阅读说明：本技术 一种钽及钽钨回收料制备钽二点五钨合金铸锭的方法 (Method for preparing tantalum two-point pentatungsten alloy ingot from tantalum and tantalum-tungsten reclaimed materials ) 是由 万军 陈飞 白掌军 颉维平 胡瑞升 牟东 黄云红 马立学 于 2020-07-27 设计创作，主要内容包括：本申请提供的钽及钽钨回收料制备钽二点五钨合金铸锭的方法,利用钽或钽钨合金加工过程产生的边角回收料,通过对以上回收料进行酸/水洗、氢化、脱氢、磨筛,制备出-200目的钽粉或钽钨合金粉,经分析检测,调配,压制、放入真空烧结炉内,制备出钽2.5钨合金烧结条,而后烧结条在真空电子束炉中熔炼,即得钽2.5钨合金锭。本申请利用钽或钽钨合金加工过程产生的边角回收料、通过多步火法处理工艺,制备出符合特定条件和相关质量标准的钽2.5钨合金铸锭。本申请实现了钽及钽钨合金回收料的短流程、高收率的回收再利用,解决了现有生产钽2.5钨合金铸锭的方法中,工艺流程复杂、工序繁多、钽及钨金属收率低,生产过程环境污染大等问题。(The method for preparing the tantalum two-point pentatungsten alloy ingot from the tantalum and tantalum tungsten reclaimed materials comprises the steps of utilizing leftover reclaimed materials generated in the tantalum or tantalum tungsten alloy processing process, carrying out acid/water washing, hydrogenation, dehydrogenation and grinding on the reclaimed materials to prepare tantalum powder or tantalum tungsten alloy powder of-200 meshes, carrying out analysis and detection, blending, pressing and placing in a vacuum sintering furnace to prepare a tantalum 2.5 tungsten alloy sintering strip, and smelting the post-sintering strip in a vacuum electron beam furnace to obtain the tantalum 2.5 tungsten alloy ingot. The method prepares the tantalum 2.5 tungsten alloy cast ingot which meets specific conditions and related quality standards by using the scrap reclaimed materials produced in the tantalum or tantalum-tungsten alloy processing process and adopting a multi-step pyrogenic process treatment process. The method realizes the recycling of the tantalum and tantalum-tungsten alloy reclaimed materials with short flow and high yield, and solves the problems of complex process flow, multiple procedures, low tantalum and tungsten metal yield, great environmental pollution in the production process and the like in the existing method for producing tantalum 2.5 tungsten alloy ingots.)

1. A method for preparing tantalum two-point pentatungsten alloy ingots by tantalum and tantalum tungsten reclaimed materials is characterized by comprising the following steps:

s1: acid washing tantalum, tantalum two-point pentatungsten alloy or tantalum 10 tungsten alloy reclaimed materials with different forms by adopting mixed acid;

s2: washing the acid-washed reclaimed materials with water by adopting ultrasonic waves to obtain impurity-removed reclaimed materials;

s3: loading the reclaimed materials after impurity removal into a hydrogenation furnace, heating in a sectional heating mode, then preserving heat, introducing hydrogen after heat preservation is finished, cooling after hydrogen introduction is finished, and discharging to obtain hydrogenated materials;

s4: grinding and screening the hydrogenated material by using a grinding and screening machine through a 200-mesh screen to obtain fine material powder;

s5: dehydrogenating the material fine powder;

s6: performing content detection analysis on the dehydrogenated material fine powder, adjusting the oxygen-carbon ratio in the mixed material, and if the O/C is less than 10, adding theoretical amount of tantalum oxide to obtain mixed powder with the oxygen-carbon ratio O/C more than or equal to 10;

s7: pressing the mixed powder into a tantalum two-point five-tungsten alloy strip;

s8: putting the pressed tantalum two-point five-alloy strip into a vacuum sintering furnace, vacuumizing, heating and sintering to prepare the tantalum two-point five-tungsten alloy strip;

s9: and smelting the tantalum two-point pentatungsten alloy strip by using a vacuum electron beam furnace to obtain the tantalum two-point pentatungsten alloy ingot.

2. The method for preparing tantalum two-point pentatungsten alloy ingots by using the tantalum and tantalum-tungsten reclaimed materials as claimed in claim 1, wherein the mixed acid is a mixed solution of hydrofluoric acid, nitric acid and phosphoric acid, and the volume ratio of the hydrofluoric acid to the nitric acid to the phosphoric acid is 1: 1: 2, the pickling time is 1-3 h.

3. The method for preparing the tantalum two-point pentatungsten alloy ingot from the tantalum and tantalum tungsten reclaimed materials according to claim 1, wherein in the step S3, the temperature is raised to the maximum temperature of 850 ℃, the holding time is 4 hours, the hydrogen introducing time is 4 hours, and the ingot is discharged after being cooled to the temperature below 60 ℃.

4. The method for preparing tantalum two-point pentatungsten alloy ingot from tantalum and tantalum-tungsten reclaimed materials according to claim 1, wherein the dehydrogenation process comprises the following steps:

and (3) carrying out programmed heating on the material fine powder from room temperature to 450 ℃ within 2 hours, then carrying out heat preservation for 2 hours, then carrying out programmed heating from room temperature to 700 ℃ within 2 hours, carrying out heat preservation for 4 hours, then carrying out programmed heating from room temperature to 850 ℃ within 2 hours, carrying out heat preservation for 6 hours, then carrying out power-off cooling when the vacuum degree is less than 30pa, and carrying out discharging when the temperature is reduced to below 60 ℃.

5. The method for preparing tantalum two-point pentatungsten alloy ingots by tantalum and tantalum tungsten reclaimed materials according to claim 1, wherein the sintering comprises: at a vacuum degree of 10^-2And under pa, carrying out sectional sintering by raising the temperature to 2400 ℃ in a programmed manner.

6. The method for preparing tantalum two-point pentatungsten alloy ingots by using the tantalum and tantalum-tungsten reclaimed materials as claimed in claim 1, wherein in the step S9, the smelting times are 2-3 times.

7. The method for preparing tantalum two-point pentatungsten alloy ingots by using the tantalum and tantalum-tungsten reclaimed materials as claimed in claim 1, wherein the grinding and screening machine is a tantalum lining grinding and screening machine.

8. The method for preparing tantalum two-point pentatungsten alloy ingot from tantalum and tantalum tungsten reclaimed materials according to claim 1, wherein the step S7 comprises the following steps:

and pressing the mixed powder into the tantalum two-point five-tungsten alloy strip by adopting an isostatic pressing or mould pressing mode under the condition that the forming pressure is more than or equal to 200 MPa.

Technical Field

The application relates to the technical field of metal material preparation, in particular to a method for preparing a tantalum two-point pentatungsten alloy ingot by using tantalum and tantalum tungsten reclaimed materials.

Background

The tantalum-tungsten binary system alloy formed by adding a certain amount of tungsten element into tantalum has the corrosion resistance of tantalum and the good high-temperature strength of tungsten. The alloy has the advantages of high temperature resistance, high strength, good fracture toughness, corrosion resistance and the like, and is applied to the fields of aviation, aerospace, chemical engineering, nuclear industry, high temperature technology and the like.

In the method for producing tantalum two-point pentatungsten (hereinafter referred to as tantalum 2.5 tungsten) alloy ingot by the traditional process, a treatment process route of hydrometallurgy purification and recovery is adopted, and as shown in figure 1, a finished ingot blank is obtained by fully mixing tantalum powder and tungsten powder and smelting for multiple times.

However, in the above method for preparing tantalum 2.5 tungsten alloy ingot, the processing route of hydrometallurgical purification and recovery requires multiple processes such as wet decomposition, extraction, crystallization, sodium reduction, oil pressure forming, vacuum sintering, and electron beam melting, and the operation flow is complicated, so that a large amount of equipment investment is required, and the comprehensive yield of tantalum and tungsten as recovered materials is low. Meanwhile, in the wet decomposition process, a large amount of mixed acid is consumed, and a large amount of acid-containing wastewater and waste gas are generated, so that the environment is polluted.

Disclosure of Invention

The application provides a method for preparing tantalum 2.5 tungsten alloy ingots by tantalum and tantalum tungsten reclaimed materials, which aims to solve the problems of complex flow, multiple working procedures, low tantalum and tungsten metal yield, great environmental pollution in the production process and the like in the traditional method for producing tantalum powder by acid decomposition and metal reduction purification of the tantalum and tantalum tungsten reclaimed materials and producing tantalum 2.5 tungsten alloy ingots by using the tantalum powder and the tungsten powder.

The technical scheme adopted by the application for solving the technical problems is as follows:

a method for preparing tantalum 2.5 tungsten alloy ingots by tantalum and tantalum tungsten reclaimed materials comprises the following steps:

s1: acid washing tantalum, tantalum 2.5 tungsten alloy or tantalum 10 tungsten alloy reclaimed materials with different forms by adopting mixed acid;

s2: washing the acid-washed reclaimed materials with water by adopting ultrasonic waves to obtain impurity-removed reclaimed materials;

s3: loading the reclaimed materials after impurity removal into a hydrogenation furnace, heating in a sectional heating mode, then preserving heat, introducing hydrogen after heat preservation is finished, cooling after hydrogen introduction is finished, and discharging to obtain hydrogenated materials;

s4: grinding and screening the hydrogenated material by using a grinding and screening machine through a 200-mesh screen to obtain fine material powder;

s5: dehydrogenating the material fine powder;

s6: performing content detection analysis on the dehydrogenated material fine powder, adjusting the oxygen-carbon ratio in the mixed material, and if the O/C is less than 10, adding theoretical amount of tantalum oxide to obtain mixed powder with the oxygen-carbon ratio O/C more than or equal to 10;

s7: pressing the mixed powder into tantalum 2.5 tungsten alloy strips;

s8: putting the pressed tantalum 2.5 alloy strip into a vacuum sintering furnace, vacuumizing, heating and sintering to prepare a tantalum 2.5 tungsten alloy strip;

s9: and smelting the tantalum 2.5 tungsten alloy strip by using a vacuum electron beam furnace to obtain a tantalum 2.5 tungsten alloy ingot.

Optionally, the mixed acid is a mixed solution of hydrofluoric acid, nitric acid and phosphoric acid, and the volume ratio of the hydrofluoric acid to the nitric acid to the phosphoric acid is 1: 1: 2, the pickling time is 1-3 h.

Optionally, in S3, the maximum temperature is 850 ℃, the holding time is 4 hours, the hydrogen introduction time is 4 hours, and the temperature is reduced to below 60 ℃ and the steel is taken out of the furnace.

Optionally, the dehydrogenation process comprises:

and (3) carrying out programmed heating on the material fine powder from room temperature to 450 ℃ within 2 hours, then carrying out heat preservation for 2 hours, then carrying out programmed heating from room temperature to 700 ℃ within 2 hours, carrying out heat preservation for 4 hours, then carrying out programmed heating from room temperature to 850 ℃ within 2 hours, carrying out heat preservation for 6 hours, then carrying out power-off cooling when the vacuum degree is less than 30pa, and carrying out discharging when the temperature is reduced to below 60 ℃.

Optionally, the sintering includes: at a vacuum degree of 10^-2And under pa, carrying out sectional sintering by raising the temperature to 2400 ℃ in a programmed manner.

Optionally, in the step S9, the number of times of smelting is 2 to 3.

Optionally, the milling and screening machine is a tantalum lining milling and screening machine.

Optionally, the S7 includes:

and pressing the mixed powder into the tantalum 2.5 tungsten alloy strip by adopting an isostatic pressing or mould pressing mode under the condition that the forming pressure is more than or equal to 200 MPa.

The technical scheme provided by the application comprises the following beneficial technical effects:

the method for preparing the tantalum 2.5 tungsten alloy ingot from the tantalum and tantalum tungsten reclaimed materials comprises the steps of utilizing leftover reclaimed materials generated in the tantalum or tantalum tungsten alloy processing process as raw materials through a multi-step pyrometallurgical treatment process, carrying out acid/water washing, hydrogenation, dehydrogenation and grinding and screening on the raw materials to prepare tantalum powder or tantalum tungsten alloy powder with the particle size of-200 meshes, carrying out analysis and detection, blending, pressing and placing in a vacuum sintering furnace to prepare a tantalum 2.5 tungsten alloy sintering strip, and smelting the sintering strip in a vacuum electron beam furnace to obtain the tantalum 2.5 tungsten alloy ingot. According to the method, the tantalum 2.5 tungsten alloy cast ingot which meets specific conditions and meets related quality standards is prepared by using the scrap reclaimed materials generated in the tantalum or tantalum-tungsten alloy processing process and adopting a multi-step pyrogenic process treatment process. The method realizes the recycling of the tantalum and tantalum-tungsten alloy reclaimed materials with short flow and high yield, and solves the problems of complicated flow, various procedures, low tantalum and tungsten metal yield, great environmental pollution in the production process and the like in the method for producing tantalum 2.5 tungsten alloy ingots by using tantalum powder and tungsten powder to produce tantalum powder by acid decomposition and metal reduction purification of the tantalum and tantalum-tungsten reclaimed materials in the traditional process.

Drawings

In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without any creative effort.

FIG. 1 is a flow chart of a method for producing tantalum 2.5 tungsten alloy ingots by a conventional wet process;

fig. 2 is a flowchart of a method for preparing a tantalum 2.5 tungsten alloy ingot according to an embodiment of the present application.

Detailed Description

In order to make the technical solutions in the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application; it is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The embodiment of the application provides a method for preparing a tantalum 2.5 tungsten alloy ingot from a tantalum and tantalum-tungsten reclaimed material, which comprises the following steps:

s1: acid cleaning tantalum, tantalum 2.5 tungsten alloy or tantalum 10 tungsten alloy reclaimed materials with different forms by adopting mixed acid, wherein the reclaimed materials can be one of tantalum, tantalum 2.5 tungsten alloy or tantalum 10 tungsten alloy, or can be a plurality of reclaimed materials mixed together; the mixed acid is a mixed solution of hydrofluoric acid, nitric acid and phosphoric acid, and the volume ratio of the hydrofluoric acid to the nitric acid to the phosphoric acid is 1: 1: 2, pickling for 1-3 h; (ii) a

S2: washing the acid-washed reclaimed materials with water by adopting ultrasonic waves to obtain impurity-removed reclaimed materials;

s3: loading the reclaimed materials after impurity removal into a hydrogenation furnace, heating in a sectional heating mode, then preserving heat, introducing hydrogen after heat preservation is finished, cooling after hydrogen introduction is finished, and discharging to obtain hydrogenated materials; the maximum temperature is 850 ℃, the heat preservation time is 4 hours, the hydrogen introduction time is 4 hours, and the temperature is reduced to below 60 ℃ and the steel plate is discharged.

S4: grinding and screening the hydrogenated material by using a tantalum lining grinding and screening machine through a 200-mesh screen to obtain fine material powder;

s5: and (3) dehydrogenating the material fine powder, wherein the dehydrogenation process comprises the following steps:

and (3) carrying out programmed heating on the material fine powder from room temperature to 450 ℃ within 2 hours, then carrying out heat preservation for 2 hours, then carrying out programmed heating from room temperature to 700 ℃ within 2 hours, carrying out heat preservation for 4 hours, then carrying out programmed heating from room temperature to 850 ℃ within 2 hours, carrying out heat preservation for 6 hours, then carrying out power-off cooling when the vacuum degree is less than 30pa, and carrying out discharging when the temperature is reduced to below 60 ℃.

S6: performing content detection analysis on the dehydrogenated material fine powder, wherein the content detection analysis comprises analyzing and detecting the dehydrogenated tantalum powder, tantalum 2.5 tungsten powder and tantalum 10 tungsten powder, and reserving the powder for blending; mixing the powder materials for 10 hours after different combinations and proportions are blended, controlling the oxygen-carbon ratio in the mixed material, and if the O/C is less than 10, adding theoretical amount of tantalum oxide to obtain the mixed powder material with the oxygen-carbon ratio O/C more than or equal to 10.

S7: pressing the mixed powder into a tantalum 2.5 tungsten alloy strip, specifically pressing the mixed powder into the tantalum 2.5 tungsten alloy strip by adopting an isostatic pressing or mould pressing mode under the condition that the forming pressure is more than or equal to 200 MPa.

S8: putting the pressed tantalum 2.5 alloy strip into a vacuum sintering furnace, vacuumizing, heating and sintering to prepare the tantalum 2.5 tungsten alloy strip, wherein the sintering process is to perform sintering under the vacuum degree of 10^-2And under pa, carrying out sectional sintering by raising the temperature to 2400 ℃ in a programmed manner.

S9: and smelting the tantalum 2.5 tungsten alloy strip for 2-3 times by using a vacuum electron beam furnace to obtain a tantalum 2.5 tungsten alloy ingot.

To further illustrate the technical means and effects of the present application for achieving the intended purpose, the following describes a specific embodiment of the present application and its effects with reference to the process flow and specific examples in fig. 2, and the following detailed description is provided.