CN113500097B - Preparation method and application of alloy thin-wall capillary tube for hydrogen purification - Google Patents
Preparation method and application of alloy thin-wall capillary tube for hydrogen purification Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B23/00—Tube-rolling not restricted to methods provided for in only one of groups B21B17/00, B21B19/00, B21B21/00, e.g. combined processes planetary tube rolling, auxiliary arrangements, e.g. lubricating, special tube blanks, continuous casting combined with tube rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/15—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting by using vacuum
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02E60/50—Fuel cells
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Abstract
The invention provides a preparation method and application of an alloy thin-wall capillary tube for hydrogen purification. The method mainly comprises the following steps: (1) Vacuum smelting the cast rod, putting each pure metal raw material into a crucible for smelting and preparing into synthetic Jin Yuanbang; (2) Vacuum tube casting, namely placing the alloy round bar into a mould and casting the alloy round bar into a pierced billet through resistance heating; (3) Pre-rolling a pierced billet, and rolling the tube blank by using a two-roller high-speed cold rolling mill to obtain a tube blank; (4) And (3) finely rolling the pipe blank, and finely rolling the semi-finished pipe by using a three-roller high-speed cold rolling mill to obtain the finished pipe. According to the invention, the rod and the tube blank are directly cast in vacuum, so that the production procedures are reduced, and raw materials and energy consumption are saved; and two types of rolling equipment are further combined, so that the efficiency is improved, and the yield of the tubes is ensured. The preparation method provided by the invention is simple in process, and the prepared ultrathin-wall hydrogen separation alloy capillary has the advantages of high precision, high yield, thin tube wall, good air tightness, large hydrogen permeation flow, stable performance and the like, and has wide application prospects in the field of high-purity hydrogen production.
Description
Technical Field
The invention relates to the technical field of hydrogen separation material processing, in particular to a preparation method and application of an alloy thin-wall capillary tube for hydrogen purification.
Background
Hydrogen has attracted extensive attention as a zero-emission fuel, a carrier of clean energy. Among them, high purity hydrogen (99.999%) is required in many fields such as rocket-launched fuel hydrogen, proton exchange membrane fuel cells, semiconductor industry, etc. However, hydrogen produced industrially generally contains a large amount of harmful impurity gases, and therefore, it is necessary to produce high-purity and ultra-pure hydrogen by a hydrogen separation and purification technique, and dense hydrogen separation metal materials are key components for producing high-purity hydrogen.
Palladium exhibits good hydrogen permeation properties in dense hydrogen separation metal materials, however, palladium metal is low in storage and expensive, further limiting the commercial application of the alloy. In order to reduce the cost, the use amount of noble palladium metal needs to be reduced, non-noble metal (Nb, V and Ta) is used for replacement, and in addition, the material thickness needs to be reduced and the specific surface area needs to be increased for further improving the hydrogen permeation flow. Compared with a flat membrane, the thin-wall capillary has the advantages of high strength, pressure bearing capacity, easiness in packaging, large specific surface area, high hydrogen permeation flow and low cost, and the preparation of the thin-wall capillary hydrogen permeation alloy membrane material is one of the main developing directions at present.
At present, the method for preparing the palladium and other alloy pipes mainly comprises the welding of flat-plate membrane materials, the combination of strip welding drawing and rolling drawing and the like. The flat-plate-shaped film material welding method is complex in preparation process, pressure bearing difference and large in pipe diameter; the strip welding and drawing method has poor air tightness and complicated production process; and the rolling and drawing method adopted in part has the disadvantages of complex process (ingot casting, forging, drilling, extruding, rolling, drawing, straightening and the like), high energy consumption, thick thickness (more than 0.1 mm) and high cost, and the production mode can hardly meet the actual industrial use requirements. Therefore, it is urgently needed to develop a method for preparing an ultra-thin-wall hydrogen separation alloy capillary tube with a thin tube diameter, a thin thickness and excellent air tightness, which has the advantages of simple process, high efficiency and low energy consumption, and meets the development of the hydrogen energy in the future.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method and application of an alloy thin-wall capillary tube for hydrogen purification, which solve the defects of the prior art for preparing palladium and other alloy thin-wall capillary tubes. The method prepares the ultrathin-wall hydrogen separation alloy capillary tube by vacuum melting and casting the tube and rolling, has simple process and high efficiency, and the prepared ultrathin-wall hydrogen separation alloy capillary tube has the advantages of high precision, high yield, thin tube wall, good air tightness, stable performance and the like.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method and application of an alloy thin-wall capillary tube for hydrogen purification are characterized in that the technical process comprises the following steps:
(1) Vacuum melting the cast rod, putting each pure metal raw material into a crucible, vacuumizing the cavity to 1 × 10 -3 To 5X 10 -4 Filling 99.999 percent high-purity argon into the chamber to 0.5bar, setting the current to be 50-500A, repeatedly smelting for 10-20min, and then casting into an alloy round bar;
(2) Vacuum casting tube, placing the alloy round bar into crucible mold, vacuumizing the cavity to 1 × 10 -3 To 5X 10 - 4 Filling 99.999% high-purity argon into the cavity to 0.5bar or keeping a vacuum state, setting the power to 10-50KW, preserving heat for 0.5-2h, and completely forming and cooling to obtain a pierced billet;
(3) Pre-rolling the pierced billet, placing the pierced billet into a two-roller high-speed cold rolling mill, carrying out 1-5 times of rolling, controlling the elongation coefficient of each time of rolling to be 1.1-5.0, and carrying out intermediate annealing heat treatment in vacuum or inert atmosphere by using a heat treatment furnace when the total rolling deformation rate reaches 0.1-0.7 to obtain a tube blank with the diameter of 6.0-9.5mm and the wall thickness of 0.6-1.2 mm;
(4) Fine rolling the pipe blank, fine rolling the semi-finished pipe blank by using a three-roller high-speed cold rolling mill to obtain a finished pipe, placing the pipe blank into the three-roller high-speed cold rolling mill, carrying out 6-15-pass rolling, controlling the elongation coefficient of each pass to be 1.1-3.0, and carrying out intermediate annealing heat treatment in vacuum or inert atmosphere by using a heat treatment furnace when the total rolling deformation rate reaches 0.05-0.60 to obtain the finished pipe with the diameter of 1.5-4mm and the wall thickness of 0.01-0.15 mm.
Preferably, the alloy round rod is made of one of palladium alloy, vanadium alloy and niobium alloy;
when the component of the alloy round rod is palladium alloy, the palladium alloy is one of Pd-Ag alloy, pd-Cu alloy, pd-Au alloy, pd-Y alloy, pd-Ru alloy, pd-Ni alloy, pd-Pt alloy, pd-Ag-Cu alloy, pd-Ag-Au alloy, pd-Ag-Y alloy, pd-Ag-Ru alloy, pd-Cu-Au alloy, pd-Cu-Y alloy, pd-Cu-Ti alloy, pd-Cu-Zr alloy, pd-Cu-Ni alloy and Pd-Ag-Au-Ni alloy;
when the component of the alloy round rod is vanadium alloy, the vanadium alloy is one of V-Ni alloy, V-Al alloy, V-Fe alloy, V-W alloy, V-Mo alloy, V-Fe-Al V-Al-Cu alloy and V-Cr-Al alloy;
when the components of the alloy round rod are niobium alloy, the niobium alloy is one of Nb-Ti-Co alloy, nb-Ti-Ni alloy, nb-Hf-Co alloy and Nb-Ti-Hf-Co alloy.
Preferably, the alloy round bar obtained in the step of vacuum melting and casting the bar has a diameter of 5-30mm and a height of 5-200mm.
Preferably, the step of vacuum melting and casting the bar adopts vacuum arc melting and suction casting or induction melting and turnover casting.
Preferably, in the vacuum tube casting step, the crucible mold is made of one of graphite, alumina and boron nitride.
Preferably, in the vacuum tube casting step, natural cooling or liquid metal cooling is performed by a protective atmosphere.
Preferably, the size of the pierced billet obtained in the vacuum tube casting step is 10-50mm in outer diameter, 1-5mm in wall thickness and 200-700mm in length.
Preferably, in the step of pre-rolling the pierced billet, the rolling passes are 1 to 4 times, the elongation coefficient of each pass is controlled to be 1.1 to 4.0, the total rolling deformation rate before the intermediate annealing heat treatment is controlled to be 0.1 to 0.7, the diameter of the pierced billet is 7 to 9.5mm, and the wall thickness is 0.6 to 1.2mm.
Preferably, in the step of finish rolling of the tube blank, the rolling passes are 7-10 times, the elongation coefficient of each pass is controlled to be 1.1-2.5, the total rolling deformation rate before the intermediate annealing heat treatment is controlled to be 0.25-0.55, the diameter of the tube blank is 1.5-4mm, and the wall thickness is 0.015-0.15mm; the temperature of the intermediate annealing heat treatment is 650-950 ℃, and the time is 20-180min.
An application of a preparation method of an alloy thin-wall capillary tube for hydrogen purification in hydrogen purification.
Compared with the prior art, the invention has at least the following advantages:
1. compared with the method for drilling and cogging after casting the rod, the method has the advantages of simple operation, easy control of the size of the tube blank, reduction of process steps and raw material waste, reduction of energy consumption and the like;
2. the seamless tube prepared by the vacuum tube casting technology has uniform structure and refined grains, and avoids the defects of rolling cracking;
3. the invention combines the two-step rolling process, solves the defect that the existing rolling process can not roll the ultrathin-wall capillary tube, and simultaneously, the prepared capillary tube has high precision, good compactness and low surface roughness;
4. the hydrogen permeable alloy capillary tube prepared by the invention has the advantages of thin thickness, small tube diameter, high density, excellent compression resistance, large hydrogen permeation flow, reduced cost, improved production efficiency, expanded application field and wide application prospect in the field of high-purity hydrogen production.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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 invention.
Example 1
The embodiment specifically comprises the following steps:
(1) Vacuum melting and casting a rod:
the metals were proportioned according to Pd: ag =0.77 and placed in a crucible, and the chamber was evacuated to 8 × 10 - 4 And (3) filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 250A, repeatedly smelting for 10-20min, further vacuumizing the mould chamber to suck the alloy melt into the mould chamber, and casting the alloy melt into an alloy round rod with the diameter of 20mm and the length of 60 mm.
(2) Vacuum tube casting:
placing the alloy round rod into a graphite mold, and vacuumizing the cavity to 9 x 10 -4 And (2) filling 99.999% of high-purity argon into the chamber to 0.5bar, enabling the power to be 20KW, enabling the molten alloy round bar to enter a graphite mould after being melted, preserving the heat for 1h, naturally cooling, taking out the alloy pierced billet with the diameter of 20mm, the wall thickness of 2mm and the length of 400mm, and cleaning the surface.
(3) Pre-rolling a pierced billet:
placing the pierced billet into a two-roller high-speed rolling mill, wherein the rolling passes are 2 times, the rolling elongation coefficient of each pass is controlled to be 1.8-2.5, when the total rolling deformation rate is 0.5, performing intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere, and the diameter and the wall thickness of the pierced billet are 8.0mm and 0.68mm respectively.
(4) Finely rolling the tube blank:
and (3) placing the tube blank into a three-roll high-speed cold rolling mill, carrying out 8-pass rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-2, and carrying out intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere when the total rolling deformation rate reaches 0.5 to obtain a finished tube with the diameter of 2.0mm and the wall thickness of 0.025 mm.
Example 2
The embodiment specifically comprises the following steps:
(1) Vacuum melting and casting a rod:
each metal was carried out as Pd: cu =0.6Proportioning, placing in crucible, vacuumizing to 8X 10 -4 And (3) filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 250A, repeatedly smelting for 10-20min, further vacuumizing the mould chamber to suck the alloy melt into the mould chamber, and casting the alloy melt into an alloy round rod with the diameter of 18mm and the length of 65 mm.
(2) Vacuum tube casting:
placing the alloy round rod into a graphite mold, and vacuumizing the cavity to 9 x 10 -4 And (2) filling 99.999% high-purity argon into the chamber to 0.5bar, setting induction current to be 20KW, melting the alloy round bar, putting the melted alloy into a graphite mould, preserving heat for 1h, naturally cooling, taking out the alloy pierced billet with the diameter of 20mm, the wall thickness of 1.9mm and the length of 380mm, and cleaning the surface.
(3) Pre-rolling a pierced billet:
placing the pierced billet into a two-roller high-speed rolling mill, wherein the rolling passes are 2 times, the rolling elongation coefficient of each pass is controlled to be 1.8-2.5, when the total rolling deformation rate is 0.5, performing intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere, and the diameter and the wall thickness of the pierced billet are 8.3mm and 0.7mm respectively.
(4) Fine rolling of the tube blank:
and (3) placing the tube blank into a three-roll high-speed cold rolling mill, carrying out 8-pass rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-2, and carrying out intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere when the total rolling deformation rate reaches 0.5 to obtain a finished tube with the diameter of 2.5mm and the wall thickness of 0.03 mm.
Example 3
The embodiment specifically comprises the following steps:
(1) Vacuum melting and casting a rod:
each metal was proportioned as Pd: Y =0.92 and placed in a crucible, and the chamber was evacuated to 8 × 10 - 4 And (3) filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 280A, repeatedly smelting for 10-20min, further vacuumizing the mould chamber to suck the alloy melt into the mould chamber, and casting the alloy melt into an alloy round rod with the diameter of 18mm and the length of 65 mm.
(2) Vacuum tube casting:
putting the alloy round bar into a graphite mould, aligning the cavitiesThe chamber is evacuated to 9X 10 -4 And (2) filling 99.999% of high-purity argon into the chamber to 0.5bar, enabling the power to be 22KW, enabling the molten alloy round bar to enter a graphite mold after being melted, preserving the heat for 1h, naturally cooling, taking out the alloy pierced billet with the diameter of 20mm, the wall thickness of 1.9mm and the length of 380mm, and cleaning the surface.
(3) Pre-rolling a pierced billet:
placing the pierced billet into a two-roller high-speed rolling mill, wherein the rolling passes are 2 times, the rolling elongation coefficient of each pass is controlled to be 1.8-2.5, when the rolling total deformation rate is 0.5, performing intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere, and the diameter and the wall thickness of the pierced billet are 8.3mm and 0.7mm respectively.
(4) Fine rolling of the tube blank:
and (3) placing the tube blank into a three-roll high-speed cold rolling mill, carrying out 8-pass rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-2, and carrying out intermediate annealing heat treatment for 45min at the temperature of 720 ℃ in an argon atmosphere when the total rolling deformation rate reaches 0.5 to obtain a finished tube with the diameter of 2.2mm and the wall thickness of 0.028 mm.
Example 4
The embodiment specifically comprises the following steps:
(1) Vacuum melting and casting a rod:
each metal was proportioned as V: ni =0.85 and placed in a crucible, and the chamber was evacuated to 8 × 10 - 4 And (3) filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 340A, repeatedly smelting for 10-20min, and then further vacuumizing the mould chamber to suck the alloy melt into the mould chamber to cast the alloy melt into an alloy round bar with the diameter of 19mm and the length of 60 mm.
(2) Vacuum tube casting:
placing the alloy round rod into a graphite mold, and vacuumizing the cavity to 9 x 10 -4 And (2) filling 99.999% high-purity argon into the chamber to 0.5bar, keeping the power at 30KW, melting the alloy round bar, putting the melted alloy into a graphite mould, preserving the heat for 1h, naturally cooling, taking out the alloy pierced billet with the diameter of 20mm, the wall thickness of 1.9mm and the length of 400mm, and cleaning the surface.
(3) Pre-rolling a pierced billet:
placing the pierced billet into a mandrel of a two-roller high-speed rolling mill, wherein the rolling passes are 2 times, the rolling elongation coefficient of each pass is controlled to be 1.7-2.2, the total rolling deformation rate is 0.5, and the pierced billet is subjected to intermediate annealing heat treatment for 60min at the temperature of 800 ℃ in an argon atmosphere, and has the diameter of 8.3mm and the wall thickness of 0.7mm.
(4) Finely rolling the tube blank:
and (3) placing the tube blank into a three-roll high-speed cold rolling mill, carrying out 8-pass rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-2, and carrying out intermediate annealing heat treatment for 60min at the temperature of 800 ℃ in an argon atmosphere when the total rolling deformation rate reaches 0.4 to obtain a finished tube with the diameter of 3mm and the wall thickness of 0.05 mm.
Example 5
The embodiment specifically comprises the following steps:
(1) Vacuum melting and casting a rod:
the metals were proportioned as Nb to Ti to Co =0.3 and placed in a crucible, the chamber was evacuated to 8 × 10 -4 And (2) filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 400A, repeatedly smelting for 10-20min, further vacuumizing the mould chamber to suck the alloy melt into the mould chamber, and casting into an alloy round rod with the diameter of 20mm and the length of 50 mm.
(2) Vacuum tube casting:
placing the alloy round rod into a graphite mould, and vacuumizing the cavity to 9 multiplied by 10 -4 And (2) filling 99.999% high-purity argon into the chamber to 0.5bar, keeping the power at 35KW, melting the alloy round bar, putting the melted alloy into a graphite mould, preserving the heat for 1h, naturally cooling, taking out the alloy pierced billet with the diameter of 20mm, the wall thickness of 1.9mm and the length of 400mm, and cleaning the surface.
(3) Pre-rolling a pierced billet:
placing the pierced billet into a mandrel of a two-roller high-speed rolling mill, wherein the rolling passes are 2 times, the rolling elongation coefficient of each pass is controlled to be 1.7-2.2, the total rolling deformation rate is 0.5, intermediate annealing heat treatment is carried out for 90min at the temperature of 900 ℃ in an argon atmosphere, the diameter of the tube blank is 8.3mm, and the wall thickness is 0.7mm.
(4) Finely rolling the tube blank:
and (3) placing the tube blank into a three-roll high-speed cold rolling mill, carrying out 8-pass rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-2, and carrying out intermediate annealing heat treatment for 90min at the temperature of 800 ℃ in an argon atmosphere when the total rolling deformation rate reaches 0.4 to obtain a finished tube with the diameter of 3mm and the wall thickness of 0.06 mm.
Compared with the prior art, the invention has at least the following advantages:
1. compared with the method for drilling and cogging after casting the rod, the method has the advantages of simple operation, easy control of the size of the tube blank, reduction of process steps and raw material waste, reduction of energy consumption and the like;
2. the seamless tube prepared by the vacuum tube casting technology has uniform structure and refined grains, and avoids the defects of rolling cracking;
3. the invention combines the two-step rolling process, solves the defect that the existing rolling process can not roll the ultrathin-wall capillary tube, and simultaneously, the prepared capillary tube has high precision, good compactness and low surface roughness;
4. the hydrogen permeable alloy capillary tube prepared by the invention has the advantages of thin thickness, small tube diameter, high density, excellent compression resistance, large hydrogen permeation flow, reduced cost, improved production efficiency, expanded application field and wide application prospect in the field of high-purity hydrogen production.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of an alloy thin-wall capillary tube for hydrogen purification is characterized by comprising the following steps:
(1) Vacuum melting the cast rod, putting each pure metal raw material into a crucible, vacuumizing the cavity to 5 x 10 -4 To 1X 10 -3 Filling 99.999% high-purity argon into the chamber to 0.5bar, setting the current to be 50-500A, repeatedly smelting for 10-20min, and then casting into an alloy round bar;
(2) Vacuum casting tube, placing the alloy round bar into crucible mold, vacuumizing the cavity to 1 × 10 -3 To 5X 10 -4 Filling 99.999% high-purity argon into the cavity to 0.5bar or keeping the vacuum state, setting the power to be 10-50KW, preserving the heat by 0.5-2h, and completely forming and cooling to obtain a pierced billet;
(3) Pre-rolling the pierced billet, placing the pierced billet into a two-roller high-speed cold rolling mill, carrying out 1-5 passes of rolling, controlling the elongation coefficient of each pass of rolling to be 1.1-5.0, and carrying out intermediate annealing heat treatment in vacuum or inert atmosphere by using a heat treatment furnace when the total rolling deformation rate reaches 0.1-0.7 to obtain a tube blank with the diameter of 6.0-9.5mm and the wall thickness of 0.6-1.2 mm;
(4) The method comprises the following steps of finely rolling a tube blank, finely rolling the semi-finished tube by using a three-roll high-speed cold rolling mill to obtain a finished tube, placing the tube blank into the three-roll high-speed cold rolling mill, rolling for 6-15 times, controlling the elongation coefficient of each rolling time to be 1.1-3.0, and performing intermediate annealing heat treatment in a vacuum or inert atmosphere by using a heat treatment furnace when the total rolling deformation rate reaches 0.05-0.60 to obtain the finished tube with the diameter of 1.5-4mm and the wall thickness of 0.01-0.15 mm.
2. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein the alloy round rod comprises one of palladium alloy, vanadium alloy and niobium alloy;
when the component of the alloy round rod is palladium alloy, the palladium alloy is one of Pd-Ag alloy, pd-Cu alloy, pd-Au alloy, pd-Y alloy, pd-Ru alloy, pd-Ni alloy, pd-Pt alloy, pd-Ag-Cu alloy, pd-Ag-Au alloy, pd-Ag-Y alloy, pd-Ag-Ru alloy, pd-Cu-Au alloy, pd-Cu-Y alloy, pd-Cu-Ti alloy, pd-Cu-Zr alloy, pd-Cu-Ni alloy and Pd-Ag-Au-Ni alloy;
when the component of the alloy round rod is vanadium alloy, the vanadium alloy is one of V-Ni alloy, V-Al alloy, V-Fe alloy, V-W alloy, V-Mo alloy, V-Fe-Al V-Al-Cu alloy and V-Cr-Al alloy;
when the components of the alloy round rod are niobium alloy, the niobium alloy is one of Nb-Ti-Co alloy, nb-Ti-Ni alloy, nb-Hf-Co alloy and Nb-Ti-Hf-Co alloy.
3. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein the diameter of the alloy round rod obtained in the step of vacuum melting and casting the rod is 5-30mm, and the height of the alloy round rod is 5-200mm.
4. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein vacuum arc melting suction casting or induction melting turnover casting is adopted in the step of vacuum melting and rod casting.
5. The method for preparing an alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein in the step of vacuum tube casting, the crucible mold is made of one of graphite, alumina and boron nitride.
6. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 5, wherein in the step of vacuum tube casting, natural cooling or liquid metal cooling is performed by a protective atmosphere.
7. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein the size of the pierced tube obtained in the step of vacuum tube casting is 10-50mm, the wall thickness is 1-5mm, and the length is 200-700mm.
8. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein in the step of pre-rolling the pierced billet, the rolling passes are 1 to 4, the rolling elongation coefficient of each pass is controlled to be 1.1 to 4.0, the total rolling deformation rate before the intermediate annealing heat treatment is controlled to be 0.1 to 0.7, the diameter of the tube blank is 7 to 9.5mm, and the wall thickness is 0.6 to 1.2mm.
9. The method for preparing the alloy thin-wall capillary tube for hydrogen purification according to claim 1, wherein in the step of finish rolling of the tube blank, the rolling passes are 7-10 times, the rolling elongation coefficient of each pass is controlled to be 1.1-2.5, the total rolling deformation rate before the intermediate annealing heat treatment is controlled to be 0.25-0.55, the diameter of the tube blank is 1.5-4mm, and the wall thickness is 0.015-0.15mm; the temperature of the intermediate annealing heat treatment is 650-950 ℃, and the time is 20-180min.
10. Use of the preparation process according to any one of claims 1 to 9 for the purification of hydrogen.
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