the jacket air cooling device can be connected to the raw material drying device 19 to provide a drying heat source therefor.

[0065] Reference Figure 1 : A blast beam 29 with air outlet holes 30 and / or a central wind hood with air outlet holes 30 are arranged at the lower part of the sublimation furnace 4; the blast beam 29 and / or the central wind hood are connected to the blast device through a pipeline, and the pipeline passes through the oxidation air inlet 9.

[0066] Reference Figure 1-2 : The device of type A structure includes more than 3 groups of vertically arranged sublimation furnaces 4, external heaters 6, feeders and slag dischargers 11; or the device of type B structure includes more than 3 groups of horizontally arranged sublimation tubes 20, material pushers 21, external heaters 6 and hoppers 17;

[0067] The cavity wind speed of the oxidation wind entering the sublimation furnace 4 / sublimation tube 20 through the oxidation wind inlet 9 is less than 1 m / s; the oxidation wind is an oxygen-rich gas with an oxygen content greater than that of air.

[0068] Embodiment 1:

[0069] A device for extracting molybdenum from molybdenum-containing waste catalyst, the device adopts one of the following two structures:

[0070] A type, the device of the A type structure comprises at least one set of vertically arranged sublimation furnace 4, external heater 6, feeder with hopper 17, slag discharger 11, and blasting device, condensation recovery device, and control system; the sublimation furnace 4 is a closed cylindrical structure mainly surrounded by furnace wall 5, and a feed port and a high-temperature molybdenum-containing gas outlet 18 are arranged on the upper part thereof, and an external heater 6 is arranged on the outer periphery of the middle part thereof, and the external heater 6 heats the molybdenum-containing waste catalyst in the sublimation furnace 4 through the furnace wall 5 in the middle part to oxidize the molybdenum to generate molybdenum oxide and sublime, and an oxidation air inlet 9 is arranged on the lower part thereof, and a slag discharger 11 is arranged at the slag outlet 10 at the bottom thereof; the outlet of the feeder is connected with the feed port of the sublimation furnace 4, the high-temperature molybdenum-containing gas outlet 18 is connected with the high-temperature molybdenum-containing gas inlet 25 of the condensation recovery device through a pipeline, and the oxidation air inlet 9 is connected with the blasting device; the external heater 6, feeder, slag discharger 11 and blasting device are all electrically connected with the control system;

[0071] Type B, the device of the type B structure comprises at least one group of horizontally arranged sublimation tubes 20, material pushers 21, external heaters 6, hoppers 17, and blasting devices, condensation recovery devices, and control systems; the sublimation tube 20 is provided with a material pusher 21, and the material pusher 21 moves the molybdenum-containing waste catalyst in the sublimation tube 20 from one end to the other end; the sublimation tube 20 is provided with a feed port at one end and a slag outlet 10 at the other end; the outer periphery of the middle part is provided with an external heater 6, and the external heater 6 heats the molybdenum-containing waste catalyst in the middle part through the tube wall in the middle part to oxidize the molybdenum to generate molybdenum oxide and sublime; a high-temperature molybdenum-containing gas outlet 18 is provided on the tube wall between the external heater 6 and the feed port, and an oxidation air inlet 9 is provided on the tube wall between the external heater 6 and the slag outlet 10; the outlet of the hopper 17 is connected to the feed port of the sublimation tube 20, and the high-temperature molybdenum-containing gas outlet 18 is connected to the high-temperature molybdenum-containing gas inlet 25 of the condensation recovery device through a pipeline. The oxidation air inlet 9 is connected to the blowing device; the material pusher 21, the external heater 6, and the blowing device are all electrically connected to the control system.

[0072] Embodiment 2:

[0073] It is basically the same as Example 1, except that: the horizontal cross-section of the middle part of the sublimation furnace 4 of the A-type structure device is circular or rectangular, the height from the feed port to the slag outlet 10 is H, that is, the working height is H, the diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross-section of the middle part of the sublimation furnace 4 of the A-type structure device is D, H / D is greater than 3; or at the same time D<1.5m, preferably D<0.5m.

[0074] The vertical cross-section of the middle part of the sublimation tube 20 of the B-type structure device is circular or rectangular, and the length from the feed port to the slag outlet 10 is L, that is, the working length is L. The diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross-section of the middle part of the sublimation tube 20 of the B-type structure device is D, and L / D is greater than 3; or at the same time D<1.5m, preferably D<0.5m.

[0075] Embodiment 3:

[0076] The method is basically the same as Example 1, except that: the device of type A structure further comprises a material level meter 1; the material level meter 1 is arranged on the top or upper side of the sublimation furnace 4 and is electrically connected to the control system to measure the height of the molybdenum waste catalyst in the sublimation furnace 4;

[0077] The feeder of the A-type structure device includes a hopper 17, a feed pipe 16 and a screw propeller 14; the feed pipe 16 is arranged horizontally and can be tilted downward along the feeding direction, and the screw propeller 14 is arranged inside the feed pipe 16, one end of the feed pipe 16 is connected to the outlet of the hopper 17, and the other end is connected to the feed port on the sublimation furnace 4; the feed pipe 16 can extend into the sublimation furnace 4 to make the material distribution uniform;

[0078] At least one thermocouple is arranged in the sublimation furnace 4 or on the furnace wall 5, or at least one thermocouple is arranged in the sublimation tube 20 or on the tube wall, and the thermocouple is electrically connected to the control system.

[0079] Embodiment 4:

[0080] The embodiment 3 is basically the same, except that: the material level meter 1 includes a high temperature resistant probe rod 3 and a probe rod up and down reciprocating device; the probe rod up and down reciprocating device drives the high temperature resistant probe rod 3 to move up and down at a frequency of once per second to once per hour, and when the high temperature resistant probe rod 3 moves downward and touches the molybdenum-containing waste catalyst, it returns upward and transmits the material level signal to the control system;

[0081] The top of the sublimation furnace 4 can be provided with a top cover 2 of a blind plate structure fastened by bolts, which is convenient for disassembly;

[0082] A sleeve 15 is arranged outside the feed pipe 16 to form a jacket structure, and the sleeve 15 passes through the furnace wall 5 and is connected to the inner cavity of the sublimation furnace 4, while its outer surface is tightly connected to the furnace wall 5; the outlet of the feed pipe 16 is the feed inlet of the sublimation furnace 4, and the annular opening between the outlet of the feed pipe 16 and the end of the sleeve 15 is the high-temperature molybdenum-containing gas outlet 18; when working, the high-temperature molybdenum-containing gas enters the condensation recovery device through the annular pipeline between the feed pipe 16 and the sleeve 15, and the molybdenum-containing waste catalyst in the feed pipe 16 is dried and preheated.

[0083] Embodiment 5:

[0084] The embodiment is basically the same as the first embodiment, except that the external heater 6 adopts one of the following two structures:

[0085] Electric heating type: The electric heating type external heater 6 includes an electric heating element and a refractory material, and the electric heating element and the refractory material constitute at least one level of independently controlled heating unit; the heating unit heats the furnace wall 5 of the sublimation furnace 4 or the tube wall of the sublimation tube 20 to a temperature of 800 to 1200 degrees Celsius;

[0086] Open flame type: The open flame type external heater 6 includes a burner 13, an annular heating chamber that surrounds the furnace wall 5 at least one level or an annular heating chamber that surrounds the tube wall of the sublimation tube 20 at least one level, the annular heating chamber is a closed annular cavity structure mainly surrounded by refractory materials and the outer surface of the furnace wall 5 or the outer surface of the sublimation tube 20, and a fire inlet and a hot air outlet 12 are arranged on it; the heating temperature of the annular heating chamber to the furnace wall 5 or the tube wall of the sublimation tube 20 is 800 degrees Celsius to 1200 degrees Celsius; the flame nozzle of the burner 13 is connected to the fire inlet, and the electric control part of the burner 13 is electrically connected to the control system;

[0087] The device of type A structure or the device of type B structure also includes a raw material drying device 19 and a condensed exhaust gas environmental protection treatment device; the discharge port of the raw material drying device 19 is arranged above the feed port of the hopper 17; the hot air outlet 12 can be connected to the raw material drying device 19 to provide it with a drying heat source.

[0088] Embodiment 6:

[0089] It is basically the same as Example 5, except that: the electric heating type external heater 6 includes a primary heating unit and a secondary heating unit; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation furnace 4, they are distributed up and down, and can heat the furnace wall 5 of the sublimation furnace 4 in sections independently, and the heating temperature of the furnace wall 5 by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the furnace wall 5 by the secondary heating unit is 300 degrees to 1050 degrees Celsius; when the primary heating unit and the secondary heating unit are surrounded by the outer periphery of the middle part of the sublimation tube 20, they are distributed left and right, and can heat the tube wall of the sublimation tube 20 in sections independently, the heating unit close to the high-temperature molybdenum-containing gas outlet 18 is the primary heating unit, the heating temperature of the tube wall of the sublimation tube 20 by the primary heating unit is 800 degrees to 1200 degrees Celsius, and the heating temperature of the tube wall of the sublimation tube 20 by the secondary heating unit is 300 degrees to 1050 degrees Celsius;

[0090] The open flame type external heater 6 includes a primary annular heating chamber 7 and a secondary annular heating chamber 8; the primary annular heating chamber 7 and the secondary annular heating chamber 8 surrounding the furnace wall 5 are distributed up and down, and can heat the furnace wall 5 of the sublimation furnace 4 in sections independently, and the heating temperature of the primary annular heating chamber 7 to the furnace wall 5 is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber 8 to the furnace wall 5 is 300 degrees to 1050 degrees Celsius; or the primary annular heating chamber 7 and the secondary annular heating chamber 8 surrounding the tube wall of the sublimation tube 20 are distributed left and right, and can heat the tube wall of the sublimation tube 20 in sections independently, the annular heating chamber near the high-temperature molybdenum-containing gas outlet 18 is the primary annular heating chamber 7, the heating temperature of the primary annular heating chamber 7 to the tube wall of the sublimation tube 20 is 800 degrees to 1200 degrees Celsius, and the heating temperature of the secondary annular heating chamber 8 to the tube wall of the sublimation tube 20 is 300 degrees to 1050 degrees Celsius;

[0091] The primary annular heating chamber 7 and the secondary annular heating chamber 8 can also be connected in series, that is, the hot air outlet 12 of the primary annular heating chamber 7 is connected to the fire inlet of the secondary annular heating chamber 8;

[0092] The top surface of the molybdenum-containing waste catalyst accumulated in the sublimation furnace 4 is the material top surface 31. The height difference between the lowest point of the material top surface 31 and the highest point of the heating part of the heating unit outside the furnace wall 5 / the highest point of the inner cavity of the annular heating chamber is less than 1.5m, and the preferred height difference is plus or minus 0.5m.

[0093] Embodiment 7:

[0094] It is basically the same as Example 1, except that: the condensation recovery device includes at least one condensation unit, and a single condensation unit includes two condensation pipes 26, a material storage bin 27 and a bin bottom discharger 28. The two condensation pipes 26 are vertically arranged and their lower ends are connected to the material storage bin 27. The material storage bin 27 is a closed chamber structure, and the bottom outlet is configured with a bin bottom discharger 28. The upper end of one condensation pipe 26 is provided with a high-temperature molybdenum-containing gas inlet 25, and the upper end of the other condensation pipe 26 is provided with an exhaust gas outlet;

[0095] The device of the A-type structure or the device of the B-type structure further includes a raw material drying device 19 and a condensed tail gas environmental protection treatment device; the discharge port of the raw material drying device 19 is arranged above the feed port of the hopper 17.

[0096] Embodiment 8:

[0097] The embodiment is basically the same as the embodiment 7, except that: the condenser 26 is further provided with a scraper; the scraper comprises a connecting rod 22, a scraper 24 and a scraper driver, the scraper 24 is arranged in the condenser 26 and connected to the connecting rod 22, and the connecting rod 22 is connected to the scraper driver; under the action of the scraper driver, the scraper 24 moves up and down in the condenser 26 to scrape off the molybdenum-containing material adhering to the inner wall of the condenser 26;

[0098] The top of the condenser tube 26 can also be provided with a condenser tube top cover 23 of a blind plate structure fastened by bolts, so as to facilitate disassembly;

[0099] The condensation recovery device is composed of no less than 2 condensation units connected in series, or no less than 2 condensation units connected in parallel;

[0100] A jacket water cooling device or a jacket air cooling device can be provided on the periphery of the condenser tube 26; the hot air outlet of the jacket air cooling device can be connected to the raw material drying device 19 to provide a drying heat source therefor.

[0101] Embodiment 9:

[0102] It is basically the same as Example 1, except that: a blast beam 29 with air outlet holes 30 and / or a central wind hood with air outlet holes 30 are provided at the lower part of the sublimation furnace 4; the blast beam 29 and / or the central wind hood are connected to the blast device through a pipeline, and the pipeline passes through the oxidation air inlet 9.

[0103] Embodiment 10:

[0104] The device is basically the same as the first embodiment, except that: the device of the type A structure comprises three or more vertical sublimation furnaces 4, external heaters 6, feeders and slag dischargers 11; or the device of the type B structure comprises three or more horizontal sublimation tubes 20, material pushers 21, external heaters 6 and hoppers 17;

[0105] The cavity wind speed of the oxidation wind entering the sublimation furnace 4 / sublimation tube 20 through the oxidation wind inlet 9 is less than 1 m / s, preferably less than 0.5 m / s; the oxidation wind is an oxygen-rich gas with an oxygen content greater than that of air, preferably 28%-70%.

Claims

1. A device for extracting molybdenum from molybdenum-containing waste catalyst, characterized in that: The device adopts the following structure: A type, the device of the A type structure comprises at least one set of vertically arranged sublimation furnaces (4), external heaters (6), a feeder with a hopper (17), a slag discharger (11), a blast device, a condensate recovery device, and a control system; the sublimation furnace (4) is a closed cylindrical structure mainly surrounded by a furnace wall (5), a feed inlet and a high-temperature molybdenum-containing gas outlet (18) are arranged at the top, an external heater (6) is arranged at the outer periphery of the middle part, and the external heater (6) radiates the molybdenum-containing gas in the sublimation furnace (4) through the furnace wall (5) in the middle part. The molybdenum waste catalyst is heated to oxidize the molybdenum to generate molybdenum oxide and sublime, an oxidation air inlet (9) is arranged at the bottom, and a slag discharger (11) is arranged at the slag discharger (10) at the bottom; the outlet of the feeder is connected to the feed inlet of the sublimation furnace (4), the high-temperature molybdenum-containing gas outlet (18) is connected to the high-temperature molybdenum-containing gas inlet (25) of the condensation recovery device through a pipeline, and the oxidation air inlet (9) is connected to the blasting device; the external heater (6), the feeder, the slag discharger (11) and the blasting device are all electrically connected to the control system; The horizontal cross section of the middle part of the sublimation furnace (4) of the A-type structure device is circular or rectangular, the height from the feed port to the slag outlet (10) is H, that is, the working height is H, the diameter or diagonal length or the diameter of the circumscribed circle of the horizontal cross section of the middle part of the sublimation furnace (4) of the A-type structure device is D, and H / D is greater than 3; or D is less than 1.5m at the same time; The device of the A-type structure further comprises a material level meter (1); the material level meter (1) is arranged on the top or upper side of the sublimation furnace (4) and is electrically connected to the control system to measure the height of the molybdenum waste catalyst in the sublimation furnace (4); The feeder of the A-type structure device comprises a hopper (17), a feed pipe (16) and a screw propeller (14); the feed pipe (16) is arranged horizontally and can be tilted downward along the feeding direction, and the screw propeller (14) is arranged inside the feed pipe; one end of the feed pipe (16) is connected to the outlet of the hopper (17), and the other end is connected to the feed port on the sublimation furnace (4); the feed pipe (16) can extend into the sublimation furnace (4) to ensure uniform distribution of the material; At least one thermocouple is arranged inside the sublimation furnace (4) or on the furnace wall (5), and the thermocouple is electrically connected to the control system; The material level meter (1) comprises a high temperature resistant probe rod (3) and a probe rod up and down reciprocating device; the probe rod up and down reciprocating device drives the high temperature resistant probe rod (3) to move up and down at a frequency of once per second to once per hour, and when the high temperature resistant probe rod (3) moves downward and touches the molybdenum-containing waste catalyst, it returns upward and transmits a material level signal to a control system; A top cover (2) of a blind plate structure fastened by bolts can be provided on the top of the sublimation furnace (4) to facilitate disassembly; A sleeve (15) is arranged outside the feed pipe (16) to form a jacket structure; the sleeve (15) passes through the furnace wall (5) and is in communication with the inner cavity of the sublimation furnace (4), while its outer surface is sealedly connected to the furnace wall (5); the outlet of the feed pipe (16) is the feed inlet of the sublimation furnace (4), and the annular opening between the outlet of the feed pipe (16) and the end of the sleeve (15) is the high-temperature molybdenum-containing gas outlet (18); when working, the high-temperature molybdenum-containing gas enters the condensation recovery device through the annular pipeline between the feed pipe (16) and the sleeve (15), and the molybdenum-containing waste catalyst in the feed pipe (16) is dried and preheated.

2. The device according to claim 1, characterized in that: The external heater (6) adopts one of the following two structures: Electric heating type: the electric heating type external heater (6) comprises an electric heating element and a refractory material, wherein the electric heating element and the refractory material constitute at least one level of independently controlled heating unit; the heating unit heats the furnace wall (5) of the sublimation furnace (4) at a temperature of 800 to 1200 degrees Celsius; Open flame type: The open flame type external heater (6) comprises a burner (13) and an annular heating chamber that surrounds the furnace wall (5) at least one level, wherein the annular heating chamber is a closed annular cavity structure mainly formed by refractory materials and the outer surface of the furnace wall (5), and a fire inlet and a hot air outlet (12) are arranged on the annular heating chamber; the heating temperature of the furnace wall (5) by the annular heating chamber is 800 to 1200 degrees Celsius; the flame nozzle of the burner (13) is connected to the fire inlet, and the electrical control part of the burner (13) is electrically connected to the control system; The device of the A-type structure also includes a raw material drying device (19) and a condensed tail gas environmental protection treatment device; the discharge port of the raw material drying device (19) is arranged above the feed port of the hopper (17); the hot air outlet (12) can be connected to the raw material drying device (19) to provide a drying heat source for it.

3. The device according to claim 2, characterized in that: The electric heating type external heater (6) comprises a primary heating unit and a secondary heating unit; when the primary heating unit and the secondary heating unit are arranged around the outer periphery of the middle part of the sublimation furnace (4), they are distributed up and down and can independently heat the furnace wall (5) of the sublimation furnace (4) in sections, the primary heating unit heating the furnace wall (5) at a temperature of 800 to 1200 degrees Celsius, and the secondary heating unit heating the furnace wall (5) at a temperature of 300 to 1050 degrees Celsius; The open flame type external heater (6) comprises a primary annular heating chamber (7) and a secondary annular heating chamber (8); the primary annular heating chamber (7) and the secondary annular heating chamber (8) surrounding the furnace wall (5) are distributed up and down and can independently heat the furnace wall (5) of the sublimation furnace (4) in sections, the primary annular heating chamber (7) heating the furnace wall (5) to a temperature of 800 to 1200 degrees Celsius, and the secondary annular heating chamber (8) heating the furnace wall (5) to a temperature of 300 to 1050 degrees Celsius; The primary annular heating chamber (7) and the secondary annular heating chamber (8) can also be connected in series, that is, the hot air outlet (12) of the primary annular heating chamber (7) is connected to the fire inlet of the secondary annular heating chamber (8); The top surface of the molybdenum-containing waste catalyst accumulated in the sublimation furnace (4) is the material top surface (31), and the height difference between the lowest point of the material top surface (31) and the highest point of the heating part of the heating unit outside the furnace wall (5) / the highest point of the inner cavity of the annular heating chamber is less than 1.5 m.

4. The device according to claim 1, characterized in that: The condensation recovery device comprises at least one condensation unit, wherein a single condensation unit comprises two condensation pipes (26), a small material storage bin (27) and a bin bottom discharger (28), wherein the two condensation pipes (26) are vertically arranged and the lower ends thereof are both connected to the small material storage bin (27), the small material storage bin (27) is a closed chamber structure, and the outlet at the bottom thereof is provided with a bin bottom discharger (28), the upper end of one condensation pipe (26) is provided with a high-temperature molybdenum-containing gas inlet (25), and the upper end of the other condensation pipe (26) is provided with an exhaust gas outlet; The device of the A-type structure further comprises a raw material drying device (19) and a condensed tail gas environmental protection treatment device; the discharge port of the raw material drying device (19) is arranged above the feed port of the hopper (17).

5. The device according to claim 4, characterized in that: The condenser (26) is also provided with a scraper; the scraper comprises a connecting rod (22), a scraper (24) and a scraper driver; the scraper (24) is arranged in the condenser (26) and connected to the connecting rod (22); the connecting rod (22) is connected to the scraper driver; under the action of the scraper driver, the scraper (24) moves up and down in the condenser (26) to scrape off the molybdenum-containing material adhering to the inner wall of the condenser (26); The top of the condenser tube (26) can also be provided with a condenser tube top cover (23) of a blind plate structure fastened by bolts, so as to facilitate disassembly; The condensation recovery device is composed of no less than 2 condensation units connected in series, or no less than 2 condensation units connected in parallel; A jacket water cooling device or a jacket air cooling device can be provided on the periphery of the condenser tube (26); the hot air outlet of the jacket air cooling device can be connected to the raw material drying device (19) to provide a drying heat source therefor.

6. The device according to claim 1, characterized in that: A blast beam (29) with an air outlet hole (30) and / or a central air hood with an air outlet hole (30) are provided at the lower part of the sublimation furnace (4); the blast beam (29) and / or the central air hood are connected to the blast device via a pipeline, and the pipeline passes through the oxidation air inlet (9).

7. The device according to claim 1, characterized in that: The A-type structure device comprises three or more vertically arranged sublimation furnaces (4), external heaters (6), feeders and slag dischargers (11); The cavity wind speed of the oxidation wind entering the sublimation furnace (4) through the oxidation wind inlet (9) is less than 1 m / s; the oxidation wind is an oxygen-rich gas with an oxygen content greater than that of air.

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