CN111003728B - Device and method for preparing titanium oxide nanorods by using waste denitration catalyst - Google Patents
Device and method for preparing titanium oxide nanorods by using waste denitration catalyst Download PDFInfo
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- CN111003728B CN111003728B CN201911193398.4A CN201911193398A CN111003728B CN 111003728 B CN111003728 B CN 111003728B CN 201911193398 A CN201911193398 A CN 201911193398A CN 111003728 B CN111003728 B CN 111003728B
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Abstract
The invention discloses a device for preparing titanium oxide nanorods by using a waste denitration catalyst, which comprises a compressed air blowing device, an acid washing device, a leaching device, a blast drying box, a crushing device, a grinding device and a storage bin, wherein the device is sequentially connected through a transmission guide rail according to the preparation and processing sequence of the titanium oxide nanorods; the method comprises the steps of sequentially carrying out purging, acid washing, leaching, drying, crushing, grinding and reacting on a waste denitration catalyst through a transmission guide rail, and finally preparing a titanium oxide nano rod by using the denitration catalyst; the device and the method realize the recycling of the waste denitration catalyst, fill the blank of the relative industry, improve the utilization rate of resources and provide a new idea for the high-efficiency and high-value utilization mode of the resources; the automatic production line has the advantages of realizing automation, reducing the number of on-site operators, improving the production efficiency, reducing the production cost and being beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of denitration catalysts, and particularly relates to a device and a method for preparing titanium oxide nanorods by using waste denitration catalysts.
Background
In recent years, the emission standard of the atmospheric pollutants in China is gradually strict, and the denitration and emission reduction work is fully developed. In the denitration technology, the Selective Catalytic Reduction (SCR) method has the advantages of high denitration efficiency (reaching more than 90 percent), mature technology and the like, and is widely applied to various industrial flue gas denitration processes of coal-fired power plants and the like in China. Common commercial catalysts are in the form of honeycomb TiO 2 -V 2 O 5 -WO 3 /MoO 3 Wherein the anatase TiO is 2 Is a carrier, V 2 O 5 As active ingredient, WO 3 Or MoO 3 Is an active and structural aid. The flue gas denitration system is generally arranged at the front end of the flue gas purification system, the dust content is high, the flue gas components are complex, and the catalyst efficiency is reduced or even deactivated after long-time operation. The deactivation caused by clogging and the like in the deactivation of the catalyst is reversible and can be recovered by a water washing regeneration process, an acid washing regeneration process, an alkali washing regeneration process, a heat regeneration process treatment and the like. The deactivation due to sintering, poisoning, abrasion and the like is irreversible deactivation and cannot be regenerated. The catalyst strength for severe abrasion is also significantly reduced and finally discarded.
The waste SCR denitration catalyst contains a large amount of valuable metal oxides, and is incorporated into dangerous solid waste (HW 49 other waste), so that the waste SCR denitration catalyst can cause environmental pollution if directly stacked, and can also cause waste of resources. In addition, from the standpoint of comprehensive utilization of resources, the waste SCR denitration catalyst has good recycling value, and the waste SCR denitration catalyst is recycled, so that the waste SCR denitration catalyst has important significance in saving resources.
Therefore, the device and the method for preparing the titanium oxide nanorod by using the waste denitration catalyst are technical problems to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to provide a device for preparing titanium oxide nanorods by using waste denitration catalysts, which solves the defects and the shortcomings of the prior art.
The technical scheme for solving the technical problems is as follows:
the invention provides a device for preparing titanium oxide nanorods by using a waste denitration catalyst, which comprises a blast drying box, a crushing device, a grinding device, a compressed air blowing device, an acid washing device, a leaching device, a bin and a controller, wherein the blowing drying box is arranged on the crushing device;
the compressed air blowing device, the acid washing device, the leaching device, the blast drying box, the crushing device, the grinding device and the storage bin are respectively and electrically connected with the controller, and the compressed air blowing device, the acid washing device, the leaching device, the blast drying box, the crushing device, the grinding device and the storage bin are sequentially connected through the transmission guide rail.
Preferably, the compressed air purging device comprises a motor, an electromagnetic valve electric pump, a purging groove, a power-assisted manipulator, a sliding rail, an air storage tank, a top plate pulley and at least one top plate;
the motor is electrically connected with the purging groove;
the top plate pulley is fixedly connected with the top end of the blowing groove, and the top plate is in sliding connection with the top plate pulley; the top plate is provided with a plurality of grooves, compressed air blowing pipes are arranged in the grooves, and the compressed air blowing pipes are fixedly connected with the air storage tank;
the electromagnetic valve electric pump is electrically connected with the sliding rail, a pulley is arranged on the lower surface of the sliding rail, and the power-assisted mechanical arm is fixedly connected with the pulley;
more preferably, the bottom of the inner surface of the purging groove is provided with a first grid bracket, and the aperture range of the first grid bracket is 50-100mm; the first grid support can filter ash blown from the denitration catalyst; the lower part of the purging groove is provided with an ash bucket.
The adoption of the preferable beneficial effects is as follows: according to the device disclosed by the invention, the catalyst can be supported by the grid support, so that the airflow is facilitated, and meanwhile, the purged ash can smoothly enter the ash bucket, so that the purging effect is improved. The pore diameter of the grid is larger, so that the catalyst pores are not blocked by the grid structure.
Preferably, the pickling device comprises a pickling tank, a second grid bracket, an ultrasonic generating device, a constant-temperature heating device, a temperature controller, a first waste liquid collecting box and a first cover plate;
the first cover plate is positioned at the top of the pickling tank;
the second grid support is fixed at the bottom of the inner surface of the pickling tank, the aperture range of the second grid support is 50-100mm, and the second grid support can be used for filtering pollutants eluted by pickling;
the ultrasonic generating device and the constant temperature heating device are both fixed in the pickling tank;
wherein the constant temperature heating device is electrically connected with the temperature controller; the bottom of the pickling tank is provided with a first liquid outlet, and the first liquid outlet is connected with the first waste liquid collecting box through a pipeline.
The adoption of the preferable beneficial effects is as follows: the ultrasonic wave adopted by the invention can improve the wettability of the pickling solution on the surface of the catalyst and promote the pickling effect.
Preferably, the leaching device comprises a spraying system, a leaching tank, a third grid bracket, a second cover plate, a sliding rail and a second waste liquid collecting box;
the spraying system comprises a spraying pipe and a plurality of nozzles, and the spraying pipe is fixedly connected with the nozzles; the spray pipe and the spray nozzle are fixed in the second cover plate, the second cover plate is fixed on the sliding rail, and the sliding rail is controlled by the servo motor;
the third grid support is fixed at the bottom of the inner surface of the leaching tank, a second liquid outlet is arranged at the bottom of the leaching tank, and the second liquid outlet is connected with the second waste liquid collecting box through a pipeline;
more preferably, the nozzle is an upright nozzle or a drooping nozzle;
the adoption of the preferable beneficial effects is as follows: the spraying system can wash the catalyst by utilizing the flow of the spraying liquid, and the cleaning effect is improved.
Preferably, the crushing device is a jaw crusher or a hammer crusher, and the grinding device is a Raymond mill;
preferably, the storage bin comprises a first reaction kettle, a second reaction kettle and a rotary evaporator; the first reaction kettle, the second reaction kettle and the rotary evaporator are sequentially connected through sliding guide rails; and a stirring device, a centrifugal device and a filtering device are arranged in the first reaction kettle.
The adoption of the preferable beneficial effects is as follows: the invention can effectively improve the cleaning effect, reduce the loss of active components of the catalyst and simplify the treatment process by crushing after pretreatment.
The invention also provides a preparation method for preparing the titanium oxide nanorod by using the waste denitration catalyst, which comprises the following steps:
(1) The denitration catalyst is vertically fixed on a booster manipulator of a compressed air purging device, and is purged through compressed air;
(2) Transferring the purged catalyst into a pickling device containing weak acid for pickling, and controlling the temperature to be 30-50 ℃;
(3) Transferring the acid-washed catalyst into a leaching device for leaching, and drying;
(4) Crushing the dried catalyst in a crushing device, and grinding in a grinding device to obtain catalyst powder;
(5) Placing the obtained catalyst powder into a first reaction kettle, cleaning with ammonia water, stirring for 10-48 hours to obtain a suspension, centrifuging the suspension, and filtering to obtain a filtered powder;
(6) Mixing and stirring the filtered powder with a sodium hydroxide solution to obtain a suspension, performing hydrothermal treatment on the suspension, adjusting the pH to 1-2 by adopting acid, performing centrifugal filtration, and washing the filtered catalyst to be neutral;
(7) Mixing the catalyst treated in the step (6) with a hydrothermal solution, uniformly stirring, adding dimethylamine, and uniformly stirring again to obtain a mixed solution; and (3) placing the mixed solution into a second reaction kettle for reaction, and placing the solution in the second reaction kettle into a rotary evaporator for rotary evaporation after the reaction is completed, so as to obtain the titanium oxide nanorod.
Further, the compressed air purging pressure in the step (1) is 0.5-1MPa, and the purging time is 30-60min;
the adoption of the method has the further beneficial effects that: the air purge pressure defined by the present invention can enhance the purge effect by utilizing an appropriate air pressure. And meanwhile, the loss of active components of the catalyst caused by overlarge purging strength is reduced.
Further, the weak acid in the step (2) is any one of acetic acid, citric acid and hydrobromic acid;
further, the mass concentration fraction of the weak acid is 5-50%; the volume ratio of the catalyst to the weak acid in the acid washing device is 1:10-20; the pickling time is 6-12h;
further, the rinsing time in the step (3) is 20-30min, the temperature of the forced air drying device is 100-110 ℃, and the drying time is 2-5h;
further, in the step (4), the crushing granularity is below 20 mm; the grinding granularity is below 200 mu m;
the adoption of the method has the further beneficial effects that: the reaction rate between the catalyst and the reaction solution can be increased within the particle size range defined by the present invention.
Further, the concentration of the ammonia water in the step (5) is 10-25%; the mass ratio of the catalyst to the ammonia water is 1:5-20;
further, in the step (6), the concentration of the sodium hydroxide solution is 5-10mol/L, and 20-50ml of sodium hydroxide solution is mixed with 1g of catalyst powder; the hydrothermal temperature is 100-150 ℃ and the hydrothermal time is 12-48h;
the regulating acid is hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the regulating acid is 0.1-0.5mol/L;
further, in the step (7), the hydrothermal solution is prepared by mixing water and an alcohol solvent according to a volume ratio of 1 (1-5).
Further, the water is deionized water; the alcohol solvent is one of ethanol, glycol and isopropanol;
further, mixing 20-50ml of the hydrothermal solution for each 1g of the catalyst in the step (7); the first stirring speed is 500-1000rpm, and the stirring time is 0.5-1h; the addition amount of dimethylamine is 1/30 of that of the hydrothermal solution; the second stirring speed is 500-1000rpm, and the stirring time is 1-2h; the reaction temperature of the reaction kettle is 150-200 ℃ and the reaction time is 8-15h;
further, the rotary evaporation process in the step (7) further comprises adding deionized water.
The adoption of the method has the further beneficial effects that: the deionized water is utilized to replace the organic solvent in the system, so that the evaporation of the organic solvent is more thorough, and the deionized water is added to control the replacement rate and improve the replacement effect.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a method for directly preparing titanium oxide nanorods by using a waste denitration catalyst and a pretreatment device, which fill the blank of the relative industry, improve the utilization rate of resources and provide a new idea for the efficient and high-value utilization mode of the resources.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an apparatus for preparing titanium oxide nanorods by using a waste denitration catalyst;
in fig. 1, the structures represented by the reference numerals are listed below: 1-compressed air purging device, 2-pickling device, 3-leaching device, 4-blast drying box, 5-crushing device, 6-grinding device and 7-bin;
FIG. 2 is a schematic view of a compressed air purge apparatus according to the present invention;
in fig. 2, the structures represented by the reference numerals are listed below:
101-motors, 102-electromagnetic valve electric pumps, 103-purge tanks, 104-power-assisted manipulators, 105-sliding rails, 106-gas storage tanks, 107-top plates, 108-top plate pulleys, 109-grooves, 110-compressed air blowing pipes, 111-first grid brackets and 112-ash hoppers;
FIG. 3 is a schematic diagram of the structure of the pickling device of the invention;
in fig. 3, the structures represented by the reference numerals are listed below: 201-a pickling tank, 202-a second grid bracket, 203-an ultrasonic generating device, 204-a constant temperature heating device, 205-a temperature controller, 206-a first waste liquid collecting box, 207-a first cover plate and 208-a first liquid outlet;
FIG. 4 is a schematic view of the construction of the leaching apparatus of the present invention;
in fig. 4, the structures represented by the reference numerals are listed below: 301-spraying pipes, 302-spraying nozzles, 303-spraying tanks, 304-third grid brackets, 305-second cover plates, 306-sliding rails, 307-second waste liquid collecting boxes, 308-servo motors and 309-second liquid drain ports;
FIG. 5 is a schematic view of the structure of the silo according to the invention;
in fig. 5, the structures represented by the reference numerals are listed below: 71-a first reaction kettle, 711-a stirring device, 712-a centrifugal device, 713-a filtering device, 72-a second reaction kettle and 73-a rotary evaporator;
FIG. 6 is a scanning electron microscope image of a titanium oxide nanorod prepared in example 1 of the present invention;
FIG. 7 is a scanning electron microscope image of a titanium oxide nanorod prepared in example 2 of the present invention;
FIG. 8 is a transmission electron microscope image of the titanium oxide nanorods prepared in example 3 of the present invention;
FIG. 9 is a transmission electron microscope image of the titanium oxide nanorods prepared in example 4 of the present invention;
FIG. 10 is a transmission electron microscope image of a titanium oxide nanorod prepared in example 5 of the present invention.
Detailed Description
The following examples are presented to illustrate the invention in detail, but are not intended to limit the invention to the preferred embodiments thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Vertically fixing a denitration catalyst on a booster manipulator of a compressed air purging device, and then purging with compressed air at 0.5MPa for 60min;
(2) Placing the purged catalyst into a pickling device containing acetic acid with the mass concentration fraction of 50% for pickling for 6 hours, wherein the volume ratio of the catalyst to weak acid is 1:20; and a constant temperature heating device is adopted to control the temperature to be 30 ℃;
(3) Placing the acid-washed catalyst into a leaching device for leaching for 20min, and drying for 2h at 110 ℃;
(4) Putting the dried catalyst into a crushing device for crushing, sieving with a 20mm sieve, and then putting the crushed catalyst into a grinding device for grinding, and sieving with a 200 mu m sieve to obtain catalyst powder;
(5) Putting the catalyst powder obtained in the step (4) into a first reaction kettle, cleaning with 10% ammonia water, performing magnetic stirring for 48 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder, wherein the mass ratio of the catalyst powder to the ammonia water is 1:20;
(6) Mixing and stirring the filter powder obtained in the step (5) with 5mol/L sodium hydroxide solution to obtain a suspension, mixing 20ml sodium hydroxide solution with each 1g of catalyst powder, performing hydrothermal treatment on the suspension at 100 ℃ for 48 hours, adjusting the pH of the suspension after the hydrothermal treatment to be 1 by adopting 0.5mol/L hydrochloric acid, centrifuging and filtering, and washing the filtered catalyst with water to be neutral;
(7) Mixing deionized water and ethanol according to the volume ratio of 1:1 to obtain a hydrothermal solution, mixing the cleaned catalyst with the hydrothermal solution, and stirring at 1000rpm for 1h, wherein 20ml of the hydrothermal solution is adopted for each 1g of the catalyst; then adding dimethylamine into the mixed solution, wherein the adding amount of dimethylamine is 1/30 of that of the hydrothermal solution, stirring for 2 hours at 1000rpm, then placing the mixed solution into a second reaction kettle for reaction, wherein the reaction temperature of the reaction kettle is 150 ℃, the reaction time is 15 hours, and then placing the reaction solution into a rotary evaporator for rotary evaporation, thus obtaining the titanium oxide nanorod.
Example 2
(1) Vertically fixing a denitration catalyst on a booster manipulator of a compressed air purging device, and then purging with compressed air for 30min at 1 MPa;
(2) Placing the purged catalyst into a pickling device containing 5% of citric acid in mass concentration for pickling for 12 hours, wherein the volume ratio of the catalyst to weak acid is 1:10; and a constant temperature heating device is adopted to control the temperature to be 50 ℃;
(3) Placing the acid-washed catalyst into a leaching device for leaching for 30min, and drying for 5h at 100 ℃;
(4) Putting the dried catalyst into a crushing device for crushing, sieving with a 20mm sieve, and then putting the crushed catalyst into a grinding device for grinding, and sieving with a 200 mu m sieve to obtain catalyst powder;
(5) Putting the catalyst powder obtained in the step (4) into a first reaction kettle, cleaning with ammonia water with the concentration of 25%, wherein the mass ratio of the catalyst powder to the ammonia water is 1:5, magnetically stirring for 10 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder;
(6) Mixing and stirring the filter powder obtained in the step (5) with 10mol/L sodium hydroxide solution to obtain a suspension, mixing 20ml sodium hydroxide solution with each 1g of catalyst powder, performing hydrothermal treatment on the suspension for 12 hours at 150 ℃, adjusting the pH of the suspension after the hydrothermal treatment to be 1 by adopting 0.1mol/L hydrochloric acid, centrifuging and filtering, and washing the filtered catalyst with water to be neutral;
(7) Mixing deionized water and ethylene glycol according to a volume ratio of 1:5 to obtain a hydrothermal solution, mixing the cleaned catalyst with the hydrothermal solution, and stirring at 500rpm for 0.5h, wherein 50ml of the hydrothermal solution is adopted for each 1g of the catalyst; then adding dimethylamine into the mixed solution, wherein the adding amount of dimethylamine is 1/30 of that of the hydrothermal solution, stirring for 1h at 500rpm, then placing the mixed solution into a second reaction kettle for reaction, wherein the reaction temperature of the reaction kettle is 200 ℃, the reaction time is 8h, and then placing the reaction solution into a rotary evaporator for rotary evaporation, thus obtaining the titanium oxide nanorod.
Example 3
(1) Vertically fixing a denitration catalyst on a booster manipulator of a compressed air purging device, and then purging with compressed air at 0.7MPa for 45min;
(2) Placing the purged catalyst into a pickling device containing hydrobromic acid with the mass concentration fraction of 30% for pickling for 9 hours, wherein the volume ratio of the catalyst to weak acid is 1:15; and a constant temperature heating device is adopted to control the temperature to be 45 ℃;
(3) Placing the acid-washed catalyst into a leaching device for leaching for 25min, and drying for 3h at 105 ℃;
(4) Putting the dried catalyst into a crushing device for crushing, sieving with a 20mm sieve, and then putting the crushed catalyst into a grinding device for grinding, and sieving with a 200 mu m sieve to obtain catalyst powder;
(5) Putting the catalyst powder obtained in the step (4) into a first reaction kettle, cleaning with 15% ammonia water, performing magnetic stirring for 30 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder, wherein the mass ratio of the catalyst powder to the ammonia water is 1:12;
(6) Mixing and stirring the filter powder obtained in the step (5) with a sodium hydroxide solution with the concentration of 8mol/L to obtain a suspension, mixing 35ml of the sodium hydroxide solution with each 1g of catalyst powder, performing hydrothermal treatment on the suspension at 125 ℃ for 30 hours, adjusting the pH of the suspension after the hydrothermal treatment to be 1.5 by adopting hydrochloric acid with the concentration of 0.3mol/L, centrifuging and filtering, and washing the filtered catalyst with water to be neutral;
(7) Mixing deionized water with ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:3 to obtain a hydrothermal solution, mixing the cleaned catalyst with the hydrothermal solution, and stirring at 700rpm for 0.7h, wherein 35ml of the hydrothermal solution is adopted for each 1g of the catalyst; then adding dimethylamine into the mixed solution, wherein the adding amount of dimethylamine is 1/30 of that of the hydrothermal solution, stirring for 1.5h at 700rpm, then placing the mixed solution into a second reaction kettle for reaction, wherein the reaction temperature of the reaction kettle is 180 ℃, the reaction time is 12h, and then placing the reaction solution into a rotary evaporator for rotary evaporation, thus obtaining the titanium oxide nanorod.
Example 4
(1) Vertically fixing a denitration catalyst on a booster manipulator of a compressed air purging device, and then purging with compressed air at 0.9MPa for 50min;
(2) Placing the purged catalyst into a pickling device containing hydrobromic acid with mass concentration fraction of 30% for pickling for 6-12h, wherein the volume ratio of the catalyst to weak acid is 1:10-20; and a constant temperature heating device is adopted to control the temperature to be 30-50 ℃;
(3) Placing the acid-washed catalyst into a leaching device for leaching for 22min, and drying for 4h at 102 ℃;
(4) Putting the dried catalyst into a crushing device for crushing, sieving with a 20mm sieve, and then putting the crushed catalyst into a grinding device for grinding, and sieving with a 200 mu m sieve to obtain catalyst powder;
(5) Putting the catalyst powder obtained in the step (4) into a first reaction kettle, cleaning with ammonia water with the concentration of 20%, wherein the mass ratio of the catalyst powder to the ammonia water is 1:8, magnetically stirring for 36 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder;
(6) Mixing and stirring the filter powder obtained in the step (5) and a sodium hydroxide solution with the concentration of 7.5mol/L to obtain a suspension, mixing 45ml of the sodium hydroxide solution with each 1g of catalyst powder, performing hydrothermal treatment on the suspension at 115 ℃ for 36h, adjusting the pH of the suspension after the hydrothermal treatment to be 1 by adopting hydrochloric acid with the concentration of 0.3mol/L, centrifuging and filtering, and washing the filtered catalyst with water to be neutral;
(7) Mixing deionized water with ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:2 to obtain a hydrothermal solution, mixing the cleaned catalyst with the hydrothermal solution, and stirring at 900rpm for 0.8h, wherein 40ml of the hydrothermal solution is adopted for each 1g of the catalyst; then adding dimethylamine into the mixed solution, wherein the adding amount of dimethylamine is 1/30 of that of the hydrothermal solution, stirring for 2 hours at 900rpm, then placing the mixed solution into a second reaction kettle for reaction, wherein the reaction temperature of the reaction kettle is 170 ℃, the reaction time is 10 hours, and then placing the reaction solution into a rotary evaporator for rotary evaporation, thus obtaining the titanium oxide nanorod.
Example 5
(1) Vertically fixing a denitration catalyst on a booster manipulator of a compressed air purging device, and then purging with compressed air at 0.6MPa for 55min;
(2) Placing the purged catalyst into a pickling device containing 15% of acetic acid in mass concentration for pickling for 7 hours, wherein the volume ratio of the catalyst to weak acid is 1:12; and a constant temperature heating device is adopted to control the temperature to be 35 ℃;
(3) Placing the acid-washed catalyst into a leaching device for leaching for 28min, and drying at 107 ℃ for 3h;
(4) Putting the dried catalyst into a crushing device for crushing, sieving with a 20mm sieve, and then putting the crushed catalyst into a grinding device for grinding, and sieving with a 200 mu m sieve to obtain catalyst powder;
(5) Putting the catalyst powder obtained in the step (4) into a first reaction kettle, cleaning with 15% ammonia water, performing magnetic stirring for 24 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder, wherein the mass ratio of the catalyst powder to the ammonia water is 1:15;
(6) Mixing and stirring the filter powder obtained in the step (5) with a sodium hydroxide solution with the concentration of 6mol/L to obtain a suspension, mixing 30ml of the sodium hydroxide solution with each 1g of catalyst powder, performing hydrothermal treatment on the suspension at 140 ℃ for 24 hours, adjusting the pH of the suspension after the hydrothermal treatment to be 2 by adopting hydrochloric acid with the concentration of 0.4mol/L, centrifuging and filtering, and washing the filtered catalyst with water to be neutral;
(7) Mixing deionized water with ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:4 to obtain a hydrothermal solution, mixing the cleaned catalyst with the hydrothermal solution, and stirring at 600rpm for 0.5h, wherein 40ml of the hydrothermal solution is adopted for each 1g of the catalyst; then adding dimethylamine into the mixed solution, wherein the adding amount of dimethylamine is 1/30 of that of the hydrothermal solution, stirring for 2 hours at 600rpm, then placing the mixed solution into a second reaction kettle for reaction, wherein the reaction temperature of the reaction kettle is 185 ℃, the reaction time is 14 hours, and then placing the reaction solution into a rotary evaporator for rotary evaporation, thus obtaining the titanium oxide nanorod.
The pretreatment device for preparing the titanium oxide nanorods by using the waste denitration catalyst provided by the embodiment of the invention is used for preparing the titanium oxide nanorods, so that the waste denitration catalyst is recycled, the blank of the relative industry is filled, the resource utilization rate is improved, and a new idea is provided for a high-efficiency and high-value utilization mode of resources; the automatic production line has the advantages of realizing automation, reducing the number of on-site operators, improving the production efficiency, reducing the production cost and being beneficial to industrial production.
Examples 1-5 preparation of titania nanorod pretreatment device using waste denitration catalyst:
the device comprises a compressed air blowing device 1, an acid washing device 2, a leaching device 3, a blast drying box 4, a crushing device 5, a grinding device 6, a storage bin 7 and a controller;
the compressed air blowing device 1, the pickling device 2, the leaching device 3, the blast drying box 4, the crushing device 5, the grinding device 6 and the storage bin 7 are respectively and electrically connected with the controller, and the compressed air blowing device 1, the pickling device 2, the leaching device 3, the blast drying box 4, the crushing device 5, the grinding device 6 and the storage bin 7 are sequentially connected through transmission guide rails.
In one embodiment, the compressed air purge device comprises a motor 101, a solenoid valve electric pump 102, a purge tank 103, a booster manipulator 104, a slide rail 105, an air storage tank 106 and two top plates 107; the motor 101 is electrically connected with the blowing groove 103, two top plates 107 are symmetrically and slidingly connected to the upper end of the blowing groove 103 through top plate pulleys 108 respectively, the top plates 107 are provided with a plurality of grooves 109, compressed air blowing pipes 110 are arranged in the grooves 109, and the compressed air blowing pipes 110 are fixedly connected with the air storage tank 106; the electromagnetic valve electric pump 102 is electrically connected with the sliding rail 105, and the power assisting manipulator 104 is slidably connected to the lower surface of the sliding rail 105.
In another embodiment, the bottom of the inner surface of the purge tank 103 is provided with a grid support 111; the bottom of the outer surface of the blowing groove 103 is provided with an ash bucket 112.
In another embodiment, the pickling device comprises a pickling tank 201, a second grid support 202, an ultrasonic generating device 203, a constant-temperature heating device 204, a temperature controller 205, a first waste liquid collecting box 206 and a first cover plate 207; a first cover plate 207 is positioned on top of the pickling tank 201; the second grid support 202 is fixed at the bottom of the inner surface of the pickling tank 201; the ultrasonic wave generating device 203 and the constant temperature heating device 204 are all fixed inside the pickling tank; wherein the constant temperature heating device 204 is electrically connected with the temperature controller 205; the bottom of the pickling tank 201 is provided with a first liquid outlet 208, and the first liquid outlet 208 is connected with a first waste liquid collecting box 206 through a pipeline.
In one embodiment, the leaching device comprises a spray system, a leaching tank 303, a third grid support 304, a second cover plate 305, a slide rail 306, and a second waste collection tank 307; the spraying system comprises a spraying pipe 301 and 14 nozzles 302, wherein the nozzles 302 are provided with 7 vertical nozzles and 7 sagging nozzles, and the spraying pipe 301 is fixedly connected with the nozzles 302; the spray pipe 301 and the spray nozzle 302 are fixed in the second cover plate 305, the second cover plate 305 is fixed on the slide rail 306, and the slide rail 306 is controlled by the servo motor 308; the third grid bracket 304 is fixed at the bottom of the inner surface of the leaching tank 303, a second liquid outlet 309 is arranged at the bottom of the leaching tank 303, and the second liquid outlet 309 is connected with a second waste liquid collecting box 307 through a pipeline;
in one embodiment, the storage bin comprises a first reaction kettle 71, a second reaction kettle 72, and a rotary evaporator 73; the first reaction kettle 71, the second reaction kettle 72 and the rotary evaporator 73 are sequentially connected through sliding guide rails; the first reaction vessel is provided with a stirring device 711, a centrifugal device 712 and a filtering device 713.
The preparation process of the pretreatment device for preparing the titanium oxide nanorod by using the waste denitration catalyst is as follows: fixing the waste denitration catalyst by adopting a power-assisted mechanical arm, and placing the waste denitration catalyst in a compressed air purging device for purging to remove surface dust; then placing the waste denitration catalyst into a pickling device through a conveying guide rail for pickling to remove soluble ions and groups such as K, na, ca and the like on the surface; after pickling, placing the waste denitration catalyst into a leaching device through a sliding guide rail for leaching, and then placing the waste denitration catalyst into a blast drying box for drying; then placing the waste denitration catalyst into a crushing device and a grinding device through a sliding guide rail for crushing and grinding; and then placing the waste denitration catalyst into a storage bin through a sliding guide rail for reaction to obtain the titanium oxide nanorod.
In the description of the present invention, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. The device for preparing the titanium oxide nanorods by using the waste denitration catalyst comprises a blast drying box, a crushing device and a grinding device, and is characterized by further comprising a compressed air blowing device, an acid washing device, a leaching device, a storage bin and a controller;
the compressed air blowing device, the pickling device, the leaching device, the blast drying box, the crushing device, the grinding device and the storage bin are respectively and electrically connected with the controller, and the compressed air blowing device, the pickling device, the leaching device, the blast drying box, the crushing device, the grinding device and the storage bin are sequentially connected through a transmission guide rail;
the feed bin comprises a first reaction kettle, a second reaction kettle and a rotary evaporator; the first reaction kettle, the second reaction kettle and the rotary evaporator are sequentially connected through sliding guide rails; and a stirring device, a centrifugal device and a filtering device are arranged in the first reaction kettle.
2. The apparatus for preparing titanium oxide nanorods by using a waste denitration catalyst according to claim 1, wherein the compressed air purging device comprises a motor, an electromagnetic valve electric pump, a purging groove, a power-assisted manipulator, a sliding rail, an air storage tank, a top plate pulley and at least one top plate;
the motor is electrically connected with the purging groove;
the top plate pulley is fixedly connected with the top end of the blowing groove, and the top plate is in sliding connection with the top plate pulley; the top plate is provided with a plurality of grooves, compressed air blowing pipes are arranged in the grooves, and the compressed air blowing pipes are fixedly connected with the air storage tank;
the electromagnetic valve electric pump is electrically connected with the sliding rail, a pulley is arranged on the lower surface of the sliding rail, and the power-assisted mechanical arm is fixedly connected with the pulley.
3. The device for preparing the titanium oxide nanorods by using the waste denitration catalyst according to claim 2, wherein a first grid bracket is arranged at the bottom of the inner surface of the purging groove; an ash bucket is arranged at the bottom of the outer surface of the blowing groove.
4. The device for preparing the titanium oxide nanorods by using the waste denitration catalyst according to claim 1, wherein the pickling device comprises a pickling tank, a second grid bracket, an ultrasonic generating device, a constant temperature heating device, a temperature controller, a first waste liquid collecting box and a first cover plate;
the first cover plate is positioned at the top of the pickling tank;
the second grid support is fixed at the bottom of the inner surface of the pickling tank;
the ultrasonic generating device and the constant temperature heating device are both fixed in the pickling tank;
wherein the constant temperature heating device is electrically connected with the temperature controller; the bottom of the pickling tank is provided with a first liquid outlet, and the first liquid outlet is connected with the first waste liquid collecting box through a pipeline.
5. The apparatus for preparing titanium oxide nanorods by using a waste denitration catalyst according to claim 1, wherein the leaching device comprises a spraying system, a leaching tank, a third grid bracket, a second cover plate, a sliding rail, a second waste liquid collecting box and a servo motor;
the spraying system comprises a spraying pipe and a plurality of nozzles, and the spraying pipe is fixedly connected with the nozzles; the spray pipe and the spray nozzle are fixed in the second cover plate, the second cover plate is fixed on the sliding rail, and the sliding rail is controlled by the servo motor;
the third grid support is fixed at the bottom of the inner surface of the leaching tank, a second liquid outlet is arranged at the bottom of the leaching tank, and the second liquid outlet is connected with the second waste liquid collecting box through a pipeline.
6. A method for preparing a titanium oxide nanorod by using a waste denitration catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) The denitration catalyst is vertically fixed on a booster manipulator of a compressed air purging device, and is purged through compressed air;
(2) Transferring the purged catalyst into a pickling device containing weak acid for pickling, and controlling the temperature to be 30-50 ℃;
(3) Transferring the acid-washed catalyst into a leaching device for leaching, and drying;
(4) Crushing the dried catalyst in a crushing device, and grinding in a grinding device to obtain catalyst powder;
(5) Placing the obtained catalyst powder into a first reaction kettle, cleaning with ammonia water, stirring for 10-48 hours to obtain a suspension, centrifuging the suspension, and filtering to obtain a filtered powder;
(6) Mixing and stirring the filtered powder with a sodium hydroxide solution to obtain a suspension, performing hydrothermal treatment on the suspension, adjusting the pH to 1-2 by adopting acid, performing centrifugal filtration, and washing the filtered catalyst to be neutral;
(7) Mixing the catalyst treated in the step (6) with a hydrothermal solution, uniformly stirring, adding dimethylamine, and uniformly stirring again to obtain a mixed solution; and (3) placing the mixed solution into a second reaction kettle for reaction, and placing the solution in the second reaction kettle into a rotary evaporator for rotary evaporation after the reaction is completed, so as to obtain the titanium oxide nanorod.
7. The method for preparing the titanium oxide nanorods by using the waste denitration catalyst according to claim 6, wherein in the step (2), the weak acid is any one of acetic acid, citric acid and hydrobromic acid, and the mass concentration fraction of the weak acid is 5-50%.
8. The method for preparing titanium oxide nanorods by using the waste denitration catalyst according to claim 6, wherein the hydrothermal solution in the step (7) is prepared by mixing water and an alcohol solvent according to a volume ratio of 1 (1-5).
9. The method for preparing titanium oxide nanorods by using the waste denitration catalyst according to claim 8, wherein the water is deionized water; the alcohol solvent is one of ethanol, glycol and isopropanol.
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