CN113909470A

CN113909470A - Zirconium or hafnium scrap-shaped standard sample pickling device and technology

Info

Publication number: CN113909470A
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: 2022-01-11
Anticipated expiration: 2041-10-29
Also published as: CN113909470B

Abstract

The invention discloses a zirconium or hafnium scrap-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 the box cover is provided with a first spray nozzle, a second spray nozzle and a third spray nozzle; the invention also discloses a process for pickling the zirconium or hafnium scrap-shaped standard sample. According to the invention, the sieve basket for containing the zirconium or hafnium scrap-shaped standard sample is connected with the vibration generator, so that the sieve basket is fully contacted with the pickling solution, and the pickling decontamination effect is improved; the invention adopts acid solution dissolution, clear water washing and ethanol solution washing respectively, and the vibration effect of the vibration generator is matched, so that the pickling decontamination effect is improved, and the over pickling is avoided.

Description

Zirconium or hafnium scrap-shaped standard sample pickling device and technology

Technical Field

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

Background

Zirconium and hafnium have excellent properties such as 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 nuclear reactor core cladding tubes, end plugs, location grids and the like; the hafnium has the characteristics of large neutron absorption cross section and high emissivity, and is mainly applied to nuclear reactor core control rod materials. In the process of research and production of zirconium and hafnium materials, the control of the contents of alloy elements, impurity elements and other components directly influences the service performance of the materials. In the analysis process of alloy elements and impurity elements, zirconium and hafnium chemical standard samples (chips) are applied to establish a calibration curve and process quality control, so that the accuracy and reliability of detection results are guaranteed.

After the formation of the chip-like standard samples for chemical analysis of zirconium and hafnium, pickling and decontamination treatment are required. Because the size of the chip-shaped sample formed by processing is small, the problem that the surface pollution of the sample is uniformly removed in the pickling process becomes one of the problems in the pickling process of the chip-shaped sample. Therefore, designing and developing a more effective pickling device and pickling process has important application value for developing standard substances for chemical analysis.

Disclosure of Invention

The invention aims to solve the technical problem of providing a zirconium or hafnium scrap-shaped standard sample pickling device aiming at the defects of the prior art. This acid dip pickle sets up the sieve square-bottomed bamboo basket that holds zirconium or hafnium bits form trade sample and is connected with vibration generator, and the horizontal vibration through control vibration generator drives the zirconium in the sieve square-bottomed bamboo basket or hafnium bits form trade sample and rock upset reciprocating motion at the pickling in-process for zirconium or hafnium bits form trade sample and pickling solution fully contact, and fully and evenly get rid of the surperficial pollutant of zirconium or hafnium bits form trade sample, have improved the effect of pickling decontamination greatly.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the utility model provides a zirconium or hafnium bits form trade 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 interior bottom plate of box, fixedly connected with pivot on the support, the lateral part of pivot is connected with the funnel, the inside holding of funnel has the sieve bamboo basket, and has sieved the bamboo basket outer cup joint and have the lantern ring, the slide opening has been seted up to the lateral wall of funnel upper level, and swing joint has the traveller in the slide opening, and the one end and the lantern ring of traveller are connected, and the other end is connected with vibration generator.

The zirconium or hafnium scrap-shaped standard sample pickling device is characterized in that the first spray head, the second spray head and the third spray head are respectively and correspondingly connected with the first liquid supply device, the second liquid supply device and the third liquid supply device, a first electromagnetic valve is arranged between the first spray head and the first liquid supply device, a second electromagnetic valve is arranged between the second spray head and the second liquid supply device, a third electromagnetic valve is arranged between the third spray head and the third liquid supply device, and the first electromagnetic valve, the second electromagnetic valve and the third electromagnetic valve are all connected with the controller.

The zirconium or hafnium scrap-shaped sample pickling device is characterized in that a first cylinder, a second cylinder and a third cylinder are respectively arranged on the inner bottom plate of the box body and below the first spray head, the second spray head and the third spray head.

The zirconium or hafnium scrap-shaped sample pickling device is characterized in that the box cover is provided with a lofting opening.

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

The zirconium or hafnium scrap-shaped 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 scrap-shaped sample pickling device is characterized in that filtering cotton cloth is laid on the inner surface of the sieve basket.

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

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

In addition, the invention also discloses a process for pickling zirconium or hafnium scrap-shaped standard samples by using the pickling device, which is characterized by comprising the following steps of:

firstly, laying zirconium or hafnium scrap-shaped samples in a sieve basket, and then rotating a rotating shaft to enable a funnel to rotate below a first spray head;

opening a first spray nozzle to spray acid liquor on the zirconium or hafnium scrap-shaped standard sample in the sieve basket, opening a vibration generator to perform acid liquor pickling on the zirconium or hafnium scrap-shaped standard sample for 10-15 s while vibrating, and then closing the first spray nozzle and the vibration generator; the spraying flow rate of the acid liquor is 0.3-0.5 m/s;

rotating the rotating shaft to enable the funnel to rotate to the position below the second spray head, starting the second spray head to spray clean water onto the zirconium or hafnium scrap-shaped standard sample in the sieve basket, starting the vibration generator to enable the zirconium or hafnium scrap-shaped standard sample after acid liquid pickling 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 speed of the clear water is 0.3-0.5 m/s;

step four, rotating the rotating shaft to enable the funnel to rotate to the position below the third spray head, starting the third spray head to spray an ethanol solution onto the zirconium or hafnium scrap-shaped standard sample in the sieve basket, starting the vibration generator to enable the zirconium or hafnium scrap-shaped standard sample washed by the clean water in the step three to be washed by the ethanol solution for 10-15 s while vibrating, then closing the third spray head and the vibration generator, and taking out the zirconium or hafnium scrap-shaped standard sample washed by the ethanol solution to be spread and dried; the spraying flow speed of the clear water is 0.3-0.5 m/s.

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

1. according to the pickling device, the sieve basket for containing the zirconium or hafnium scrap-shaped standard sample is placed in the funnel, the sieve basket is connected with the vibration generator through the sliding columns movably connected in the sliding holes in the side wall of the funnel, the horizontal vibration of the vibration generator is controlled to drive the zirconium or hafnium scrap-shaped standard sample in the sieve basket to shake, turn and reciprocate in the pickling process, so that the zirconium or hafnium scrap-shaped standard sample is fully contacted with a pickling solution, pollutants on the surface of the zirconium or hafnium scrap-shaped standard sample are fully and uniformly removed, and the pickling decontamination effect is greatly improved.

2. According to the pickling device, the spray nozzle is arranged on the box cover to spray pickling solution on the zirconium or hafnium scrap-shaped standard sample in the sieve basket in the vertical direction, so that the vibration direction of the sieve basket is vertical to the spraying direction of the pickling solution, the splashing of the pickling solution caused by the vibration of the sieve basket is greatly reduced, the continuous pickling is realized by arranging special spray nozzles for different pickling solutions, and the pickling efficiency is improved.

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

4. According to the pickling device, the filtering cotton cloth is laid on the inner surface of the sieve basket, so that the flow speed of the pickling solution is effectively reduced, the vibration amplitude is buffered, the leakage loss of the zirconium or hafnium filiform standard sample with smaller size is avoided, the contact action time of the pickling solution is prolonged by intercepting the pickling solution, and pollutants on the surface of the zirconium or hafnium filiform standard sample are further fully removed.

5. Aiming at the pickling process of the zirconium or hafnium chip-shaped standard sample, the invention respectively adopts acid solution dissolution, clear water washing and ethanol solution washing, and the vibration action of the vibration generator is matched to promote the zirconium or hafnium chip-shaped standard sample to turn over and fully contact with each pickling solution, thereby greatly improving the pickling decontamination effect and avoiding excessive consumption of the zirconium or hafnium chip-shaped standard sample caused by excessive local pickling reaction in the zirconium or hafnium chip-shaped standard sample.

The technical solution of the present invention is further described in detail by the accompanying drawings and examples.

Drawings

FIG. 1 is a sectional view of a pickling apparatus for a zirconium or hafnium flake-like specimen according to the present invention.

Fig. 2 is a cross-sectional view taken along the plane a-a in fig. 1.

FIG. 3 is a plan view of the pickling apparatus for zirconium or hafnium shavings-like samples according to the present invention.

Description of reference numerals:

1-box cover; 1-1 — a first showerhead; 1-2-a second spray head;

1-3-a third spray head; 1-4-a first solenoid valve; 1-5-a second solenoid valve;

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

2-1-scaffold; 2-power unit; 2-3-a rotating shaft;

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

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

4-3-a collar; 4-a spool; 4-5-vibration generator;

5-corrosion resistant plate; 6-liquid discharge port.

Detailed Description

Example 1

As shown in fig. 1, 2 and 3, the zirconium or hafnium scrap-shaped sample pickling device of the present embodiment includes a box body 2 with an open top and a box cover 1 fitted to the box body 2, the box cover 1 is provided with a first spray head 1-1, a second spray head 1-2 and a third spray head 1-3, a bracket 2-1 is arranged on the inner bottom plate of the box body 2, a rotating shaft 2-3 is fixedly connected on the bracket 2-1, the side part of the rotating shaft 2-3 is connected with a funnel 4, a sieve basket 4-1 is contained in the funnel 4, and a lantern ring 4-3 is sleeved outside the sieve basket 4-1, a sliding hole is horizontally formed in the side wall of the funnel 4, a sliding column 4-4 is movably connected in the sliding hole, one end of the sliding column 4-4 is connected with the lantern ring 4-3, and the other end of the sliding column 4-4 is connected with a vibration generator 4-5.

The zirconium or hafnium filings-shaped sample pickling device of the embodiment comprises two main parts: the cleaning device comprises a box body 2 and a box cover 1 matched with the box body 2, wherein the box cover 1 is provided with three spray heads, namely a first spray head 1-1, a second spray head 1-2 and a third spray head 1-3, and the cleaning of pollutants on the surface of a conventional zirconium or hafnium chip-shaped standard sample is divided into three stages: in the embodiment, three spray heads are sequentially and correspondingly arranged for introducing the acid solution, the clear water and the ethanol solution to spray respectively, and the funnel 4 is driven to rotate by combining the rotation action of the rotating shaft 2-3, so that the zirconium or hafnium filiform standard sample placed in the sieve basket 4-1 in the funnel 4 is sequentially rotated to the positions below the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3, and the zirconium or hafnium filiform standard sample is sprayed with different pickling solutions to perform pickling work in different cleaning stages, the acid washing solution does not need to be frequently replaced at the same spray head, so that the cross contamination of the acid washing solution is avoided, the continuous acid washing is realized, and the acid washing efficiency is improved.

Meanwhile, the bracket 2-1 is arranged on the inner bottom plate of the box body 2, the rotating shaft 2-3 is fixedly connected to the bracket 2-1, the funnel 4 is connected to the side part of the rotating shaft 2-3, the bracket 2-1 is used as a base for bearing the rotating shaft 2-3, so that the stable work 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 the rotation of the funnel 4 is facilitated; in the device, a sieve basket 4-1 is placed in a funnel 4 and used as a place for placing and pickling zirconium or hafnium scrap-shaped samples, a lantern ring 4-3 is sleeved outside the sieve basket 4-1, a sliding hole is formed in the side wall of the funnel 4, one end of a sliding column 4-4 movably connected in the sliding hole is connected with the lantern ring 4-3, the other end of the sliding column is connected with a 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 vibration generator 4-5 is started to drive the sliding column 4-4 to move in the sliding hole, under the limiting action of the sliding hole, the sliding column 4-4 can only vibrate along the axial direction of the sliding hole, namely the horizontal direction, so that the lantern ring 4-3 drives the sieve basket 4-1 to vibrate along the horizontal direction, and the zirconium or hafnium scrap-shaped samples shake, turn and reciprocate in the pickling process, the zirconium or hafnium standard sample is fully contacted with the acid washing solution, so that all zirconium or hafnium standard samples can be washed by the acid washing solution, pollutants on the surface of the zirconium or hafnium standard samples are fully and uniformly removed, the acid washing decontamination effect is greatly improved, and excessive consumption of the zirconium or hafnium standard samples caused by excessive local acid washing reaction in the zirconium or hafnium standard samples is avoided; after pickling, the pickling waste liquid containing pollutants leaks out of the sieve holes of the sieve basket 4-1 and flows out along the discharge spout of the funnel 4, so that the pollutants are prevented from remaining in the sieve basket 4-1 to cause secondary pollution to zirconium or hafnium scrap-shaped standard samples, and the concentration of the pickling solution sprayed subsequently is ensured to improve the cleaning effect. Usually, the sieve basket 4-1 is horizontally placed in the hopper 4, and the pickling solution is sprayed on the zirconium or hafnium filings in the sieve basket 4-1 along the vertical direction through a spray head arranged on the box cover 1, at this time, the movement direction of the sieve 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 sieve basket 4-1 is greatly reduced.

Furthermore, 2 sliding holes are symmetrically formed in the side wall of the funnel 4 horizontally, wherein one end of each sliding column 4-4 in the sliding hole close to the vibration generator 4-5 is connected with the lantern ring 4-3, the other end of each sliding column 4-4 in the sliding hole far away from the vibration generator 4-5 is connected with the lantern ring 4-3, and the other end of each sliding column 4-4 penetrates through the side wall of the funnel 4 and is connected with a limiting block at the end part. In the embodiment, 2 sliding holes are horizontally and symmetrically formed in the side wall of the funnel 4, and the sieve basket 4-1 vibrates in the horizontal direction opposite to the two sliding holes by utilizing the connection action of the sliding columns in the sliding holes and the lantern ring 4-3, so that the zirconium or hafnium scrap-shaped standard sample is prevented from being irregularly collided and scattered outside the sieve basket 4-1 to cause loss due to vibration in multiple horizontal directions on the premise of ensuring full contact of the zirconium or hafnium scrap-shaped standard sample and the pickling solution; meanwhile, the sliding column 4-4 at only one end is limited to be connected with the vibration generator 4-5, so that the sieve basket 4-1 only vibrates under the vibration action of the vibration generator 4-5 at one end, and the phenomenon of offsetting 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 a lantern ring 4-3, so that the sieve basket 4-1 is ensured to vibrate along the horizontal direction, the other end penetrates through the side wall of the funnel 4 and is connected with a limiting block at the end part, the sliding column 4-4 is prevented from falling off, and the smooth vibration of the sieve basket 4-1 is ensured.

Furthermore, in this embodiment, the side of the rotating shaft 2-3 is connected with more than 2 identical funnels 4. Through setting up more than 2 the same funnels 4, place zirconium or hafnium bits form trade sample in proper order in the sieve bamboo basket 4-1 of funnel 4, then according to three rotatory pivot 2-3 in washing stage and drive each funnel 4 rotatory for each funnel 4 rotates in proper order to the shower nozzle below that corresponds, and sprays corresponding pickling solution, thereby has realized going on of the continuous pickling work of different zirconium or hafnium bits form trade sample at same pickling in-process, has 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 and correspondingly connected to the first liquid supply device, the second liquid supply device, and the third liquid supply device, 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 nozzles are different, the first nozzle 1-1, the second nozzle 1-2 and the third nozzle 1-3 are respectively and correspondingly connected with the first liquid supply device, the second liquid supply device and the third liquid supply device, so that different pickling solutions are sprayed through special nozzles, cross contamination of different pickling solutions is further avoided, and continuous pickling work is facilitated. Generally, the first nozzle 1-1, the second nozzle 1-2 and the third nozzle 1-3 are respectively used for spraying acid liquid, clean water and ethanol solution, and the corresponding first liquid supply device, the second liquid supply device and the third liquid supply device are respectively used for supplying acid liquid, clean water and ethanol solution. 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 valves 1-4, the second electromagnetic valves 1-5 and the third electromagnetic valves 1-6 according to different stages of the set pickling work, so that the spraying on-off and the spraying flow rate of the pickling solution in the first spray heads 1-1, the second spray heads 1-2 and the third spray heads 1-3 are controlled, the pickling reaction process is accurately controlled, the continuous pickling work is ensured, and the pickling process is convenient, rapid and accurate in regulation and control.

Furthermore, in the embodiment, a first cylinder 3-1, a second cylinder 3-2 and a third cylinder 3-3 are respectively arranged on the inner bottom plate of the box body 2 below the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3. In the embodiment, the first cylinder 3-1, the second cylinder 3-2 and the third cylinder 3-3 are respectively arranged below the first spray head 1-1, the second spray head 1-2 and the third spray head 1-3 and are respectively used for receiving the pickling waste liquid discharged from the funnel 4, namely the waste acid liquid, the waste water and the waste ethanol solution, so that the pickling waste liquid can be conveniently classified, collected and treated in a centralized manner, and the environmental pollution is effectively prevented.

As shown in fig. 2 and 3, in the present embodiment, the box cover 1 is provided with lofting openings 1-7. In the embodiment, the lofting openings 1-7 are formed in the box cover 1 and used as channels for placing zirconium or hafnium chip-shaped standard samples, lofting can be performed without opening the box cover 1, convenience and labor saving are achieved, and the pickling efficiency is improved.

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

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

Generally, the controller connected with the first solenoid valves 1-4, the second solenoid valves 1-5 and the third solenoid valves 1-6, the controller connected with the vibration generator 4-5 and the controller connected with the power device 2-2 in the embodiment are commonly named Mitsubishi FX3U-48 MR/ES-A. The volume accuracy of the acid washing solution sprayed in each spray head is improved through the action of the controller matched with the servo motor, the accuracy of the rotating position of the zirconium or hafnium scrap-shaped standard sample placed in the sieve basket 4-1 in the hopper 4 is improved, and the accuracy of the vibration generator 4-5 for driving the zirconium or hafnium scrap-shaped standard sample to shake, turn and reciprocate in the acid washing process is improved.

Furthermore, in the embodiment, the inner surface of the sieve basket 4-1 is paved with filtering cotton cloth 4-2. In the embodiment, the filtering cotton cloth 4-2 is laid on the inner surface of the sieve basket 4-1 and used for containing zirconium or hafnium filings, so that the flow rate of the pickling solution is effectively reduced, the vibration amplitude is buffered, the zirconium or hafnium filings with small sizes are prevented from leaking out of sieve holes of the sieve basket 4-1 under the spraying action of the pickling solution or the vibration action of the sieve basket 4-1, the zirconium or hafnium filings are prevented from being lost, the filtering 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 filings is prolonged, pollutants on the surface of the zirconium or hafnium filings are fully removed, the filtering characteristic of the filtering cotton cloth 4-2 ensures that the outflow of pickling waste liquid is not affected, 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 after each four-wheel acid washing operation, so that the filter cotton cloth 4-2 is prevented from being damaged due to excessive acid washing operation.

Further, in the present embodiment, a corrosion-resistant plate 5 is laid on the inner bottom plate of the box body 2. In the 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 out of the funnel 4, so that the corrosion of the acidic liquid on the inner bottom plate of the box body 2 is prevented, and the service life of the pickling device is prolonged.

Further, in this embodiment, a liquid outlet 6 is disposed on a lower side wall of the box body 2. This embodiment is through offering leakage fluid dram 6 on the lower lateral wall of box 2 to the pickling solution or the pickling waste liquid that flow or spill from funnel 4 discharge from the box, avoided the corrosive damage effect of acid liquid to other structures in the acid dip pickle.

Furthermore, in the embodiment, the first nozzle 1-1, the second nozzle 1-2, the third nozzle 1-3, the funnel 4, the sieve basket 4-1, the first cylinder 3-1, the second cylinder 3-2 and the third cylinder 3-3 are all made of white polyethylene plastics, and the corrosion resistance of the white polyethylene plastics is utilized to effectively prevent the corrosion damage of the parts in the pickling process, prolong the service life of the pickling device and avoid the pollution of zirconium or hafnium scrap-shaped standard samples.

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

Example 2

The embodiment comprises the following steps:

firstly, a zirconium chip-shaped standard sample is laid in a sieve basket 4-1 through a lofting opening 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 position below a first spray nozzle 1-1;

step two, opening a first spray nozzle 1-1 to spray acid liquor onto the zirconium chip-shaped standard sample in the sieve 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 nozzle 1-1 and the vibration generator 4-5; the spraying flow rate of the acid liquor is 0.3 m/s;

step three, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate to the position below the second spray nozzle 1-2, starting the second spray nozzle 1-2 to spray clean water onto the zirconium chip-shaped standard sample in the sieve basket 4-1, starting the vibration generator 4-5 to enable the zirconium chip-shaped standard sample after acid liquid pickling in the step two to be washed with clean water for 30s while vibrating, and then closing the second spray nozzle 1-2 and the vibration generator 4-5; the spraying flow speed of the clear water is 0.3 m/s;

step four, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate to the position below the third spray head 1-3, starting the third spray head 1-3 to spray an ethanol solution onto the zirconium chip-shaped standard sample in the sieve basket 4-1, starting the vibration generator 4-5 to enable the zirconium chip-shaped standard sample washed by the clean water in the step three to be washed by the ethanol solution for 15 seconds 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, laying flat and airing; the spraying flow speed of the clear water is 0.3 m/s.

Through detection, the mass contents of the elements Cr, Fe, Nb, and Sn in the zirconium chip-shaped standard sample before the acid washing treatment are 0.082%, 0.332%, 0.302%, and 0.958%, respectively, and the mass contents of the elements Cr, Fe, Nb, and Sn in the zirconium chip-shaped standard sample after the acid washing treatment are 0.080%, 0.328%, 0.302%, and 0.960%, respectively, that is, the mass contents of the main elements in the zirconium chip-shaped standard sample before and after the acid washing treatment are substantially the same, which indicates that the acid washing process of the present invention effectively removes the contaminants on the surface of the zirconium chip-shaped standard sample, and does not affect the components of the zirconium chip-shaped standard sample by excessive acid washing.

Example 3

The embodiment comprises the following steps:

firstly, a hafnium scrap-shaped standard sample is laid in a sieve basket 4-1 through a lofting opening 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 nozzle 1-1 to spray acid liquor onto the hafnium scrap-shaped standard sample in the sieve 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 scrap-shaped standard sample to be subjected to acid liquor pickling for 10s while vibrating, and then closing the first spray nozzle 1-1 and the vibration generator 4-5; the spraying flow rate of the acid liquor is 0.5 m/s;

step three, rotating the rotating shaft 2-3 to enable the funnel 4 to rotate to the position below the second spray head 1-2, starting the second spray head 1-2 to spray clean water onto the hafnium scrap-shaped standard sample in the sieve basket 4-1, starting the vibration generator 4-5 to enable the hafnium scrap-shaped standard sample after being pickled by the acid solution in the step two to be washed by clean water for 40s while vibrating, and then closing the second spray head 1-2 and the vibration generator 4-5; the spraying flow speed of the clear water is 0.5 m/s;

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

Through detection, the mass content of the Zr element in the hafnium scrap sample before the pickling process is 0.24%, and the mass content of the Zr element in the hafnium scrap sample after the pickling process is still 0.24%, that is, the mass contents of the Zr element in the hafnium scrap sample before and after the pickling process are substantially consistent, which indicates that the pickling process of the present invention effectively removes the contaminants on the surface of the hafnium scrap sample, and the component of the hafnium scrap sample is not affected by excessive pickling.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims

1. The zirconium or hafnium scrap-shaped standard sample pickling device is characterized by comprising a box body (2) with an open top and a box cover (1) matched with the box body (2), wherein the box cover (1) is provided with a first spray nozzle (1-1), a second spray nozzle (1-2) and a third spray nozzle (1-3), a bracket (2-1) is arranged on an inner bottom plate of the box body (2), a rotating shaft (2-3) is fixedly connected onto the bracket (2-1), the side part of the rotating shaft (2-3) is connected with a funnel (4), 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 sliding hole is horizontally formed in the side wall of the funnel (4), a sliding column (4-4) is movably connected into the sliding hole, one end of the sliding column (4-4) is connected with the lantern ring (4-3), the other end is connected with a vibration generator (4-5).

2. The zirconium or hafnium scrap-shaped standard sample pickling device according to claim 1, wherein the first nozzle (1-1), the second nozzle (1-2) and the third nozzle (1-3) are respectively and correspondingly connected with the first liquid supply device, the second liquid supply device and the third liquid supply device, a first electromagnetic valve (1-4) is arranged between the first nozzle (1-1) and the first liquid supply device, a second electromagnetic valve (1-5) is arranged between the second nozzle (1-2) and the second liquid supply device, a third electromagnetic valve (1-6) is arranged 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 with a controller.

3. The zirconium or hafnium scrap-shaped standard sample pickling device according to claim 1, wherein a first cylinder (3-1), a second cylinder (3-2) and a third cylinder (3-3) are respectively arranged on the bottom plate in the box body (2) below the first spray nozzle (1-1), the second spray nozzle (1-2) and the third spray nozzle (1-3).

4. The pickling device for zirconium or hafnium shavings standard samples according to claim 1, wherein the box cover (1) is provided with a lofting opening (1-7).

5. The pickling apparatus for standard samples in zirconium or hafnium shavings form according to claim 1, wherein said vibration generator (4-5) is connected to a controller.

6. The pickling device for zirconium or hafnium shavings shaped samples according to claim 1, wherein the rotating shaft (2-3) is connected with a power device (2-2), and the power device (2-2) is connected with a controller.

7. The pickling device for the zirconium or hafnium shavings-shaped standard samples according to claim 1, wherein the inner surface of the sieve basket (4-1) is paved with filtering cotton cloth (4-2).

8. The pickling device for standard samples in zirconium or hafnium shavings form according to claim 1, characterized in that a corrosion-resistant plate (5) is laid on the inner bottom plate of the box body (2).

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

10. A process for pickling zirconium or hafnium shavings by using the pickling device of any one of claims 1 to 9, comprising the steps of:

firstly, laying zirconium or hafnium scrap-shaped standard samples in a sieve basket (4-1), and then rotating a rotating shaft (2-3) to enable a funnel (4) to rotate to the lower part of a first spray nozzle (1-1);

step two, opening a first spray nozzle (1-1) to spray acid liquor on the zirconium or hafnium scrap-shaped standard sample in the sieve basket (4-1), opening a vibration generator (4-5) to perform acid liquor pickling on the zirconium or hafnium scrap-shaped standard sample for 10-15 s while vibrating, and then closing the first spray nozzle (1-1) and the vibration generator (4-5); the spraying flow rate of the acid liquor is 0.3-0.5 m/s;

step three, rotating the rotating shaft (2-3) to enable the funnel (4) to rotate to the position below the second spray head (1-2), starting the second spray head (1-2) to spray clean water onto the zirconium or hafnium scrap-shaped standard sample in the sieve basket (4-1), starting the vibration generator (4-5) to enable the zirconium or hafnium scrap-shaped standard sample after acid liquid pickling 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 speed of the clear water is 0.3-0.5 m/s;

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