CN111003728A - 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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Abstract
The invention discloses a device for preparing titanium oxide nanorods by using waste denitration catalysts, 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 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 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 blowing, acid washing, leaching, drying, crushing, grinding and reacting on the waste denitration catalyst through a transmission guide rail, and finally preparing the titanium oxide nanorod by using the denitration catalyst; the device and the method provided by the invention realize the recycling of the waste denitration catalyst, fill up the blank of relative industries, improve the resource utilization rate and provide a new idea for the efficient and high-value utilization mode of resources; the automation is realized, the number of field operators is reduced, the production efficiency is improved, the production cost is reduced, and the industrial production is facilitated.
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 atmospheric pollutants in China is gradually strict, and the work of denitration and emission reduction is comprehensively developed. In the denitration technology, a Selective Catalytic Reduction (SCR) method has the advantages of high denitration efficiency (up to more than 90 percent), mature technology and the like, and is widely applied to the denitration process of various industrial flue gases of coal-fired power plants and the like in China. Common commercial catalysts are honeycomb TiO2-V2O5-WO3/MoO3In which anatase type TiO2As a carrier, V2O5As an active ingredient, WO3Or MoO3Is an active and structural assistant. 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 can be reduced or even inactivated after long-time operation. Deactivation due to clogging or the like in deactivation of the catalyst is reversible, and can be recovered by treatment with a water washing regeneration process, an acid washing regeneration process, an alkali washing regeneration process, a thermal regeneration process, or the like. The deactivation caused by sintering, poisoning, abrasion and the like is irreversible deactivation and cannot be regenerated. The strength of the catalyst, which is severely abraded, is also remarkably reduced and is finally discarded.
The waste SCR denitration catalyst contains a large amount of valuable metal oxides, and is incorporated into hazardous solid waste (HW49 other waste), and if the hazardous solid waste is directly stacked, the environmental pollution is caused, and the waste of resources is caused. In addition, from the perspective of comprehensive utilization of resources, the waste SCR denitration catalyst has a good recycling value, is recycled, and has an important significance for saving resources.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide an apparatus and a method for preparing titanium oxide nanorods using waste denitration catalysts.
Disclosure of Invention
The invention aims to provide a device for preparing titanium oxide nanorods by using waste denitration catalysts, and the device is used for solving the defects and shortcomings in 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 waste denitration catalysts, 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 storage bin and a controller, wherein the blast drying box is connected with the crushing device;
compressed air sweeps device, acid dip pickle, drip washing device, air blast drying cabinet, breaker, grinder and feed bin respectively with controller electric connection, compressed air sweeps device, acid dip pickle, drip washing device, air blast drying cabinet, breaker, grinder and feed bin and connects gradually through drive rail.
Preferably, the compressed air purging device comprises a motor, an electromagnetic valve electric pump, a purging groove, a power-assisted mechanical arm, 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 tank;
the top plate pulley is fixedly connected with the top end of the blowing groove, and the top plate is connected with the top plate pulley in a sliding manner; the top plate is provided with a plurality of grooves, compressed air injection pipes are arranged in the grooves, and the compressed air injection 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 support, and the aperture range of the first grid support is 50-100 mm; the first grid support can filter ash blown from the denitration catalyst; an ash bucket is arranged at the lower part of the blowing groove.
The preferable beneficial effects are as follows: the device can support the catalyst by using the grid support, is favorable for airflow flowing, and can ensure that the swept ash can smoothly enter the ash bucket, thereby improving the sweeping effect. The mesh aperture is large, and the catalyst holes cannot be shielded by the mesh structure.
Preferably, the pickling device comprises a pickling tank, a second grid support, 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 pore size 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 inside the pickling tank;
the constant-temperature heating device is electrically connected with the temperature control instrument; the bottom of the pickling tank is provided with a first liquid discharge port, and the first liquid discharge port is connected with the first waste liquid collecting box through a pipeline.
The preferable beneficial effects are as follows: the ultrasonic wave adopted by the invention can improve the wetting property 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 support, 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 spraying pipe and the 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 formed in 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 a vertical type nozzle or a drooping type nozzle;
the preferable beneficial effects are as follows: the spraying system provided by the invention can flush the catalyst by utilizing the flow of the spraying liquid, so that the cleaning effect is improved.
Preferably, the crushing device is a jaw crusher or hammer crusher, and the grinding device is a Raymond mill;
preferably, the 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 a sliding guide rail; and a stirring device, a centrifugal device and a filtering device are arranged in the first reaction kettle.
The preferable beneficial effects are as follows: the invention can effectively improve the cleaning effect by crushing after the pretreatment, reduce the loss of the active components of the catalyst and simplify the treatment process.
The invention also provides a preparation method of the titanium oxide nanorod by using the waste denitration catalyst, which comprises the following steps:
(1) vertically fixing a denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing by compressed air;
(2) transferring the purged catalyst to an acid washing device containing weak acid for acid washing, and controlling the temperature to be 30-50 ℃;
(3) transferring the acid-washed catalyst to a leaching device for leaching, and then drying;
(4) crushing the dried catalyst in a crushing device, and then grinding the crushed catalyst in a grinding device to obtain catalyst powder;
(5) putting the obtained catalyst powder into a first reaction kettle, washing the catalyst powder by using ammonia water, stirring the catalyst powder for 10 to 48 hours to obtain a suspension, centrifuging the suspension, and filtering the suspension to obtain filtered powder;
(6) mixing and stirring the filtered powder and a sodium hydroxide solution to obtain a suspension, carrying out hydrothermal treatment on the suspension, adjusting the pH to 1-2 by using an acid, carrying out centrifugal filtration, and washing the filtered catalyst to be neutral;
(7) mixing the catalyst treated in the step (6) with the 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 finished 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 30-60 min;
adopt above-mentioned further beneficial effect to lie in: the air blowing pressure defined by the invention can improve the blowing effect by using proper air pressure. And simultaneously reduces the loss of active components of the catalyst caused by overlarge purging strength.
Further, the weak acid in the step (2) is any one of acetic acid, citric acid and hydrobromic acid;
furthermore, 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 6-12 h;
further, the leaching time in the step (3) is 20-30min, the temperature of the forced air drying device is 100-;
further, the crushing particle size in the step (4) is less than 20 mm; grinding to a particle size of 200 μm or less;
adopt above-mentioned further beneficial effect to lie in: the reaction speed between the catalyst and the reaction solution can be increased within the particle size range defined in the present invention.
Further, the concentration of ammonia water in the step (5) is 10-25%; the mass ratio of the catalyst to the ammonia water is 1: 5-20;
further, the concentration of the sodium hydroxide solution in the step (6) is 5-10mol/L, and 20-50ml of the sodium hydroxide solution is mixed with every 1g of the catalyst powder; the hydrothermal temperature is 100-150 ℃, and the hydrothermal time is 12-48 h;
the adjusting acid is hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the adjusting acid is 0.1-0.5 mol/L;
further, 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).
Further, the water is deionized water; the alcohol solvent is one of ethanol, ethylene glycol and isopropanol;
further, in the step (7), each 1g of catalyst is mixed by adopting 20-50ml of hydrothermal solution; the first stirring speed is 500-; the addition amount of dimethylamine is 1/30 of the hydrothermal solution; the second stirring speed is 500-1000rpm, and the stirring time is 1-2 h; the reaction temperature of the reaction kettle is 150-;
furthermore, the rotary evaporation process in the step (7) further comprises adding deionized water.
Adopt above-mentioned further beneficial effect to lie in: the deionized water is utilized to replace the organic solvent in the system, so that the organic solvent is evaporated more thoroughly, the replacement rate can be controlled by adding the deionized water, and the replacement effect is improved.
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 waste denitration catalysts and a pretreatment device, which fill up the blank of relative industries, improve the utilization rate of resources and provide a new idea for an efficient and high-value utilization mode of resources.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic view of an apparatus for preparing titanium oxide nanorods using a waste denitration catalyst according to the present invention;
in fig. 1, the structure represented by each reference numeral is listed as follows: 1-compressed air blowing device, 2-acid cleaning device, 3-leaching device, 4-blast drying box, 5-crushing device, 6-grinding device and 7-stock bin;
FIG. 2 is a schematic view of the compressed air purging device of the present invention;
in fig. 2, the structure represented by each reference numeral is listed as follows:
101-motor, 102-electromagnetic valve electric pump, 103-blowing groove, 104-power-assisted mechanical arm, 105-slide rail, 106-air storage tank, 107-top plate, 108-top plate pulley, 109-groove, 110-compressed air blowing pipe, 111-first grid bracket and 112-ash bucket;
FIG. 3 is a schematic view of the pickling apparatus according to the present invention;
in fig. 3, the structure represented by each reference numeral is listed as follows: 201-a pickling tank, 202-a second grid support, 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 discharging port;
FIG. 4 is a schematic view of the leaching apparatus according to the present invention;
in fig. 4, the structure represented by each reference numeral is listed as follows: 301-a spray pipe, 302-a nozzle, 303-a spray tank, 304-a third grid support, 305-a second cover plate, 306-a slide rail, 307-a second waste liquid collecting box, 308-a servo motor and 309-a second liquid outlet;
FIG. 5 is a schematic view of a storage bin according to the present invention;
in fig. 5, the structure represented by each reference numeral is 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 the titanium oxide nanorods prepared in example 1 of the present invention;
FIG. 7 is a scanning electron microscope image of the titanium oxide nanorods 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 the titanium oxide nanorods prepared in example 5 of the present invention.
Detailed Description
The following examples are intended to illustrate the present invention, but are not intended to limit the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Vertically fixing the denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing the denitration catalyst for 60min by using compressed air under the pressure of 0.5 MPa;
(2) placing the purged catalyst into an acid washing device containing 50% of acetic acid by mass concentration for acid washing for 6 hours, wherein the volume ratio of the catalyst to weak acid is 1: 20; and controlling the temperature to be 30 ℃ by adopting a constant-temperature heating device;
(3) the acid-washed catalyst is put into a leaching device for leaching for 20min and then dried for 2h at 110 ℃;
(4) putting the dried catalyst into a crushing device, crushing the catalyst by using a 20mm sieve, and then putting the catalyst into a grinding device, grinding the catalyst by using a 200 mu m sieve to obtain catalyst powder;
(5) putting the catalyst powder obtained in the step (4) into a first reaction kettle, washing the catalyst powder with 10% ammonia water in a mass ratio of 1:20, magnetically stirring the catalyst powder and the ammonia water for 48 hours to obtain a suspension, centrifuging the obtained suspension, and filtering the suspension to obtain filtered powder;
(6) mixing and stirring the filtered powder obtained in the step (5) with a sodium hydroxide solution with the concentration of 5mol/L to obtain a suspension, mixing 20ml of the sodium hydroxide solution with every 1g of catalyst powder, then carrying out hydrothermal treatment on the suspension at 100 ℃ for 48h, adjusting the pH of the suspension subjected to the hydrothermal treatment to be 1 by adopting hydrochloric acid with the concentration of 0.5mol/L, then centrifuging and filtering, and washing the filtered catalyst to be neutral by using water;
(7) mixing deionized water and ethanol according to the volume ratio of 1:1 to prepare a hydrothermal solution, mixing the cleaned catalyst and the hydrothermal solution, stirring at 1000rpm for 1h, and mixing 20ml of hydrothermal solution for every 1g of catalyst; and then adding dimethylamine into the mixed solution, wherein the addition amount of the dimethylamine is 1/30 of the hydrothermal solution, stirring at 1000rpm for 2h, then placing the mixed solution into a second reaction kettle for reaction, the reaction temperature of the reaction kettle is 150 ℃, the reaction time is 15h, and then placing the reaction solution into a rotary evaporator for rotary evaporation to obtain the titanium oxide nanorod.
Example 2
(1) Vertically fixing the denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing the denitration catalyst for 30min by using compressed air at 1 MPa;
(2) putting the purged catalyst into an acid washing device containing citric acid with the mass concentration fraction of 5% for acid washing for 12 hours, wherein the volume ratio of the catalyst to weak acid is 1: 10; and controlling the temperature to be 50 ℃ by adopting a constant-temperature heating device;
(3) the acid-washed catalyst is put into a leaching device for leaching for 30min and then dried for 5h at 100 ℃;
(4) putting the dried catalyst into a crushing device, crushing the catalyst by using a 20mm sieve, and then putting the catalyst into a grinding device, grinding the catalyst by using a 200 mu m sieve to obtain catalyst powder;
(5) putting the catalyst powder obtained in the step (4) into a first reaction kettle, washing the catalyst powder with 25% ammonia water in a mass ratio of 1:5, magnetically stirring the catalyst powder and the ammonia water for 10 hours to obtain a suspension, centrifuging the obtained suspension, and filtering the suspension to obtain filtered powder;
(6) mixing and stirring the filtered powder obtained in the step (5) with a sodium hydroxide solution with the concentration of 10mol/L to obtain a suspension, mixing 20ml of the sodium hydroxide solution with every 1g of catalyst powder, then carrying out hydrothermal treatment on the suspension at 150 ℃ for 12h, adjusting the pH of the suspension subjected to the hydrothermal treatment to be 1 by adopting hydrochloric acid with the concentration of 0.1mol/L, then carrying out centrifugation and filtration, and washing the filtered catalyst to be neutral by using water;
(7) mixing deionized water and ethylene glycol according to the volume ratio of 1:5 to prepare a hydrothermal solution, mixing the cleaned catalyst and the hydrothermal solution, stirring at 500rpm for 0.5h, and mixing 50ml of hydrothermal solution for every 1g of catalyst; and then adding dimethylamine into the mixed solution, wherein the addition amount of the dimethylamine is 1/30 of the hydrothermal solution, stirring for 1h at 500rpm, then placing the mixed solution into a second reaction kettle for reaction, 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 to obtain the titanium oxide nanorod.
Example 3
(1) Vertically fixing the denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing the denitration catalyst for 45min by using compressed air at 0.7 MPa;
(2) putting the purged catalyst into an acid washing device containing hydrobromic acid with the mass concentration fraction of 30% for acid washing for 9 hours, wherein the volume ratio of the catalyst to weak acid is 1: 15; and controlling the temperature to be 45 ℃ by adopting a constant-temperature heating device;
(3) the acid-washed catalyst is put into a leaching device for leaching for 25min and then dried for 3h at 105 ℃;
(4) putting the dried catalyst into a crushing device, crushing the catalyst by using a 20mm sieve, and then putting the catalyst into a grinding device, grinding the catalyst by using a 200 mu m sieve to obtain catalyst powder;
(5) putting the catalyst powder obtained in the step (4) into a first reaction kettle, washing with ammonia water with the concentration of 15%, wherein the mass ratio of the catalyst powder to the ammonia water is 1:12, then carrying out magnetic stirring for 30 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder;
(6) mixing and stirring the filtered 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 every 1g of catalyst powder, performing hydrothermal treatment on the suspension at 125 ℃ for 30h, adjusting the pH of the suspension subjected to the hydrothermal treatment to be 1.5 by using hydrochloric acid with the concentration of 0.3mol/L, centrifuging and filtering, and washing the filtered catalyst to be neutral by using water;
(7) mixing deionized water, ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:3 to prepare a hydrothermal solution, mixing the cleaned catalyst and the hydrothermal solution, stirring at 700rpm for 0.7h, and mixing 35ml of hydrothermal solution for every 1g of catalyst; and then adding dimethylamine into the mixed solution, wherein the addition amount of the dimethylamine is 1/30 of the hydrothermal solution, stirring at 700rpm for 1.5h, then placing the mixed solution into a second reaction kettle for reaction, 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 to obtain the titanium oxide nanorod.
Example 4
(1) Vertically fixing the denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing the denitration catalyst for 50min by using compressed air under the pressure of 0.9 MPa;
(2) putting the purged catalyst into an acid washing device containing hydrobromic acid with the mass concentration fraction of 30% for acid washing for 6-12h, wherein the volume ratio of the catalyst to weak acid is 1: 10-20; and controlling the temperature to be 30-50 ℃ by adopting a constant temperature heating device;
(3) the acid-washed catalyst is put into a washing device for washing for 22min and then dried for 4h at 102 ℃;
(4) putting the dried catalyst into a crushing device, crushing the catalyst by using a 20mm sieve, and then putting the catalyst into a grinding device, grinding the catalyst by using a 200 mu m sieve to obtain catalyst powder;
(5) putting the catalyst powder obtained in the step (4) into a first reaction kettle, washing the catalyst powder with ammonia water with the concentration of 20%, wherein the mass ratio of the catalyst powder to the ammonia water is 1:8, then carrying out magnetic stirring for 36 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder;
(6) mixing and stirring the filtered powder obtained in the step (5) with a sodium hydroxide solution with the concentration of 7.5mol/L to obtain a suspension, mixing 45ml of the sodium hydroxide solution with every 1g of catalyst powder, then carrying out hydrothermal treatment on the suspension at 115 ℃ for 36h, adjusting the pH of the suspension subjected to the hydrothermal treatment to be 1 by adopting hydrochloric acid with the concentration of 0.3mol/L, then carrying out centrifugation and filtration, and washing the filtered catalyst with water to be neutral;
(7) mixing deionized water, ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:2 to prepare a hydrothermal solution, mixing the cleaned catalyst and the hydrothermal solution, stirring at 900rpm for 0.8h, and mixing 40ml of hydrothermal solution for every 1g of catalyst; and then adding dimethylamine into the mixed solution, wherein the addition amount of the dimethylamine is 1/30 of the hydrothermal solution, stirring the mixture for 2 hours at 900rpm, then placing the mixed solution into a second reaction kettle for reaction, 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 to obtain the titanium oxide nanorod.
Example 5
(1) Vertically fixing the denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing the denitration catalyst for 55min by using compressed air at 0.6 MPa;
(2) placing the purged catalyst into an acid washing device containing 15% of acetic acid by mass concentration for acid washing for 7 hours, wherein the volume ratio of the catalyst to weak acid is 1: 12; and controlling the temperature to be 35 ℃ by adopting a constant-temperature heating device;
(3) the acid-washed catalyst is placed into a leaching device for leaching for 28min and then dried for 3h at 107 ℃;
(4) putting the dried catalyst into a crushing device, crushing the catalyst by using a 20mm sieve, and then putting the catalyst into a grinding device, grinding the catalyst by using a 200 mu m sieve to obtain catalyst powder;
(5) putting the catalyst powder obtained in the step (4) into a first reaction kettle, washing with ammonia water with the concentration of 15%, wherein the mass ratio of the catalyst powder to the ammonia water is 1:15, then carrying out magnetic stirring for 24 hours to obtain a suspension, centrifuging the obtained suspension, and filtering to obtain filter powder;
(6) mixing and stirring the filtered powder obtained in the step (5) and a sodium hydroxide solution with the concentration of 6mol/L to obtain a suspension, mixing 30ml of the sodium hydroxide solution with every 1g of catalyst powder, performing hydrothermal treatment on the suspension at 140 ℃ for 24h, adjusting the pH of the suspension subjected to the hydrothermal treatment to be 2 by using hydrochloric acid with the concentration of 0.4mol/L, centrifuging and filtering, and washing the filtered catalyst to be neutral by using water;
(7) mixing deionized water, ethanol, ethylene glycol and isopropanol according to the volume ratio of 1:4 to prepare a hydrothermal solution, mixing the cleaned catalyst and the hydrothermal solution, stirring at 600rpm for 0.5h, and mixing 40ml of hydrothermal solution for every 1g of catalyst; and then adding dimethylamine into the mixed solution, wherein the addition amount of the dimethylamine is 1/30 of the hydrothermal solution, stirring for 2 hours at 600rpm, then placing the mixed solution into a second reaction kettle for reaction, 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 to obtain 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 relative industries is filled, the resource utilization rate is improved, and a new idea is provided for an efficient and high-value resource utilization mode; the automation is realized, the number of field operators is reduced, the production efficiency is improved, the production cost is reduced, and the industrial production is facilitated.
Examples 1-5 a pretreatment apparatus for preparing titanium oxide nanorods using a waste denitration catalyst is:
the device comprises a compressed air blowing device 1, a pickling 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;
compressed air sweeps device 1, acid dip pickle 2, drip washing device 3, air blast drying cabinet 4, breaker 5, grinder 6 and feed bin 7 respectively with controller electric connection, compressed air sweeps device 1, acid dip pickle 2, drip washing device 3, air blast drying cabinet 4, breaker 5, grinder 6 and feed bin 7 and connects gradually through drive rail.
In one embodiment, the compressed air purging device comprises an electric motor 101, a solenoid valve electric pump 102, a purging groove 103, a power-assisted manipulator 104, a slide rail 105, an air storage tank 106 and two top plates 107; the motor 101 is electrically connected with the purging tank 103, the two top plates 107 are symmetrically and slidably connected to the upper end of the purging tank 103 through top plate pulleys 108 respectively, the top plates 107 are provided with a plurality of grooves 109, compressed air injection pipes 110 are arranged in the grooves 109, and the compressed air injection pipes 110 are fixedly connected with the air storage tank 106; the electromagnetic valve electric pump 102 is electrically connected with the slide rail 105, and the power-assisted manipulator 104 is slidably connected with the lower surface of the slide rail 105.
In another embodiment, the bottom of the inner surface of the purging groove 103 is provided with a grid support 111; an ash hopper 112 is arranged at the bottom of the outer surface of the purging groove 103.
In another embodiment, the pickling device comprises a pickling tank 201, a second grid support 202, an ultrasonic generator 203, a constant temperature heater 204, a temperature controller 205, a first waste liquid collecting box 206 and a first cover plate 207; the first cover plate 207 is positioned on the 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 both fixed in 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 drainage port 208, and the first drainage port 208 is connected with a first waste liquid collecting tank 206 through a pipeline.
In one embodiment, the leaching apparatus comprises a spraying 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, the nozzles 302 are 7 vertical nozzles and 7 vertical nozzles, and the spraying pipe 301 is fixedly connected with the nozzles 302; the shower pipe 301 and the nozzle 302 are fixed in a second cover plate 305, the second cover plate 305 is fixed on a slide rail 306, and the slide rail 306 is controlled by a servo motor 308; the third grid support 304 is fixed at the bottom of the inner surface of the leaching tank 303, a second liquid outlet 309 is formed in 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 silo includes a first reaction vessel 71, a second reaction vessel 72, a rotary evaporator 73; the first reaction kettle 71, the second reaction kettle 72 and the rotary evaporator 73 are connected in sequence through a sliding guide rail; 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 nano-rod by using the waste denitration catalyst comprises the following steps: fixing the waste denitration catalyst by using a power-assisted manipulator, and placing the waste denitration catalyst in a compressed air blowing device for blowing to remove surface dust; then the waste denitration catalyst is placed in an acid washing device for acid washing through a conveying guide rail, and soluble ions and groups such as K, Na and Ca on the surface are removed; after acid washing, placing the waste denitration catalyst in a leaching device through a sliding guide rail for leaching, and then placing the waste denitration catalyst in a blast drying oven for drying; then putting the waste denitration catalyst into a crushing device and a grinding device for crushing and grinding through a sliding guide rail; and then the waste denitration catalyst is placed in a bin through a sliding guide rail for reaction to obtain the titanium oxide nanorod.
In the description of the present invention, it is to 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 those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A device for preparing titanium oxide nanorods by using waste denitration catalysts comprises a blast drying oven, a crushing device and a grinding device, and is characterized by also comprising a compressed air blowing device, an acid washing device, a leaching device, a storage bin and a controller;
compressed air sweeps device, acid dip pickle, drip washing device, air blast drying cabinet, breaker, grinder and feed bin respectively with controller electric connection, compressed air sweeps device, acid dip pickle, drip washing device, air blast drying cabinet, breaker, grinder and feed bin and connects gradually through drive rail.
2. The apparatus of claim 1, wherein the compressed air purging device comprises a motor, a solenoid valve motor pump, a purging tank, a power-assisted manipulator, a slide rail, a gas storage tank, a top plate pulley, and at least one top plate;
the motor is electrically connected with the purging tank;
the top plate pulley is fixedly connected with the top end of the blowing groove, and the top plate is connected with the top plate pulley in a sliding manner; the top plate is provided with a plurality of grooves, compressed air injection pipes are arranged in the grooves, and the compressed air injection 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 apparatus of claim 2, wherein the bottom of the inner surface of the purge tank is provided with a first mesh support; an ash hopper is arranged at the bottom of the outer surface of the blowing groove.
4. The apparatus of claim 1, wherein the pickling device comprises a pickling tank, a second grid support, an ultrasonic generator, a constant temperature heater, a temperature controller, a first waste liquid collection 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 inside the pickling tank;
the constant-temperature heating device is electrically connected with the temperature control instrument; the bottom of the pickling tank is provided with a first liquid discharge port, and the first liquid discharge port is connected with the first waste liquid collecting box through a pipeline.
5. The apparatus of claim 1, wherein the leaching apparatus comprises a spraying system, a leaching tank, a third grid support, a second cover plate, a slide rail and a second waste liquid collection box;
the spraying system comprises a spraying pipe and a plurality of nozzles, and the spraying pipe is fixedly connected with the nozzles; the spraying pipe and the 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 to the bottom of the inner surface of the leaching tank, a second liquid outlet is formed in the bottom of the leaching tank, and the second liquid outlet is connected with the second waste liquid collecting box through a pipeline.
6. The apparatus for preparing titanium oxide nanorods by using the waste denitration catalyst according to claim 1, wherein the silo comprises a first reaction kettle, a second reaction kettle, a rotary evaporator; the first reaction kettle, the second reaction kettle and the rotary evaporator are sequentially connected through a sliding guide rail; and a stirring device, a centrifugal device and a filtering device are arranged in the first reaction kettle.
7. The method for preparing the titanium oxide nanorods by using the waste denitration catalyst according to any one of claims 1 to 6, comprising the steps of:
(1) vertically fixing a denitration catalyst on a power-assisted manipulator of a compressed air blowing device, and blowing by compressed air;
(2) transferring the purged catalyst to an acid washing device containing weak acid for acid washing, and controlling the temperature to be 30-50 ℃;
(3) transferring the acid-washed catalyst to a leaching device for leaching, and then drying;
(4) crushing the dried catalyst in a crushing device, and then grinding the crushed catalyst in a grinding device to obtain catalyst powder;
(5) putting the obtained catalyst powder into a first reaction kettle, washing the catalyst powder by using ammonia water, stirring the catalyst powder for 10 to 48 hours to obtain a suspension, centrifuging the suspension, and filtering the suspension to obtain filtered powder;
(6) mixing and stirring the filtered powder and a sodium hydroxide solution to obtain a suspension, carrying out hydrothermal treatment on the suspension, adjusting the pH to 1-2 by using an acid, carrying out centrifugal filtration, and washing the filtered catalyst to be neutral;
(7) mixing the catalyst treated in the step (6) with the 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 finished to obtain the titanium oxide nanorod.
8. The method for preparing titanium oxide nanorods by using the waste denitration catalyst according to claim 7, wherein the weak acid in the step (2) is any one of acetic acid, citric acid and hydrobromic acid, and the mass concentration fraction of the weak acid is 5-50%.
9. The method for preparing titanium oxide nanorods by using the waste denitration catalyst as claimed in claim 7, wherein the hydrothermal solution in the step (7) is prepared by mixing water and alcohol solvent in a volume ratio of 1 (1-5).
10. The method for preparing titanium oxide nanorods by using the waste denitration catalyst according to claim 9, wherein the water is deionized water; the alcohol solvent is one of ethanol, ethylene glycol and isopropanol.
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