CN114262821B - Pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material and preparation method thereof - Google Patents
Pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material and preparation method thereof Download PDFInfo
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Abstract
The application relates to a pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material and a preparation method thereof, wherein the material comprises the following components in percentage by mass: cr:2.0 to 10.0 percent; mo:23.0 to 31.0 percent; w:1.0 to 3.0 percent; nb:0.5 to 1.5 percent; fe: less than or equal to 0.5 percent; ce: less than or equal to 0.05 percent; c: less than or equal to 0.05 percent; si:0.5 to 2.0 percent; co is less than or equal to 0.1 percent; the balance being Ni. The material is used for a container in a pure phosphoric acid corrosion environment with 200-250 ℃ resistance for nuclear field post-treatment, has excellent corrosion resistance and better mechanical property, can be applied to the manufacture of equipment and parts in post-treatment related environments, and prolongs the service life of the equipment and the parts.
Description
Technical Field
The invention relates to a nickel-based corrosion-resistant alloy material resistant to pure phosphoric acid corrosion, in particular to a nickel-based corrosion-resistant alloy material resistant to pure phosphoric acid corrosion at 200-250 ℃ and a preparation method thereof.
Background
Tributyl phosphate (TBP) is an extracting agent with excellent performance, and the extraction and refining of TBP is a method adopted by all nuclear industry countries in the world at present and becomes a standard process for uranium refining. The Purex process using TBP as extractant has become a nuclear fuel post-treatment process which is widely adopted in the world nowadays. The performance of the extractant degraded by chemical action and irradiation after multiple use is poor, so that the operation of the extractant can not be carried out any more. These organic solvents will eventually be stored as radioactive waste, due to the small amount of radionuclides contained, as radioactive spent organic phase. The main components of the waste organic phase comprise TBP, kerosene, a small amount of degradation products and radionuclide, and the waste organic phase belongs to flammable and explosive substances. The annual generation amount of the wastes is small, but the wastes are accumulated and stored for many years, the storage amount is increased year by year, potential safety hazards exist, and the wastes need to be treated urgently.
There are many research methods for treating waste organic phase, and the following methods are currently used: 1) Incineration processes such as excess air incineration, controlled air incineration (thermal cracking incineration), and plasma processes; 2) Wet oxidation treatment processes such as acid digestion, electrochemical oxidation treatment, supercritical water oxidation, direct chemical oxidation, fenton oxidation; 3) Adduct formation phase separation-incineration treatment; 4) An alkaline hydrolysis method; 5) Absorption method; 6) A cement curing method; 7) Distillation method. Wherein, the incineration treatment method can obtain a very high volume reduction ratio, but radioactive ash flies, the tail gas entrainment is serious, but a high-efficiency tail gas treatment system needs to be arranged, or the problems of high construction cost, energy consumption, high cost and the like exist; the wet oxidation treatment method has the advantages that the organic waste liquid with a wider treatment range can be treated, and has the disadvantages that the mixed acid has extremely strong corrosivity, the requirement on the corrosion resistance of equipment is extremely strong, the treatment cost is increased, a high-performance tail gas treatment system needs to be arranged, or the reaction control condition is relatively complex, the treatment cost is high, the pipeline is blocked, the reaction kettle is seriously corroded, and the like; the adduct-forming phase separation treatment process is relatively simple, but concentrated phosphoric acid or even pure phosphoric acid is required, so that the equipment is seriously corroded; the absorption method is simple in principle, but the used absorbent mainly depends on an inlet and needs to be subjected to secondary cement curing; the cement curing method has low cost and simple and convenient operation, but the volume of a cured body is greatly increased, and the treatment pressure of a subsequent cured body is higher; the distillation method can obtain higher volume reduction ratio, but also needs secondary treatment; the alkaline hydrolysis method has mature technology and low operation temperature, but has complex secondary components and needs further treatment.
It can be seen that the above nuclear power plant waste liquid treatment technologies all have their own advantages and disadvantages, wherein the adduct formation phase separation treatment technology is one of the waste organic phase treatment technologies currently studied in various countries, and the basic principle thereof is as follows: the contaminated TBP/diluent is contacted with concentrated phosphoric acid in a conventional mixer-settler or a pulsed column at ambient temperature, the TBP is quantitatively dissolved in the phosphoric acid, producing polar compounds of TBP and phosphoric acid. Almost all of the radioactivity is transferred to the adduct which can be further processed to recover phosphoric acid and dispose of the radioactive TBP. The method is adopted to treat waste TBP/n-dodecane in Germany and Belgium. In recent years, the phase separation-incineration treatment technology of formed added substances is researched in China, solid phosphoric acid is adopted to be heated and melted into liquid pure phosphoric acid, and the liquid pure phosphoric acid reacts at the temperature of 200-250 ℃ to carry out phase separation, but the structural material for equipment at the stage is seriously corroded by the pure phosphoric acid at the temperature of 200-250 ℃, is not enough to support multiple and long-term phase separation technical researches, and seriously influences the experimental and research effects. Therefore, the development of a novel metal material with pure phosphoric acid corrosion resistance, which is used for equipment structure materials and parts of pure phosphoric acid in an environment of 200-250 ℃, has important significance for the development of a post-treatment technology of a nuclear field waste organic phase.
Disclosure of Invention
The invention aims to provide a pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material and a preparation method thereof, the material is used for manufacturing a container of a nuclear field post-treatment environment resistant to pure phosphoric acid corrosion at 200-250 ℃, has excellent corrosion resistance and better mechanical property, is used for manufacturing equipment and parts of the nuclear field post-treatment related environment, and can prolong the service life and the operation life.
In order to achieve the purpose, the invention adopts the technical scheme that:
the nickel-based corrosion-resistant alloy material resisting pure phosphoric acid corrosion comprises the following components in percentage by mass:
cr:2.0 to 10.0 percent; mo:23.0 to 31.0 percent; w:1.0 to 3.0 percent; nb:0.5 to 1.5 percent; fe: less than or equal to 0.5 percent; ce: less than or equal to 0.05 percent; c: less than or equal to 0.05 percent; si:0.5 to 2.0 percent; co is less than or equal to 0.1 percent; the balance being Ni.
The better technical scheme is that the material comprises the following components in percentage by mass:
cr:2.1 to 9.5 percent; mo:23.5 to 30.1 percent; w:1.2 to 2.8 percent; nb:0.6 to 1.4 percent; fe:0.1 percent; ce:0.01 to 0.03 percent; c:0.01 to 0.02 percent; si:0.55 to 1.62 percent; 0 to 0.01 percent of Co; the balance being Ni.
The preparation method of the material comprises the following steps:
1) Smelting: taking the components according to the proportion of the materials, smelting in vacuum, refining at 1510-1550 ℃, wherein the vacuum degree in the refining period is more than or equal to 1Pa, and the pouring temperature is 1460-1500 ℃ to obtain a vacuum ingot, and remelting by using ternary slag system electroslag to obtain an electroslag ingot;
2) Forging: forging the blank into a plate blank or a square blank at the initial temperature of 1150-1180 ℃ and the final forging temperature of more than 980 ℃;
3) Hot rolling: heating the forging stock to 1150-1180 ℃, hot rolling and processing the forging stock into a plate or a bar, and air cooling the plate or the bar to room temperature;
4) Cold rolling and cold drawing: and (3) cold-rolling the plate blank into a plate belt material or cold-drawing the bar material into a wire material, and eliminating work hardening by annealing in the cold-rolling and cold-drawing processes to obtain the pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material.
The ternary slag system in the step 1) is CaF 2 +CaO+Al 2 O 3 60% by mass of CaF 2 +30％CaO+10％Al 2 O 3 。
And 4) during cold rolling and cold drawing, annealing at 1040-1080 ℃ for eliminating work hardening, wherein the annealing time is 30-75 minutes.
The thickness of the plate blank in the step 2) is 30-50 mm; the cross section of the billet is 45X 45mm.
The thickness of the plate in the step 3) is 8-20 mm; the phi of the bar is 10 mm-15 mm.
The nickel-based corrosion-resistant alloy material can be used for manufacturing various containers and parts which can resist the corrosion of pure phosphoric acid at 200-250 ℃ in the post-treatment of a nuclear field.
In the nickel-based corrosion-resistant alloy material resistant to pure phosphoric acid corrosion, mo has obvious corrosion resistance on pure phosphoric acid, has good effects on resisting uniform corrosion, intergranular corrosion and the like, and the mass percent is 23.0-31.0%.
Fe: the mass percent is less than or equal to 0.5 percent, and in a pure phosphoric acid system, the corrosion resistance can be reduced along with the increase of the content of Fe, and the Fe must be controlled at a low level.
W: 1.0-3.0% by mass, tungsten carbide is attached and deposited on the grain boundary, and the tungsten carbide has a good effect of preventing intergranular stress corrosion besides a strengthening effect, and the processing performance is influenced if the tungsten carbide is too high, and the tungsten carbide and Nb are added together to have a better intergranular corrosion resistance effect.
Nb: 0.5-1.5 wt%, certain amount of Ni-base austenite for improving pitting corrosion resistance and crevice corrosion resistance and intergranular corrosion resistance, and high machinability.
C: the mass percent is less than or equal to 0.05 percent, and the carbon carbide can influence the mechanical property and the corrosion resistance of a weld structure and cause the degradation of the post-treatment performance of welding. However, a small amount of Nb can fix residual carbon content and can act as a carbide strengthening effect.
Co: co content is less than or equal to 0.1 percent by mass, the post-treatment process environment has certain radioactivity, and the post-treatment process environment can be converted into radioactive elements under the action of neutrons in nuclear field 60 Co， 60 Co has a longer half-life, and the content of Co should be controlled at a lower level.
In the preparation process, special parameters are formulated and used as follows:
aiming at the characteristic of complex alloy components, a smelting mode of vacuum smelting and electroslag remelting is adopted, and the purpose is to obtain an electroslag cast ingot with high purity and uniform components, and reduce the processing performance deterioration and the finished product performance instability caused by inclusions and nonuniform components.
Hot rolling is a necessary process means for obtaining various finished products of the corrosion resistant alloy, and provides necessary intermediate transition slabs and bar blanks for the subsequent cold processing process.
The cold rolling and cold drawing are used for obtaining nickel-based corrosion resistant alloy finished products in different forms, the plate is used for preparing an integral structure of container equipment, and the rod and wire are used for preparing a corresponding structure or welding materials in the container.
The annealing treatment is to eliminate the processing stress of cold processing, anneal the material to recrystallize it, improve the plastic toughness of the material, and ensure the smooth cold processing of the material.
The material has good corrosion resistance in a solid phosphoric acid melting environment and an ultrahigh-concentration high-temperature phosphoric acid liquid environment for post-treatment of a nuclear field, has a corrosion rate of below 0.2mm/a in a solid phosphoric acid melting environment of 200-250 ℃, can ensure the safety and stability of radioactive waste liquid treatment at about 200-250 ℃ of pure phosphoric acid, can greatly improve the safety and the production capacity and efficiency, and can be used for manufacturing various containers, such as a reaction kettle and the like, in a high-concentration phosphoric acid environment of a corresponding post-treatment process of the nuclear field.
Detailed Description
Example 1
The weight percentage of the nickel-based corrosion-resistant alloy material applied to the pure phosphoric acid corrosion resistance is shown in the table 1.
TABLE 1 chemical composition (wt%) of pure phosphoric acid corrosion resistant Ni-based anticorrosion alloy material
| Number of | Cr | Mo | W | Nb | Si | Fe | Ce | Co | C | Ni |
| 1 | 2.1 | 30.1 | 2.8 | 1.0 | 0.55 | 0.1 | 0.01 | 0.0 | 0.01 | Surplus |
| 2 | 6.5 | 26.5 | 1.9 | 0.6 | 1.62 | 0.1 | 0.02 | 0.01 | 0.02 | Surplus |
| 3 | 9.5 | 23.5 | 1.2 | 1.4 | 1.36 | 0.1 | 0.03 | 0.01 | 0.01 | Surplus |
Example 2
The pure phosphoric acid corrosion resistant nickel-based corrosion resistant alloy material of the present invention was prepared by the following method, taking the components according to table 1.
The pure phosphoric acid corrosion resistant nickel-based corrosion resistant alloy material is processed into corrosion resistant alloy materials in different product forms by adopting vacuum induction furnace smelting and electroslag furnace refining through the working procedures of forging, hot rolling, heat treatment, cold rolling and the like, and the processing and heat treatment processes are as follows:
smelting: vacuum induction smelting and electroslag furnace remelting refining are adopted, wherein the refining temperature during vacuum induction smelting is 1510-1560 ℃, the vacuum degree in the refining period is more than or equal to 1Pa, the pouring temperature is 1460-1500 ℃, a vacuum ingot is obtained, and then slag system protective electroslag remelting is adopted, so that an electroslag ingot with smooth surface quality is obtained; forging: after forging and cogging, the initial temperature is 1150-1180 ℃, the finish forging temperature is not lower than 980 ℃, and the blank can be forged into a primary rolled plate blank or a bar blank as required; hot rolling: heating the forging stock to 1150-1180 ℃, hot rolling and processing the forging stock into a plate with the thickness of 8-20 mm or a bar with the diameter of 10-15 mm, and air cooling to room temperature; cold rolling and cold drawing: cold rolling the plate blank into a cold-rolled strip material with required specification, cold drawing the bar material into a wire material with required specification, and annealing at 1050 ℃ for 30-75 min to eliminate work hardening in the cold-rolling and cold-drawing process.
According to the set chemical composition range, a vacuum induction furnace is adopted to smelt a three-furnace nickel-based corrosion-resistant alloy material, and the corrosion-resistant alloy material in a required form is obtained after electroslag remelting, forging, rolling and drawing.
Example 3 results of the experiment
1. Performance testing of materials
The drill cuttings on the electroslag ingot described in example 2 were sampled, and the measured chemical compositions are shown in table 1; the mechanical properties of the finished product were tested by sampling in the machine direction and are shown in Table 2.
Mechanical properties of the corrosion-resistant alloy materials prepared in Table 2
| Numbering | Tensile strength Rm/MPa | Yield strength R p0.2 /MPa | Elongation A/%) |
| 1 | 1020 | 500 | 41 |
| 2 | 985 | 490 | 41 |
| 3 | 1005 | 485 | 42 |
The prepared corrosion-resistant alloy material has good mechanical property and high strength, and can be used as a structural material; the elongation is high, which indicates that the product has good cold processing performance, and can provide powerful plastic toughness support for processing plate, strip and wire rod finished products required by preparing containers.
2. Environmental Corrosion testing of materials
According to the materials of the embodiment, the corrosion rate is measured by adopting a uniform corrosion test method through simulating a liquid corrosion environment after solid phosphoric acid is melted according to the actual use temperature range of 200-250 ℃, and compared with corrosion resistant alloy Has C-2000, the corrosion resistance is verified to be good by a corrosion resistance test, and the annual corrosion rate is shown in Table 3.
TABLE 3 comparison of the corrosion resistance of the alloy prepared in phosphoric acid solution with that of Has C-2000
Note: the pure phosphoric acid is liquid pure phosphoric acid obtained by melting solid phosphoric acid at the temperature of 200-250 ℃.
And (4) conclusion: the annual corrosion rate of the corrosion-resistant alloy disclosed by the invention in liquid phosphoric acid with a nuclear field temperature of 200-250 ℃ is lower than 0.2mm & alpha -1 The alloy is superior to the corrosion-resistant alloy Has C-2000 of the comparative example by a plurality of times, has good corrosion resistance and does not generate intergranular corrosion; the better mechanical property shows that the material can be used as a structural material.
Claims (3)
1. The pure phosphoric acid corrosion resistant nickel-based corrosion-resistant alloy material is characterized by comprising the following components in percentage by mass:
cr:2.0 to 10.0 percent; mo:23.0 to 31.0 percent; w:1.0 to 3.0 percent; nb:0.5 to 1.5 percent; fe: less than or equal to 0.5 percent; ce: less than or equal to 0.05 percent; c: less than or equal to 0.05 percent; si:0.5 to 2.0 percent; co is less than or equal to 0.1 percent; the balance being Ni.
2. The material of claim 1, wherein: the material comprises the following components in percentage by mass:
cr:2.1 to 9.5 percent; mo:23.5 to 30.1 percent; w:1.2 to 2.8 percent; nb:0.6 to 1.4 percent; fe:0.1 percent; ce:0.01 to 0.03 percent; c:0.01 to 0.02 percent; si:0.55 to 1.62 percent; 0 to 0.01 percent of Co; the balance being Ni.
3. Use of the nickel base corrosion resistant alloy material according to any one of claims 1-2 for the manufacture of a vessel for nuclear field post-treatment in a pure phosphoric acid corrosion resistant environment at 200 ℃ to 250 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818486A (en) * | 1988-01-11 | 1989-04-04 | Haynes International, Inc. | Low thermal expansion superalloy |
| CN106756245A (en) * | 2016-10-31 | 2017-05-31 | 重庆材料研究院有限公司 | A kind of alloy material for nuclear field liquid waste processing tankage and preparation method thereof |
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| US7922969B2 (en) * | 2007-06-28 | 2011-04-12 | King Fahd University Of Petroleum And Minerals | Corrosion-resistant nickel-base alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818486A (en) * | 1988-01-11 | 1989-04-04 | Haynes International, Inc. | Low thermal expansion superalloy |
| CN106756245A (en) * | 2016-10-31 | 2017-05-31 | 重庆材料研究院有限公司 | A kind of alloy material for nuclear field liquid waste processing tankage and preparation method thereof |
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