CN113909470B

CN113909470B - Zirconium or hafnium chip-shaped standard sample pickling device and process

Info

Publication number: CN113909470B
Application number: CN202111268518.XA
Authority: CN
Inventors: 白新房; 贾远; 朱波; 李建峰; 周恺; 房永强; 樊建勋; 杨军红
Original assignee: Xi'an Hantang Analysis Detection Co ltd; Northwest Institute for Non Ferrous Metal Research
Current assignee: Xi'an Hantang Analysis Detection Co ltd; Northwest Institute for Non Ferrous Metal Research
Priority date: 2021-10-29
Filing date: 2021-10-29
Publication date: 2023-04-28
Anticipated expiration: 2041-10-29
Also published as: CN113909470A

Abstract

The invention discloses a zirconium or hafnium chip-shaped standard sample pickling device which comprises a box body with an opening at the top and a box cover matched with the box body, wherein a first spray head, a second spray head and a third spray head are arranged on the box cover; the invention also discloses a process for pickling the zirconium or hafnium chip-shaped standard sample. According to the invention, the screen basket for containing the zirconium or hafnium chip-shaped standard sample is connected with the vibration generator, so that the screen basket is fully contacted with the pickling solution, and the pickling decontamination effect is improved; the invention adopts acid liquor dissolution, clear water washing and ethanol solution washing respectively, and improves the pickling decontamination effect by matching with the vibration action of the vibration generator, thereby avoiding excessive pickling.

Description

Zirconium or hafnium chip-shaped standard sample pickling device and process

Technical Field

The invention belongs to the technical field of chemical experimental equipment, and particularly relates to a zirconium or hafnium chip-shaped standard sample pickling device and a process.

Background

Zirconium and hafnium have the excellent performances of high melting point, good corrosion resistance, excellent processability and the like, and are applied to the field of nuclear industry. The zirconium alloy has the characteristic of small neutron absorption section and is mainly used for key structural materials such as a nuclear reactor core cladding tube, an end plug, a positioning grid and the like; hafnium has the characteristics of large neutron absorption section and high emissivity, and is mainly applied to nuclear reactor core control rod materials. In the development and production process of zirconium and hafnium materials, the content control of alloying elements, impurity elements and other components directly influences the usability of the materials. In the analysis process of alloy elements and impurity elements, a calibration curve and process quality control are established by using zirconium and hafnium chemical standard samples (scraps) so as to ensure the accuracy and reliability of detection results.

The chip-shaped standard sample for zirconium and hafnium chemical analysis needs to be subjected to acid washing and decontamination treatment after molding processing. Because the size of the chip-shaped sample formed by processing is small, ensuring uniform removal of sample surface pollution in the pickling process becomes one of the difficulties in the pickling process of the chip-shaped sample. Therefore, the design and development of a more effective pickling device and pickling process have important application value for developing standard substances for chemical analysis.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a zirconium or hafnium chip-shaped standard sample pickling device aiming at the defects of the prior art. The screen basket for containing the zirconium or hafnium chip-shaped standard sample is arranged on the pickling device and is connected with the vibration generator, the zirconium or hafnium chip-shaped standard sample in the screen basket is driven to swing, overturn and reciprocate in the pickling process by controlling the horizontal vibration of the vibration generator, so that the zirconium or hafnium chip-shaped standard sample is fully contacted with a pickling solution, pollutants on the surface of the zirconium or hafnium chip-shaped standard sample are fully and uniformly removed, and the pickling decontamination effect is greatly improved.

In order to solve the technical problems, the invention adopts the following technical scheme: zirconium or hafnium bits form standard sample acid dip pickle, its characterized in that, including open-top's box and with box complex case lid, first shower nozzle, second shower nozzle and third shower nozzle have been seted up on the case lid, be provided with the support on the inner bottom plate of box, fixedly connected with pivot on the support, the lateral part of pivot is connected with the funnel, the inside accommodation of funnel has the sieve basket, and the sieve basket overcoat has connect the lantern ring, the slide opening has been seted up to the level on the lateral wall of funnel, swing joint has the slide column in the slide opening, and the one end and the lantern ring of slide column are connected, and the other end is connected with vibration generator.

The zirconium or hafnium bits form standard sample pickling device, a serial communication port, first shower nozzle, second shower nozzle and third shower nozzle correspond respectively with first liquid supply device, second liquid supply device and third liquid supply device are connected, and be provided with first solenoid valve between first shower nozzle and the first liquid supply device, be provided with the second solenoid valve between second shower nozzle and the second liquid supply device, be provided with the third solenoid valve between third shower nozzle and the third liquid supply device, and first solenoid valve, second solenoid valve and third solenoid valve all are connected with the controller.

The zirconium or hafnium chip standard sample pickling device is characterized in that a first cylinder body, a second cylinder body and a third cylinder body are respectively arranged below the inner bottom plate of the box body, which corresponds to the first spray head, the second spray head and the third spray head.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that a sample outlet is formed in the box cover.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that the vibration generator is connected with the controller.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that the rotating shaft is connected with the power device, and the power device is connected with the controller.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that filter cotton cloth is paved on the inner surface of the screen basket.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that a corrosion-resistant plate is paved on the inner bottom plate of the box body.

The zirconium or hafnium chip-shaped standard sample pickling device is characterized in that a liquid outlet is formed in the lower side wall of the box body.

In addition, the invention also discloses a process for pickling the zirconium or hafnium chip standard sample by using the pickling device, which is characterized by comprising the following steps:

step one, paving a zirconium or hafnium chip-shaped standard sample in a screen basket, and then rotating a rotating shaft to enable a funnel to rotate below a first spray head;

step two, opening a first spray head to spray acid liquor onto a zirconium or hafnium chip-shaped standard sample in the screen basket, opening a vibration generator to enable the zirconium or hafnium chip-shaped standard sample to be subjected to acid liquor pickling for 10-15 s while vibrating, and then closing the first spray head and the vibration generator; the spraying flow rate of the acid liquor is 0.3 m/s-0.5 m/s;

step three, rotating the rotating shaft to enable the funnel to rotate below the second spray head, starting the second spray head to spray clean water onto the zirconium or hafnium chip-shaped standard sample in the screen basket, starting the vibration generator to enable the zirconium or hafnium chip-shaped standard sample subjected to acid washing in the step two to be washed with clean water for 30-40 s while vibrating, and then closing the second spray head and the vibration generator; the spraying flow rate of the clean water is 0.3 m/s-0.5 m/s;

turning a rotating shaft to enable a funnel to rotate below a third spray head, starting the third spray head to spray an ethanol solution onto zirconium or hafnium chip-shaped standard samples in a screen basket, starting a vibration generator to enable the zirconium or hafnium chip-shaped standard samples washed by clean water in the third step to be washed by the ethanol solution for 10 s-15 s while vibrating, then closing the third spray head and the vibration generator, taking out the zirconium or hafnium chip-shaped standard samples washed by the ethanol solution, tiling and airing; the spraying flow rate of the clean water is 0.3 m/s-0.5 m/s.

Compared with the prior art, the invention has the following advantages:

1. according to the pickling device disclosed by the invention, the sieve basket for containing the zirconium or hafnium chip-shaped standard sample is placed in the funnel, the sieve basket is connected with the vibration generator through the sliding column movably connected in the sliding hole on the side wall of the funnel, and the zirconium or hafnium chip-shaped standard sample in the sieve basket is driven to shake, overturn and reciprocate in the pickling process by controlling the horizontal vibration of the vibration generator, so that the zirconium or hafnium chip-shaped standard sample is fully contacted with a pickling solution, pollutants on the surface of the zirconium or hafnium chip-shaped standard sample are fully and uniformly removed, and the pickling decontamination effect is greatly improved.

2. According to the pickling device disclosed by the invention, the spray heads are arranged on the box cover to spray the pickling solution on the zirconium or hafnium chip-shaped standard samples in the screen basket in the vertical direction, so that the spraying direction of the pickling solution in the vibration direction of the screen basket is vertical, splashing of the pickling solution caused by vibration of the screen basket is greatly reduced, continuous pickling is realized by arranging the special spray heads for different pickling solutions, and the pickling efficiency is improved.

3. According to the pickling device, the cylinder bodies are arranged below the corresponding spray heads respectively and are used for receiving the pickling waste liquid discharged from the hopper, so that the pickling waste liquid can be conveniently classified and collected and intensively treated, and the environmental pollution is effectively prevented.

4. According to the pickling device disclosed by the invention, the filter cotton cloth is paved on the inner surface of the screen basket, so that the flow velocity of a pickling solution is effectively reduced, the vibration amplitude is buffered, the leakage loss of a zirconium or hafnium chip-shaped standard sample with a smaller size is avoided, meanwhile, the contact action time of the pickling solution is prolonged by intercepting the pickling solution, and the pollutants on the surface of the zirconium or hafnium chip-shaped standard sample are further fully removed.

5. According to the invention, aiming at the acid washing process of the zirconium or hafnium chip-shaped standard sample, acid liquor dissolution, clear water washing and ethanol solution washing are respectively adopted, and the turnover of the zirconium or hafnium chip-shaped standard sample and the full contact of each acid washing solution are promoted by matching with the vibration action of the vibration generator, so that the acid washing decontamination effect is greatly improved, and the excessive consumption of the zirconium or hafnium chip-shaped standard sample caused by excessive local acid washing reaction in the zirconium or hafnium chip-shaped standard sample is avoided.

The technical scheme of the invention is further described in detail through the drawings and the embodiments.

Drawings

FIG. 1 is a cross-sectional view of a zirconium or hafnium chip sample pickling device according to the present invention.

FIG. 2 is a cross-sectional view taken along the A-A plane of FIG. 1.

FIG. 3 is a top view of a zirconium or hafnium chip sample pickling device according to the present invention.

Reference numerals illustrate:

1-a box cover; 1-a first nozzle; 1-2-a second nozzle;

1-3-third nozzle; 1-4-a first solenoid valve; 1-5-a second electromagnetic valve;

1-6-a third electromagnetic valve; 1-7, a lofting port; 2, a box body;

2-1-a bracket; 2-a power device; 2-3-rotating shaft;

3-1-a first cylinder; 3-2-a second cylinder; 3-a third cylinder;

4, a funnel; 4-1-sieving basket; 4-2-filtering cotton cloth;

4-3-collar; 4-slide column; 4-5-vibration generator;

5-a corrosion-resistant plate; 6-liquid outlet.

Detailed Description

Example 1

As shown in fig. 1, 2 and 3, the zirconium or hafnium chip-shaped standard sample pickling device of the embodiment comprises a box body 2 with an opening at the top and a box cover 1 matched with the box body 2, wherein a first spray head 1-1, a second spray head 1-2 and a third spray head 1-3 are arranged on the box cover 1, a support 2-1 is arranged on an inner bottom plate of the box body 2, a rotating shaft 2-3 is fixedly connected to the support 2-1, a funnel 4 is connected to the side part of the rotating shaft 2-3, a sieve basket 4-1 is accommodated in the funnel 4, a lantern ring 4-3 is sleeved outside the sieve basket 4-1, a slide hole is horizontally formed in the side wall of the funnel 4, a slide column 4-4 is movably connected to the slide hole, one end of the slide column 4-4 is connected with the lantern ring 4-3, and the other end of the slide column is connected with a vibration generator 4-5.

The zirconium or hafnium chip standard pickling device according to this embodiment comprises two main body portions: the box body 2 and the box cover 1 matched with the box body 2, and three spray heads, namely a first spray head 1-1, a second spray head 1-2 and a third spray head 1-3 are arranged on the box cover 1, and the cleaning of pollutants on the surface of a conventional zirconium or hafnium chip standard sample is divided into three stages: the first stage adopts the acidizing fluid to dissolve and clear away impurity such as oxide on zirconium or hafnium bits form standard sample surface, the second stage adopts clear water to wash and continue to get rid of impurity that the first stage was dissolved, the third stage adopts ethanol solution to further get rid of impurity such as impurity that the first stage was dissolved and remaining greasy dirt, this embodiment is directed at three pickling solution acidizing fluid that pickling is related, clear water and ethanol solution, set up three shower nozzle in proper order correspondingly, with be used for introducing acidizing fluid, clear water and ethanol solution respectively and spray, combine the rotation effect of pivot 2-3 to drive funnel 4 rotation, make zirconium or hafnium bits form standard sample that sieve basket 4-1 placed in funnel 4 rotate to the below of first shower nozzle 1-1 in proper order, second shower nozzle 1-2 and third shower nozzle 1-3, thereby spray different pickling solutions to zirconium or hafnium bits form standard sample in different cleaning stages and carry out the pickling work, need not frequently change the pickling solution in same shower nozzle department, the cross contamination of pickling solution has been avoided, continuous pickling efficiency has been realized.

Meanwhile, the device is characterized in that the support 2-1 is arranged on the inner bottom plate of the box body 2, the rotating shaft 2-3 is fixedly connected to the support 2-1, the funnel 4 is connected to the side part of the rotating shaft 2-3, the support 2-1 is adopted as a base for supporting the rotating shaft 2-3, stable operation of the rotating shaft 2-3 is guaranteed, a certain distance is kept between the funnel 4 and the inner bottom plate of the box body 2, and rotation of the funnel 4 is facilitated; according to the device, the sieve basket 4-1 is placed in the funnel 4 and serves as a place for placing and pickling zirconium or hafnium chip-shaped standard samples, the sleeve ring 4-3 is sleeved outside the sieve basket 4-1, the sleeve ring 4-3 is arranged on the side wall of the funnel 4, one end of the sliding column 4-4 movably connected in the sliding hole is connected with the sleeve ring 4-3, the other end of the sliding column 4-4 is connected with the vibration generator 4-5, namely the sieve basket 4-1 is indirectly connected with the vibration generator 4-5 through the sliding column 4-4, in the pickling process, the sliding column 4-5 is started to drive the sliding column 4-4 to move in the sliding hole, and under the limiting effect of the sliding hole, the sliding column 4-4 only can vibrate along the axial direction of the sliding hole, namely the horizontal direction, so that the sleeve ring 4-3 drives the sieve basket 4-1 to vibrate along the sliding direction, the zirconium or hafnium chip-shaped standard samples shake and overturn in the pickling process, and fully contact with the pickling solution, so that all zirconium or hafnium chip-shaped standard samples can be washed by the pickling solution, zirconium or hafnium chip-shaped standard samples can be fully and evenly removed, and zirconium or zirconium chip-shaped standard samples are greatly polluted, and zirconium sample excessive consumption or zirconium sample local excessive consumption is avoided; after pickling, the pickling waste liquid containing pollutants leaks from the sieve holes of the sieve basket 4-1 and flows out along the discharge spout of the funnel 4, so that the secondary pollution of the residual pollutants on the sieve basket 4-1 to zirconium or hafnium filings is avoided, and the concentration of the pickling solution sprayed subsequently is ensured to improve the cleaning effect. Generally, the screen basket 4-1 is horizontally placed in the funnel 4, and the pickling solution is sprayed on zirconium or hafnium chip-shaped standard samples in the screen basket 4-1 along the vertical direction through a spray nozzle arranged on the box cover 1, at the moment, the movement direction of the screen basket 4-1 is vertical to the spraying direction of the pickling solution, so that the splashing of the pickling solution caused by the vibration of the screen basket 4-1 is greatly reduced.

Further, 2 sliding holes are horizontally and symmetrically formed in the side wall of the funnel 4, wherein a sliding column 4-4 in the sliding hole close to the vibration generator 4-5 is connected with the lantern ring 4-3 at one end, the other end is connected with the vibration generator 4-5, a sliding column 4-4 in the sliding hole far away from the vibration generator 4-5 is connected with the lantern ring 4-3 at one end, and the other end penetrates out of the side wall of the funnel 4 and is connected with a limiting block at the end. According to the embodiment, 2 slide holes are horizontally and symmetrically formed in the side wall of the funnel 4, the screen basket 4-1 vibrates in the horizontal direction opposite to the two slide holes by utilizing the connection effect of the slide column and the lantern ring 4-3 in each slide hole, and on the premise that the zirconium or hafnium chip-shaped standard sample is ensured to be fully contacted with the pickling solution, the phenomenon that the zirconium or hafnium chip-shaped standard sample collides irregularly due to vibration in a plurality of horizontal directions and is scattered outside the screen basket 4-1 to cause loss is avoided; meanwhile, the sliding column 4-4 limited at only one end is connected with the vibration generator 4-5, so that the screen basket 4-1 only vibrates under the vibration action of the vibration generator 4-5 at one end, and the phenomenon of counteracting the vibration action of the vibration generator 4-5 in different directions, particularly in the symmetrical direction, is avoided; one end of a sliding column 4-4 in a sliding hole far away from the vibration generator 4-5 is connected with the lantern ring 4-3, so that the vibration of the screen basket 4-1 along the horizontal direction is ensured, the other end penetrates out of the side wall of the funnel 4 and is connected with a limiting block at the end part, the falling off of the sliding column 4-4 is avoided, and the smooth running of the vibration of the screen basket 4-1 is ensured.

Further, in this embodiment, more than 2 identical funnels 4 are connected to the side of the rotating shaft 2-3. Through setting up more than 2 identical funnels 4, place zirconium or hafnium form standard sample at the screen basket 4-1 of funnel 4 in proper order, then according to three washing stage rotatory pivot 2-3 and drive each funnel 4 rotation for each funnel 4 rotates in proper order and reaches corresponding shower nozzle below, and sprays corresponding pickling solution, thereby realized going on of different zirconium or hafnium form standard sample continuous pickling work in same pickling process, improved pickling efficiency greatly.

Further, in this embodiment, the first nozzle 1-1, the second nozzle 1-2, and the third nozzle 1-3 are respectively connected to the first liquid supply device, the second liquid supply device, and the third liquid supply device correspondingly, and a first electromagnetic valve 1-4 is disposed between the first nozzle 1-1 and the first liquid supply device, a second electromagnetic valve 1-5 is disposed between the second nozzle 1-2 and the second liquid supply device, a third electromagnetic valve 1-6 is disposed between the third nozzle 1-3 and the third liquid supply device, and the first electromagnetic valve 1-4, the second electromagnetic valve 1-5, and the third electromagnetic valve 1-6 are all connected to the controller. Because the pickling solutions sprayed in the spray heads are different, the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3 are respectively correspondingly connected with the first liquid supply device, the second liquid supply device and the third liquid supply device, so that the spraying of different pickling solutions through the special spray heads is realized, the cross contamination of different pickling solutions is further avoided, and the continuous carrying out of pickling work is facilitated. In general, the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3 are used for spraying acid solution, clear water and ethanol solution, respectively, and the corresponding first liquid supply device, second liquid supply device and third liquid supply device are used for supplying acid solution, clear water and ethanol solution, respectively. Meanwhile, electromagnetic valves are arranged between the spray heads and the corresponding liquid supply devices, all the electromagnetic valves are connected with a controller, and the controller is used for controlling the opening and closing of the electromagnetic valves, namely the first electromagnetic valve 1-4, the second electromagnetic valve 1-5 and the third electromagnetic valve 1-6, according to different stages of the set pickling work, so that the spraying on-off and the spraying flow rate of each pickling solution in the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3 are controlled, the pickling reaction process is accurately controlled, the continuous carrying out of the pickling work is ensured, and the pickling device is convenient, quick and accurate in regulation and control.

Further, in this embodiment, a first cylinder 3-1, a second cylinder 3-2, and a third cylinder 3-3 are disposed on the inner bottom plate of the case 2, corresponding to the lower portions of the first nozzle 1-1, the second nozzle 1-2, and the third nozzle 1-3, respectively. According to the embodiment, the first cylinder body 3-1, the second cylinder body 3-2 and the third cylinder body 3-3 are respectively arranged below the corresponding first spray head 1-1, the second spray head 1-2 and the third spray head 1-3 and are respectively used for receiving waste pickle liquor discharged from the hopper 4, namely waste acid liquor, waste water and waste ethanol solution, so that the waste pickle liquor can be conveniently classified, collected and intensively treated, and the environmental pollution is effectively prevented.

As shown in fig. 2 and 3, further, in this embodiment, the case cover 1 is provided with a loft hole 1-7. According to the embodiment, the lofting ports 1-7 are formed in the case cover 1 and serve as channels for placing zirconium or hafnium chip-shaped standard samples, lofting can be performed without opening the case cover 1, convenience and labor saving are achieved, and pickling efficiency is improved.

Further, the vibration generator 4-5 is connected to a controller in this embodiment. In the embodiment, the opening and closing of the vibration generator 4-5 and the vibration process are regulated and controlled by the controller, so that the vibration process of the screen basket 4-1 along the horizontal direction is effectively controlled.

Further, in this embodiment, the rotating shaft 2-3 is connected to the power unit 2-2, and the power unit 2-2 is connected to the controller. In the embodiment, the rotating shaft 2-3 is connected with the power device 2-2, the power device 2-2 is connected with the controller, and the controller is used for controlling the work of the power device 2-2 to drive the rotating shaft 2-3 to rotate, so that the funnel 4 is driven to rotate to the spray heads to perform pickling work in different cleaning stages, the rotating shaft 2-3 does not need to be manually rotated, the automation degree of the pickling device is improved, and the pickling work efficiency of zirconium or hafnium chip standard samples is further improved.

In general, the controller to which the first solenoid valve 1-4, the second solenoid valve 1-5 and the third solenoid valve 1-6 are connected, the controller to which the vibration generator 4-5 is connected and the controller to which the power generator 2-2 is connected in this embodiment are commonly used in the model of Mitsubishi FX3U-48MR/ES-A. The volume accuracy of the acid pickling solution sprayed in each spray head is improved through the action of the controller and the servo motor, the rotating position accuracy of the zirconium or hafnium chip-shaped standard sample placed in the screen basket 4-1 in the funnel 4 and the accuracy of the vibration generator 4-5 in the shaking, overturning and reciprocating motion of the zirconium or hafnium chip-shaped standard sample in the acid pickling process are improved.

Further, in this embodiment, a filter cotton cloth 4-2 is laid on the inner surface of the screen basket 4-1. In the embodiment, the filter cotton cloth 4-2 is paved on the inner surface of the screen basket 4-1 for containing zirconium or hafnium chip-shaped standard samples, so that on one hand, the flow rate of the pickling solution is effectively reduced, the vibration amplitude is buffered, the phenomenon that zirconium or hafnium chip-shaped standard samples with smaller sizes leak out of the screen holes of the screen basket 4-1 under the spraying action of the pickling solution or the vibration action of the screen basket 4-1 is avoided, the loss of the zirconium or hafnium chip-shaped standard samples is caused, on the other hand, the filter cotton cloth 4-2 is favorable for intercepting the pickling solution to a certain extent, the contact action time of the pickling solution and the zirconium or hafnium chip-shaped standard samples is prolonged, the pollutants on the surface of the zirconium or hafnium chip-shaped standard samples are sufficiently removed, the filtering characteristic of the filter cotton cloth 4-2 ensures that the outflow of the pickling waste liquid is not influenced, and the pickling effect is improved. Generally, the warp and weft density of the filter cotton cloth 4-2 is about 200-300, and the filter cotton cloth 4-2 is replaced once every four times of pickling work, so that the filter cotton cloth 4-2 is prevented from being damaged due to excessive pickling work.

Further, in this embodiment, a corrosion-resistant plate 5 is laid on the inner bottom plate of the case 2. In this embodiment, the corrosion-resistant plate 5 is laid on the inner bottom plate of the box body 2 to block the acidic liquid flowing out or splashing from the funnel 4, so as to prevent the acidic liquid from corroding the inner bottom plate of the box body 2, and prolong the service life of the pickling device.

Further, in this embodiment, a drain port 6 is formed on the lower side wall of the case 2. According to the embodiment, the liquid outlet 6 is formed in the lower side wall of the box body 2, so that the pickling solution or pickling waste liquid flowing out or splashing from the funnel 4 can be discharged from the box body, and the corrosion damage effect of the acid liquid on other structures in the pickling device is avoided.

Further, in this embodiment, the first spray head 1-1, the second spray head 1-2, the third spray head 1-3, the hopper 4, the screen basket 4-1, the first cylinder body 3-1, the second cylinder body 3-2 and the third cylinder body 3-3 are all made of white polyethylene plastics, and corrosion resistance of the white polyethylene plastics is utilized to effectively prevent the corrosion damage of the components in the pickling process, prolong the service life of the pickling device, and simultaneously avoid pollution to zirconium or hafnium chip standard samples.

The process of pickling zirconium or hafnium chip-shaped standard samples by using the pickling device according to the present invention is described in detail by examples 2 to 3.

Example 2

The embodiment comprises the following steps:

step one, paving a zirconium chip-shaped standard sample in a sieve basket 4-1 through a lofting port 1-7, and then controlling the work of a power device 2-2 to drive a rotating shaft 2-3 to rotate by utilizing a controller so that a funnel 4 rotates to the lower part of a first spray head 1-1;

step two, opening a first spray head 1-1 to spray acid liquor onto the zirconium chip-shaped standard sample in the screen basket 4-1, controlling the spraying flow rate through a first electromagnetic valve 1-4, simultaneously opening a vibration generator 4-5 through a controller to enable the zirconium chip-shaped standard sample to be subjected to acid liquor pickling for 15s while vibrating, and then closing the first spray head 1-1 and the vibration generator 4-5; the spraying flow rate of the acid liquor is 0.3m/s;

step three, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate below the second spray head 1-2, starting the second spray head 1-2 to spray clean water onto the zirconium chip-shaped standard sample in the screen basket 4-1, starting the vibration generator 4-5, enabling the zirconium chip-shaped standard sample subjected to acid washing in the step two to be washed with clean water for 30s while vibrating, and then closing the second spray head 1-2 and the vibration generator 4-5; the spraying flow rate of the clean water is 0.3m/s;

step four, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate below the third spray head 1-3, opening the third spray head 1-3 to spray ethanol solution onto the zirconium chip-shaped standard sample in the screen basket 4-1, opening the vibration generator 4-5 to enable the zirconium chip-shaped standard sample washed by clean water in the step three to be washed by ethanol solution for 15s while vibrating, then closing the third spray head 1-3 and the vibration generator 4-5, taking out the zirconium chip-shaped standard sample washed by the ethanol solution, tiling and airing; the spraying flow rate of the clean water is 0.3m/s.

According to detection, the mass contents of Cr, fe, nb, sn elements in the zirconium chip-shaped standard sample before the pickling treatment are respectively 0.082%, 0.332%, 0.302% and 0.958%, and the mass contents of Cr, fe, nb, sn elements in the zirconium chip-shaped standard sample after the pickling treatment are respectively 0.080%, 0.328%, 0.302% and 0.960%, namely the mass contents of main elements in the zirconium chip-shaped standard sample before and after the pickling treatment are basically consistent, which indicates that the pickling process effectively fills and removes pollutants on the surface of the zirconium chip-shaped standard sample and does not influence the components of the zirconium chip-shaped standard sample by excessive pickling.

Example 3

The embodiment comprises the following steps:

step one, a hafnium chip-shaped standard sample is paved in a sieve basket 4-1 through a lofting port 1-7, and then a controller is used for controlling the work of a power device 2-2 to drive a rotating shaft 2-3 to rotate, so that a funnel 4 rotates to the lower part of a first spray head 1-1;

step two, opening a first spray head 1-1 to spray acid liquor onto hafnium chip-shaped standard samples in a screen basket 4-1, controlling the spraying flow rate through a first electromagnetic valve 1-4, simultaneously opening a vibration generator 4-5 through a controller to enable the zirconium chip-shaped standard samples to be subjected to acid liquor pickling for 10s while vibrating, and then closing the first spray head 1-1 and the vibration generator 4-5; the spraying flow rate of the acid liquor is 0.5m/s;

step three, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate below the second spray head 1-2, starting the second spray head 1-2 to spray clear water onto hafnium chip-shaped standard samples in the screen basket 4-1, starting the vibration generator 4-5, enabling the hafnium chip-shaped standard samples subjected to acid washing in the step two to be washed with clear water for 40s while vibrating, and then closing the second spray head 1-2 and the vibration generator 4-5; the spraying flow rate of the clean water is 0.5m/s;

step four, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate below the third spray head 1-3, starting the third spray head 1-3 to spray ethanol solution onto hafnium chip-shaped standard samples in the screen basket 4-1, starting the vibration generator 4-5 to enable the hafnium chip-shaped standard samples washed by clean water in the step three to be washed by ethanol solution for 10s while vibrating, then closing the third spray head 1-3 and the vibration generator 4-5, taking out the hafnium chip-shaped standard samples washed by the ethanol solution, tiling and airing; the spraying flow rate of the clean water is 0.5m/s.

According to detection, the mass content of Zr element in the hafnium-chip standard sample before the pickling treatment is 0.24%, and the mass content of Zr element in the hafnium-chip standard sample after the pickling treatment is still 0.24%, namely the mass content of Zr element in the hafnium-chip standard sample before and after the pickling treatment is basically consistent, which indicates that the pickling process of the invention effectively removes pollutants on the surface of the hafnium-chip standard sample and does not excessively influence the composition of the hafnium-chip standard sample.

The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims

1. The utility model provides a zirconium or hafnium bits form standard sample pickling device, its characterized in that includes open-top box (2) and with box (2) complex case lid (1), first shower nozzle (1-1), second shower nozzle (1-2) and third shower nozzle (1-3) have been seted up on case lid (1), first shower nozzle (1-1), second shower nozzle (1-2) and third shower nozzle (1-3) correspond respectively with first liquid supply device, second liquid supply device and third liquid supply device are connected, first shower nozzle (1-1), second shower nozzle (1-2) and third shower nozzle (1-3) are used for spraying acidizing fluid, clear water and ethanol solution respectively, correspond first liquid supply device, second liquid supply device and third liquid supply device and are used for supplying acidizing fluid, clear water and ethanol solution respectively, be provided with support (2-1) on the inner bottom plate of box (2), fixedly connected with pivot (2-3) on support (2-1), side portion (2-3) are connected with funnel (4) in the pivot (2-3), slide column (4) have in the side of slide screen (4) have, slide screen (4) have in the side wall (4) open in the level screen (4) has, slide screen (4) has a horizontal screen (4), one end of the sliding column (4-4) is connected with the lantern ring (4-3), and the other end is connected with the vibration generator (4-5).

2. The zirconium or hafnium chip standard pickling device according to claim 1, wherein a first electromagnetic valve (1-4) is arranged between the first spray head (1-1) and the first liquid supply device, a second electromagnetic valve (1-5) is arranged between the second spray head (1-2) and the second liquid supply device, a third electromagnetic valve (1-6) is arranged between the third spray head (1-3) and the third liquid supply device, and the first electromagnetic valve (1-4), the second electromagnetic valve (1-5) and the third electromagnetic valve (1-6) are all connected with the controller.

3. The zirconium or hafnium chip standard pickling device according to claim 1, wherein the inner bottom plate of the box body (2) is provided with a first cylinder body (3-1), a second cylinder body (3-2) and a third cylinder body (3-3) corresponding to the lower parts of the first spray head (1-1), the second spray head (1-2) and the third spray head (1-3) respectively.

4. The zirconium or hafnium chip standard pickling device according to claim 1, wherein the case cover (1) is provided with a sample outlet (1-7).

5. A zirconium or hafnium chip standard pickling device according to claim 1, wherein the vibration generator (4-5) is connected to a controller.

6. The zirconium or hafnium chip standard pickling device according to claim 1, wherein the rotating shaft (2-3) is connected with the power unit (2-2), and the power unit (2-2) is connected with the controller.

7. A zirconium or hafnium chip standard pickling device according to claim 1, wherein the inside surface of the basket (4-1) is coated with a filter cotton cloth (4-2).

8. The zirconium or hafnium chip standard pickling device according to claim 1, wherein the inner bottom plate of the tank (2) is provided with a corrosion resistant plate (5).

9. The zirconium or hafnium chip standard pickling device according to claim 1, wherein a liquid outlet (6) is formed in the lower side wall of the box body (2).

10. A method for pickling a zirconium or hafnium chip standard sample by using the pickling device according to any one of claims 1 to 9, wherein the method comprises the following steps:

firstly, laying a zirconium or hafnium chip-shaped standard sample in a screen basket (4-1), and then rotating a rotating shaft (2-3) to enable a funnel (4) to rotate below a first spray head (1-1);

step two, opening a first spray head (1-1) to spray acid liquor onto zirconium or hafnium chip-shaped standard samples in the screen basket (4-1), opening a vibration generator (4-5) to enable the zirconium or hafnium chip-shaped standard samples to be subjected to acid liquor pickling for 10 s-15 s while vibrating, and then closing the first spray head (1-1) and the vibration generator (4-5); the spraying flow rate of the acid liquor is 0.3 m/s-0.5 m/s;

step three, rotating the rotating shaft (2-3) to enable the funnel (4) to rotate below the second spray head (1-2), opening the second spray head (1-2) to spray clean water onto zirconium or hafnium chip-shaped standard samples in the screen basket (4-1), opening the vibration generator (4-5), enabling the zirconium or hafnium chip-shaped standard samples subjected to acid washing in the step two to be washed with clean water for 30-40 s while vibrating, and then closing the second spray head (1-2) and the vibration generator (4-5); the spraying flow rate of the clean water is 0.3 m/s-0.5 m/s;

step four, rotating a rotating shaft (2-3) to enable a funnel (4) to rotate below a third spray head (1-3), opening the third spray head (1-3) to spray an ethanol solution onto zirconium or hafnium chip-shaped standard samples in a screen basket (4-1), opening a vibration generator (4-5) to enable the zirconium or hafnium chip-shaped standard samples washed by clear water in the step three to be washed by the ethanol solution for 10 s-15 s while vibrating, then closing the third spray head (1-3) and the vibration generator (4-5), taking out the zirconium or hafnium chip-shaped standard samples washed by the ethanol solution, tiling and airing; the spraying flow rate of the clean water is 0.3 m/s-0.5 m/s.