Equipment and method for cleaning high-temperature alloy return scraps instantly generated by hydroiodic acid

Abstract

The invention belongs to the technical field of high-temperature alloy cleaning and purifying, and relates to a cleaning device and method for high-temperature alloy return scraps generated instantly through hydroiodic acid. A vibration plate, an ultrasonic vibration head and a fixed base are fixed to the lower end of a box body, a nitrogen bottom blowing device is fixed in the box body, and a gas pipeline is arranged in the vibration plate; a gas outlet of the gas pipeline is communicated with the nitrogen bottom blowing device, and a heating cleaning area is arranged in the box body and located above the nitrogen bottom blowing device. The method comprises the following steps: shearing the high-temperature alloy return scrap; cleaning with alcohol and drying; performing ultrasonic enhanced cleaning; cleaning with alcohol; and drying. According to the invention, immediate generation and uniform diffusion of hydroiodic acid are realized. The method is mainly used for cleaning the high-temperature alloy return scrap, and the performance of the regenerated high-temperature alloy after remelting is guaranteed.

Description

Technical Field

[0001] The invention belongs to the technical field of high-temperature alloy cleaning and purification, and relates to a high-temperature alloy return material cleaning device and method that generates hydroiodic acid instantly. Background Art

[0002] High-temperature alloys have superior performance, high creep strength, fracture strength, and good corrosion resistance, fatigue resistance and oxidation resistance under high temperature conditions, making them widely used in aerospace, nuclear reactors and petroleum industries.

[0003] The utilization rate of high-temperature alloy materials from production, processing to use is only about 20% to 30%, and a large amount of cuttings will be generated during the processing. After the service, the high-temperature alloy will cause the material performance to deteriorate due to long-term high-intensity operation. When it can no longer be used, it will become high-temperature alloy waste. These cuttings and high-temperature alloy waste are collectively referred to as high-temperature alloy return materials. High-temperature alloy return materials have a very large recycling value, and the main recycling method is high-temperature remelting recycling. High-temperature remelting recycling has fewer process steps, lower production costs, simple equipment structure, easy operation, and easy industrialization.

[0004] Since high-temperature alloys have been in service for a long time in high temperature and highly corrosive environments, a dense non-metallic layer will form on the surface of the high-temperature alloy return material. If these non-metallic layers are not removed and the high-temperature alloy return material is directly remelted, the non-metallic elements will enter the regenerated high-temperature alloy during the remelting process, resulting in an excessively high content of non-metallic elements in the regenerated high-temperature alloy and deterioration of material properties. Therefore, the non-metallic layer on the surface of the high-temperature alloy return material should be removed by cleaning before high-temperature remelting to reduce the content of non-metallic elements in the regenerated high-temperature alloy and ensure its material properties.

[0005] The existing cleaning technologies for high-temperature alloy return materials mainly include direct pickling and electrolytic pickling. Among them, direct pickling uses strong acid to clean high-temperature alloy return materials, and directly dissolves the non-metallic layer on the surface of the high-temperature alloy return materials in the strong acid. Since most of the non-metallic layer on the surface of the high-temperature alloy return materials are nitrogen oxides of aluminum and chromium, it is very easy to form a passivation layer when reacting with acid, which inhibits the cleaning reaction and causes the efficiency of direct pickling to be extremely low. Electrolytic pickling cleans the high-temperature alloy return materials by means of an external electric field. The electrolyte is usually a strong acidic solution. The high-temperature alloy return materials are used as the anode to dissolve the non-metallic layer on the surface of the high-temperature alloy return materials into the electrolyte. However, the electrolytic pickling equipment has a complex structure, the cleaning current poses a hidden danger to personal safety, and the equipment process cost is high, which is not conducive to industrial production.

[0006] In order to increase the utilization ratio of returned materials, reduce production costs, and achieve the goals of saving resources and protecting the environment, it is necessary to develop a green and efficient returned material cleaning technology. Summary of the invention

[0007] Purpose of the Invention

[0008] In order to solve the problems existing in the prior art of return material cleaning, the present invention provides a high-temperature alloy return material cleaning device and method for instantly generating hydroiodic acid, the purpose of which is to clean the non-metallic layer on the surface of the high-temperature alloy return material to ensure the performance of the regenerated high-temperature alloy after remelting and recovery.

[0009] Technical Solution

[0010] A high-temperature alloy return material cleaning device generated instantly by hydroiodic acid comprises a box body, a box cover is fixedly connected to the upper end of the box body, a vibration plate is fixed to the lower end of the box body, an ultrasonic vibrator and a fixed base are arranged in sequence at the lower end of the vibration plate, the vibration end of the ultrasonic vibrator is pressed against the bottom surface of the vibration plate, the bottom end of the ultrasonic vibrator is arranged on the fixed base, a nitrogen bottom blowing device is fixed at the upper end of the vibration plate and located in the box body, a gas pipeline is arranged inside the vibration plate, the gas outlet of the gas pipeline is connected to the nitrogen bottom blowing device, the gas inlet of the gas pipeline is connected to a nitrogen bottle through a gas pipe, a heating cleaning area is arranged inside the box body above the nitrogen bottom blowing device, and when cleaning liquid is contained in the box body, the cleaning liquid can immerse the heating cleaning area.

[0011] Furthermore, the heating and cleaning area includes a heating and cleaning tank bottom plate and a heating rod. The cleaning tank bottom plate is horizontally arranged, and bottom plate holes are evenly arranged in the vertical direction of the cleaning tank bottom plate. The cleaning tank bottom plate is fixedly connected to a fixing rod, and the fixing rod is fixedly connected to the box cover. A heating rod is fixedly arranged at the lower end of one side of the fixing rod. The fixing rod is hollow, and the power cord of the heating rod extends to the outside of the box cover through the hollow fixing rod.

[0012] Furthermore, the number of the fixing rods is greater than or equal to 2, the fixing rods are evenly arranged and fixed on the bottom plate of the cleaning tank, and the number of the heating rods on each fixing rod is greater than or equal to 1.

[0013] Furthermore, the heating rod is fixed to the fixing rod by a fixing sleeve, the fixing sleeve is connected to the fixing rod, a heating rod fixing groove is opened on one side of the fixing sleeve, a section of the heating rod is fixed in the heating rod fixing groove, the heating rod fixing groove and the inner cavity of the heating rod fixing groove are connected, the fixing sleeve is fixed to the fixing rod by a top screw, and then the power lines of all the heating rods are connected in parallel and in series with the temperature control device.

[0014] Furthermore, the ultrasonic vibrator is evenly arranged in multiple numbers, the fixed base is provided with multiple grooves matching the shape of the lower end of the ultrasonic vibrator, and a fixing frame is also arranged on the fixed base, the fixed base is provided with a groove matching the shape of the lower end of the fixing frame, and the fixing frame is fixedly connected to the vibration plate.

[0015] Furthermore, the temperature control device is electrically connected to power source a, and the ultrasonic vibrator is electrically connected to power source b.

[0016] Furthermore, the nitrogen bottom blowing device is a porous inverted cone, and nitrogen coming out of the nitrogen bottom blowing device can form nitrogen bubbles. The diameter of the outlet hole of the nitrogen bottom blowing device is 2 to 40 mm.

[0017] A method for instant generation of uniform diffusion cleaning alloy return material based on hydroiodic acid using the device as described, comprising the following steps:

[0018] Step 1: Shear the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50mm;

[0019] Step 2: Use alcohol to clean the surface dirt of the high-temperature alloy return material obtained in step 1, and put it into a vacuum drying oven for drying to prevent the dirt from affecting the subsequent process;

[0020] Step 3: placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0021] Step 4: Use alcohol to clean the high-temperature alloy return material obtained in step 3, and then use deionized water to rinse the high-temperature alloy return material to remove the acid residue on the surface of the high-temperature alloy return material;

[0022] Step 5: Place the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0023] Furthermore, in step 3, the cleaning liquid used is a mixed solution of HCl and KI, the concentration of HCl is 8-15 mol / L, the concentration of KI is 25-35 g / L, and the ratio of high-temperature alloy return material to cleaning liquid is (1:20)-(1:100) kg / L. Under the action of ultrasound, HI is generated in the mixed solution, and the cleaning liquid becomes a mixed solution of HCl, KI and HI. After 10-30 minutes after the ultrasound stops, HI decomposes and the cleaning liquid is restored to a mixed solution of HCl and KI.

[0024] Furthermore, in step 3, the cleaning temperature is 40-55°C, the ultrasonic power is 500W-600W, the ultrasonic time is 20-40 minutes, and the nitrogen flow rate is 0.5m 3 / h.

[0025] Advantages and effects

[0026] The ultrasonic cleaning method for high-temperature alloy return material based on instant generation of hydroiodic acid of the present invention innovatively applies ultrasonic wave to the pickling process of high-temperature alloy return material. The cavitation effect generated by ultrasonic wave can not only accelerate the material transfer process, but also improve the oxidation performance of the cleaning liquid by generating hydroxyl radicals, and can also promote HCl and KI to generate HI, increase the acidity of the cleaning liquid, and promote the dissolution of the non-metallic layer on the surface of the high-temperature alloy return material. HI is very easy to decompose and difficult to store, but the HI in the present invention is instantly generated and recycled, which effectively avoids the problem of HI storage and easy decomposition failure. Compared with the direct pickling process, the present invention has high cleaning efficiency and good cleaning effect. Compared with the electrolytic cleaning process, the ultrasonic equipment has a simple structure, high process safety and low equipment cost. At the same time, the cleaning method of the present invention realizes the efficient cleaning of non-metallic elements on the surface of high-temperature alloy return material. The removal rate of non-metallic elements on the surface of the high-temperature alloy return material after cleaning reaches a high level, among which the removal rate of oxygen element is greater than 90%, and the removal rate of nitrogen and sulfur elements is greater than 70%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The present invention is further described below in conjunction with the accompanying drawings and specific implementation methods. The protection scope of the present invention is not limited to the following description.

[0028] Figure 1 It is a schematic diagram of the structure of the high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid;

[0029] Figure 2 It is a schematic diagram of the structure of the top view of the bottom plate of the heating cleaning tank;

[0030] Figure 3 It is a schematic diagram of the connection structure between the fixed sleeve, the fixed rod and the heating rod;

[0031] Figure 4 This is a microstructure diagram of the surface of the high-temperature alloy return material after cleaning in Example 1 of the present invention;

[0032] Figure 5 This is an element distribution analysis diagram of the surface of the high-temperature alloy return material after cleaning in Example 2 of the present invention;

[0033] Figure 6 This is a microstructure diagram of the surface of the high-temperature alloy return material after cleaning in Comparative Example 1 of the present invention;

[0034] Figure 7 This is an element distribution analysis diagram of the surface of the high-temperature alloy return material after cleaning in Comparative Example 1 of the present invention;

[0035] Figure 8 This is a microstructure diagram of the surface of the high-temperature alloy return material after cleaning in Comparative Example 2 of the present invention.

[0036] Description of reference numerals:

[0037] 1. Box cover, 2. Box body, 3. Fixing rod, 4. Temperature control device, 5. Heating cleaning tank bottom plate, 6. Heating rod, 7. Heating cleaning area, 8. Cleaning liquid, 9. Nitrogen bubbles, 10. Nitrogen bottom blowing device, 11. Vibrating plate, 12. Ultrasonic vibrator, 13. Fixed base, 14. Pressure gauge, 15. Air pipe, 16. Nitrogen bottle, 17. Nitrogen bottle fixing device, 18. Power supply a, 19. Power supply b, 20. Bottom plate hole, 21. Fixing sleeve, 22. Top screw. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0039] A high-temperature alloy return material cleaning device for instant generation of hydroiodic acid, comprising a box body 2, a box cover 1 is fixedly connected to the upper end of the box body 2, the circumference of the box cover 1 is covered on the outer side of the box body 2, and is fixedly connected together by bolts, a vibration plate 11 is fixedly bonded to the lower end of the box body 2 by silicone sealant, an ultrasonic vibrator 12 and a fixed base 13 are sequentially arranged at the lower end of the vibration plate 11, the vibration end of the ultrasonic vibrator 12 is pressed against the bottom surface of the vibration plate 11, the bottom end of the ultrasonic vibrator 12 is arranged on the fixed base 13, the upper end of the vibration plate 11 and located in the box body 2 is fixedly bonded with a nitrogen bottom blower by silicone sealant The device 10 and the vibration plate 11 are provided with a gas pipeline inside, the gas outlet of the gas pipeline is connected to the nitrogen bottom blowing device 10, the gas inlet of the gas pipeline is connected to the nitrogen bottle 16 through the air pipe 15, the nitrogen bottle 16 is provided with a pressure gauge 14, the pressure gauge 14 is used to monitor the gas state in the nitrogen bottle 16, and the nitrogen bottle 16 is also reinforced with a nitrogen bottle fixing device 17 on the periphery to prevent the nitrogen bottle 16 from being vibrated and knocked down by the air pipe 15 to cause danger. The interior of the box 2 is located above the nitrogen bottom blowing device 10 and is provided with a heating cleaning area 7. When the cleaning liquid 8 is contained in the box 2, the cleaning liquid 8 can immerse the heating cleaning area 7. The ultrasonic vibration of the ultrasonic vibrator 12 will be transmitted to the cleaning liquid 8, causing the cleaning liquid 8 to vibrate. The heating and cleaning area 7 includes a heating and cleaning tank bottom plate 5 and a heating rod 6. The cleaning tank bottom plate 5 is horizontally arranged, and the cleaning tank bottom plate 5 is evenly provided with bottom plate holes 20 in the vertical direction. The bottom plate holes 20 allow nitrogen bubbles to pass through. The cleaning tank bottom plate 5 is welded and fixedly connected with a fixing rod 3. The outer periphery of the fixing rod 3 is provided with a thread. The upper end of the fixing rod 3 passes through the box cover 1. The fixing rod 3 is fixedly connected to the box cover 1 through two nuts above and below the box cover 1. The lower end of one side of the fixing rod 3 is fixedly provided with a heating rod 6. The fixing rod 3 is hollow, and the power cord of the heating rod 6 extends to the outside of the box cover 1 through the hollow of the fixing rod 3. The number of the fixing rods 3 is greater than or equal to 2, and the fixing rods 3 are evenly arranged and fixed on the cleaning tank bottom plate 5. The number of the heating rods 6 on each fixing rod 3 is greater than or equal to 1. The heating rod 6 is fixed to the fixing rod 3 through a fixing sleeve 21, and the fixing sleeve 21 is sleeved on the fixing rod 3. A fixing groove for the heating rod 6 is opened on one side of the fixing sleeve 21. A section of the heating rod 6 is fixed in the fixing groove of the heating rod 6 by interference fit or threaded fit. The fixing groove of the heating rod 6 is connected to the inner cavity of the fixing groove of the heating rod 6. The fixing sleeve 21 is fixedly connected to the fixing rod 3 through a top screw 22. A temperature control device 4 for adjusting the current is fixed to one of the fixing rods 3. The power lines of all the heating rods 6 are connected in parallel and then connected in series with the temperature control device 4. The temperature control device 4 can use an ordinary variable resistor sold in the prior art on the market.

[0040] There are multiple evenly arranged ultrasonic vibrators 12, and the fixed base 13 is provided with multiple grooves matching the shape of the lower end of the ultrasonic vibrator 12. A fixing frame is also provided on the fixed base 13, and the fixed base 13 is provided with a groove matching the shape of the lower end of the fixing frame. The fixing frame is fixedly connected to the vibration plate 11 by screws. The fixed base 13 cooperates with the ultrasonic vibrator 12 and the fixing frame in this way, so that when the ultrasonic vibrator 12 vibrates, the overall equipment will not be vibrated apart.

[0041] The temperature control device 4 is electrically connected to the power supply a18, the power supply a18 forms a loop with the temperature control device 4 and the ultrasonic vibrator 12, and the ultrasonic vibrator 12 is electrically connected to the power supply b19 to form a loop.

[0042] The nitrogen bottom blowing device 10 is a porous inverted cone. Nitrogen coming out of the nitrogen bottom blowing device 10 can form nitrogen bubbles 9. The diameter of the outlet hole of the nitrogen bottom blowing device 10 is 2 to 40 mm. Nitrogen can be evenly released into the cleaning liquid 8 through the nitrogen bottom blowing device 10.

[0043] A method for using the above device to instantly generate uniform diffusion cleaning alloy return material based on hydroiodic acid, comprising the following steps:

[0044] Step 1: Shear the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50mm;

[0045] Step 2: Use alcohol to clean the surface dirt of the high-temperature alloy return material obtained in step 1, and put it into a vacuum drying oven for drying to prevent the dirt from affecting the subsequent process;

[0046] Step 3: Place the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device that generates hydroiodic acid immediately for ultrasonic intensive cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material; the cleaning liquid used is a mixed solution of HCl and KI, the concentration of HCl is 8-15 mol / L, the concentration of KI is 25-35 g / L, and the ratio of high-temperature alloy return material to cleaning liquid is (1:20)-(1:100) kg / L. Under the action of ultrasonic waves, HI is generated in the mixed solution, and the cleaning liquid becomes a mixed solution of HCl, KI and HI. After 10-30 minutes after the ultrasonic wave stops, HI decomposes and the cleaning liquid returns to a mixed solution of HCl and KI. The cleaning temperature is 40-55°C, the ultrasonic power is 500W-600W, the ultrasonic time is 20-40 minutes, and the nitrogen flow rate is 0.5m 3 / h;

[0047] Step 4: Use alcohol to clean the high-temperature alloy return material obtained in step 3, and then use deionized water to rinse the high-temperature alloy return material to remove the acid residue on the surface of the high-temperature alloy return material;

[0048] Step 5: Place the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0049] In step 3, the role of ultrasound is to:

[0050] Physical effects: The cavitation effect caused by ultrasound breaks the attraction between liquid medium molecules, forming a cavitation core with a lifespan of about 0.1μs in the solution. The cavitation core explosion generates high-speed microjets in the solution. The high-speed microjets generate strong impact force at the liquid-solid interface, destroying the solid film layer at the contact interface, so that the unreacted non-metallic layer on the surface of the high-temperature alloy return material is continuously exposed and fully contacted with the cleaning liquid, thereby improving the cleaning efficiency. In addition, the high-speed microjets can reduce the thickness of the liquid film layer at the contact interface, shorten the diffusion path of reactants and products, and improve the mass transfer efficiency of the chemical reaction between the non-metallic layer and the cleaning liquid.

[0051] In terms of chemical effects: the cavitation nuclear explosion can instantly produce a local high temperature and high pressure environment, forming a local "hot spot", promoting the cleavage of the OH bond in the water molecule and generating hydroxyl free radicals. The reaction is as follows. Hydroxyl free radicals are one of the strongest oxidants, which can increase the oxidation potential of the system and promote the dissolution of the non-metallic layer on the surface of the high-temperature alloy return material.

[0052] H 2 O→H·+·OH

[0053] In step 3, the role of the HCl and KI system is: under the action of ultrasound, hydroxyl radicals and KI react in the solution to generate free iodine. Subsequently, under the action of hydroxyl radicals, this free iodine continues to react with hydrochloric acid to generate HI, as shown in the following reaction formula. - The radius of Cl - Big, so H + The degree of electrolysis in HI is greater than that in HCl. + The concentration increases, making the solution more acidic and its ability to dissolve the non-metallic layer on the surface of the high-temperature alloy return material stronger.

[0054] 2·OH+2KI→2KOH+I 2

[0055] 2I 2 +2HCl+2·OH→4HI+2·Cl+O 2

[0056] Since HI is very unstable, when the ultrasound stops, the concentration of hydrogen radicals and hydroxyl radicals in the cleaning solution decreases, and HI immediately decomposes into I - and H + In the cleaning solution, I - With K +Recombines to generate KI. The reaction is as follows, and the cleaning liquid composition changes back to HCl + KI. This achieves the instant generation of HI and avoids the transportation and storage problems of HI.

[0057] HI→H + +I -

[0058] I - +K + →KI

[0059] The present invention is further described below by specific experimental examples:

[0060] Example 1

[0061] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0062] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0063] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0064] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0065] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0066] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0067] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0068] The removal rates of oxygen, nitrogen and sulfur in this embodiment are 91.2%, 70% and 73.6% respectively.

[0069] The surface microstructure of the high-temperature alloy return material after cleaning in this embodiment is as follows: Figure 4 As shown. Figure 4 It can be seen that the non-metallic layered substances on the surface of the high-temperature alloy return material after cleaning in this embodiment are removed.

[0070] The element distribution analysis on the surface of the high-temperature alloy return material after cleaning in this embodiment is as follows: Figure 5 As shown. Figure 5 It can be seen that the non-metallic elements on the surface of the high-temperature alloy return material after cleaning in this embodiment are removed.

[0071] Example 2

[0072] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0073] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0074] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0075] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0076] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0077] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 10 mol / L, the concentration of KI is 25 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0078] In step 3, the cleaning temperature is 45° C., the ultrasonic power is 500 W, and the ultrasonic time is 20 minutes.

[0079] The removal rates of oxygen, nitrogen and sulfur in this embodiment are 90.4%, 70.8% and 73.6% respectively.

[0080] Example 3

[0081] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0082] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0083] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0084] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0085] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0086] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 14 mol / L, the concentration of KI is 35 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0087] In step 3, the cleaning temperature is 55° C., the ultrasonic power is 600 W, and the ultrasonic time is 40 minutes.

[0088] The removal rates of oxygen, nitrogen and sulfur in this embodiment are 91.6%, 71.7% and 73.6% respectively.

[0089] Comparative Example 1

[0090] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0091] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0092] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0093] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0094] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0095] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 5 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0096] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0097] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 53.6%, 32.7% and 23.6% respectively.

[0098] The surface microstructure of the high temperature alloy return material after cleaning in this comparative example is as follows Figure 6 As shown. Figure 6 It can be seen that the non-metallic granular structure on the surface of the high-temperature alloy return material after cleaning in this comparative example has not been significantly removed.

[0099] The surface element distribution analysis of the high-temperature alloy return material after cleaning in this comparative example is as follows Figure 7 As shown. Figure 7 It can be seen that the effect of removing non-metallic elements on the surface of the high-temperature alloy return material after cleaning in this comparative example is not obvious.

[0100] Comparative Example 2

[0101] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0102] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0103] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0104] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0105] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0106] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 18 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0107] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0108] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 92.6%, 73.5% and 79.4% respectively.

[0109] The surface microstructure of the high temperature alloy return material after cleaning in this comparative example is as follows Figure 8 As shown. Figure 8It can be seen that the surface structure of the high-temperature alloy return material after cleaning in this comparative example is destroyed.

[0110] Comparative Example 3

[0111] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0112] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0113] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0114] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0115] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0116] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 10 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0117] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0118] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 67.5%, 54.3% and 47.9% respectively.

[0119] Comparative Example 4

[0120] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0121] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0122] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0123] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0124] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0125] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 50 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0126] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0127] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 91.2%, 70% and 73.6% respectively.

[0128] Comparative Example 5

[0129] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0130] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0131] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0132] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0133] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0134] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0135] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 200 W, and the ultrasonic time is 30 minutes.

[0136] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 59.4%, 41.7% and 29.6% respectively.

[0137] Comparative Example 6

[0138] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0139] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0140] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0141] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0142] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0143] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0144] In step 3, the cleaning temperature is 20° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0145] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 62.8%, 46.5% and 32.4% respectively.

[0146] Comparative Example 7

[0147] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0148] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0149] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0150] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0151] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0152] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0153] In step 3, the cleaning temperature is 70° C., the ultrasonic power is 600 W, and the ultrasonic time is 30 minutes.

[0154] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 91.2%, 70% and 73.6% respectively.

[0155] Comparative Example 8

[0156] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0157] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0158] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0159] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0160] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0161] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0162] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 10 minutes.

[0163] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 66.8%, 58.4% and 37.6% respectively.

[0164] Comparative Example 9

[0165] Step 1, shearing the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50 mm for standby use;

[0166] Step 2, using alcohol to clean the dirt on the surface of the high-temperature alloy return material obtained in step 1, and putting it into a vacuum drying oven for drying to prevent the dirt from affecting the pickling process;

[0167] Step 3, placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material;

[0168] Step 4, washing the high-temperature alloy return material obtained in step 3 with alcohol, and then rinsing the high-temperature alloy return material with deionized water to remove the acid residue on the surface of the high-temperature alloy return material;

[0169] Step 5, placing the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

[0170] In step 3, the cleaning solution used is a mixed solution of HCl and KI, the concentration of HCl is 12 mol / L, the concentration of KI is 30 g / L, and the ratio of high-temperature alloy return material to cleaning solution is 1:50 (kg / L).

[0171] In step 3, the cleaning temperature is 50° C., the ultrasonic power is 600 W, and the ultrasonic time is 60 minutes.

[0172] The removal rates of oxygen, nitrogen and sulfur in this comparative example are 91.2%, 70% and 73.6% respectively.

[0173] The non-metallic elements on the surface of the high-temperature alloy return material after cleaning in the above-mentioned embodiment and comparative example were tested, and the test results are shown in Table 1.

[0174] Table 1

[0175]

[0176]

[0177] From the above examples, comparative examples and the data in Table 1, it can be seen that:

[0178] (1) Through Examples 1-3, it can be seen from the data in Table 1 that the process of the embodiment of the present invention can effectively remove non-metallic elements on the surface of the high-temperature alloy return material by ultrasonic cleaning of the high-temperature alloy return material under the specified HCl concentration, KI concentration, ultrasonic power, ultrasonic time and ultrasonic temperature.

[0179] (2) Through comparative examples 1-2, it can be seen from the data in Table 1 that: when the HCl concentration used does not reach the standard specified in the present invention, the non-metallic elements on the surface of the high-temperature alloy return material cannot be effectively cleaned; when the HCl concentration used is greater than the standard specified in the present invention, although the non-metallic elements on the surface of the high-temperature alloy return material can be effectively cleaned, the structure of the high-temperature alloy return material will be damaged.

[0180] (3) Through comparative examples 3-4, it can be seen from the data in Table 1 that: when the KI concentration used does not reach the standard specified in the present invention, the non-metallic elements on the surface of the high-temperature alloy return material cannot be effectively cleaned; when the KI concentration used is greater than the standard specified in the present invention, the cleaning effect on the high-temperature alloy return material is not further enhanced.

[0181] (4) Through comparative example 5, it can be seen from the data in Table 1 that when the ultrasonic power used does not reach the standard specified in the present invention, the non-metallic elements on the surface of the high-temperature alloy return material cannot be effectively cleaned.

[0182] (5) Through comparative examples 6-7, it can be seen from the data in Table 1 that: when the ultrasonic temperature used does not reach the standard specified in the present invention, the non-metallic elements on the surface of the high-temperature alloy return material cannot be effectively cleaned; when the ultrasonic temperature used is greater than the standard specified in the present invention, the cleaning effect on the high-temperature alloy return material is not further enhanced.

[0183] (6) Through comparative examples 8-9, it can be seen from the data in Table 1 that: when the ultrasonic time used does not reach the standard specified in the present invention, the non-metallic elements on the surface of the high-temperature alloy return material cannot be effectively cleaned; when the ultrasonic time used is greater than the standard specified in the present invention, the cleaning effect on the high-temperature alloy return material is not further enhanced.

[0184] In summary, the cleaning method proposed in the embodiment of the present invention optimizes the process flow of cleaning high-temperature alloy return materials and improves the cleaning efficiency. The cleaning method of the present invention achieves efficient cleaning of the non-metallic layer on the surface of the high-temperature alloy return material by adding an ultrasonic external field and using an instantly generated, recyclable, high-cleaning-efficiency HCl+KI pickling solution. The disadvantage of HI being easy to decompose is solved, and the storage and transportation process of HI is avoided. A theoretical reference is provided for the pretreatment of high-temperature alloy waste before remelting and recycling. Therefore, the cleaning method proposed in the embodiment of the present invention has good application value and prospects in the field of cleaning and purification technology for high-temperature alloys.

[0185] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the embodiments of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the embodiments here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A high-temperature alloy return material cleaning device with instant generation of hydroiodic acid, characterized in that: The invention comprises a box body (2), the upper end of the box body (2) is fixedly connected to a box cover (1), the lower end of the box body (2) is fixedly connected to a vibration plate (11), the lower end of the vibration plate (11) is sequentially provided with an ultrasonic vibration head (12) and a fixed base (13), the vibration end of the ultrasonic vibration head (12) is pressed against the bottom surface of the vibration plate (11), the bottom end of the ultrasonic vibration head (12) is arranged on the fixed base (13), the upper end of the vibration plate (11) is fixedly connected to the box body (2), and the upper end of the vibration plate (11) is fixedly connected to the box body (2). A nitrogen bottom blowing device (10) is provided, a gas pipeline is provided inside the vibration plate (11), the gas outlet of the gas pipeline is connected to the nitrogen bottom blowing device (10), the gas inlet of the gas pipeline is connected to a nitrogen bottle (16) through a gas pipe (15), and a heating cleaning area (7) is provided inside the box body (2) above the nitrogen bottom blowing device (10). When a cleaning liquid (8) is contained in the box body (2), the cleaning liquid (8) can immerse the heating cleaning area (7).

2. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 1 is characterized in that: The heating and cleaning area (7) comprises a heating and cleaning tank bottom plate (5) and a heating rod (6); the cleaning tank bottom plate (5) is arranged horizontally, and the cleaning tank bottom plate (5) is evenly provided with bottom plate holes (20) in the vertical direction; the cleaning tank bottom plate (5) is fixedly connected with a fixing rod (3); the fixing rod (3) is fixedly connected with the box cover (1); a heating rod (6) is fixedly arranged at the lower end of one side of the fixing rod (3); the fixing rod (3) is hollow, and a power line of the heating rod (6) extends through the hollow of the fixing rod (3) to the outside of the box cover (1).

3. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 2 is characterized in that: The number of the fixed rods (3) is greater than or equal to 2, the fixed rods (3) are evenly arranged and fixed on the bottom plate (5) of the cleaning tank, and the number of the heating rods (6) on each fixed rod (3) is greater than or equal to 1.

4. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 3 is characterized in that: The heating rod (6) is fixed to the fixing rod (3) via a fixing sleeve (21), the fixing sleeve (21) is sleeved on the fixing rod (3), a heating rod (6) fixing groove is formed on one side of the fixing sleeve (21), a section of the heating rod (6) is fixed in the heating rod (6) fixing groove, the heating rod (6) fixing groove and the inner cavity of the heating rod (6) fixing groove are communicated, the fixing sleeve (21) is fixedly connected to the fixing rod (3) via a top screw (22), and the power lines of all the heating rods (6) are connected in parallel and then connected in series with the temperature control device (4).

5. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 1 or 2, characterized in that: The ultrasonic vibrators (12) are evenly arranged in plurality, the fixed base (13) is provided with a plurality of grooves matching the shape of the lower ends of the ultrasonic vibrators (12), a fixed frame is also provided on the fixed base (13), the fixed base (13) is provided with a groove matching the shape of the lower ends of the fixed frame, and the fixed frame is fixedly connected to the vibration plate (11).

6. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 3 is characterized in that: The temperature control device (4) is electrically connected to a power source a (18), and the ultrasonic vibrator (12) is electrically connected to a power source b (19).

7. The high-temperature alloy return material cleaning equipment with instant generation of hydroiodic acid according to claim 1 is characterized in that: The nitrogen bottom blowing device (10) is in the shape of a porous inverted cone. Nitrogen coming out of the nitrogen bottom blowing device (10) can form nitrogen bubbles (9). The diameter of the outlet hole of the nitrogen bottom blowing device (10) is 2 to 40 mm.

8. A method for cleaning alloy return material based on instant generation of uniform diffusion of hydroiodic acid using the apparatus as claimed in claim 1, characterized in that: The following steps are involved: Step 1: Shear the high-temperature alloy return material to control the size of the high-temperature alloy return material to 20-50mm; Step 2: Use alcohol to clean the surface dirt of the high-temperature alloy return material obtained in step 1, and put it into a vacuum drying oven for drying to prevent the dirt from affecting the subsequent process; Step 3: placing the high-temperature alloy return material obtained in step 2 in a high-temperature alloy return material cleaning device in which hydroiodic acid is instantly generated for ultrasonic enhanced cleaning to remove the non-metallic layer on the surface of the high-temperature alloy return material; Step 4: Use alcohol to clean the high-temperature alloy return material obtained in step 3, and then use deionized water to rinse the high-temperature alloy return material to remove the acid residue on the surface of the high-temperature alloy return material; Step 5: Place the high-temperature alloy return material obtained in step 4 into a vacuum drying oven for drying to obtain clean high-temperature alloy return material.

9. The method according to claim 8, characterized in that: In step 3, the cleaning liquid used is a mixed solution of HCl and KI, the concentration of HCl is 8-15 mol / L, the concentration of KI is 25-35 g / L, the ratio of high-temperature alloy return material to cleaning liquid is (1:20)-(1:100) kg / L, and under the action of ultrasound, HI is generated in the mixed solution, and the cleaning liquid becomes a mixed solution of HCl, KI and HI. After 10-30 minutes after the ultrasound stops, HI decomposes and the cleaning liquid returns to a mixed solution of HCl and KI.

10. The method according to claim 8, characterized in that: In step 3, the cleaning temperature is 40-55°C, the ultrasonic power is 500W-600W, the ultrasonic time is 20-40 minutes, and the nitrogen flow rate is 0.5m 3 / h.

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