Thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material and preparation method and application thereof
阅读说明：本技术 一种薄带状晶态Nb-Ti-Co氢分离材料及其制备方法和应用 (Thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material and preparation method and application thereof ) 是由 闫二虎 刘威 王豪 陈运灿 王金华 狄翀博 王星粤 孙立贤 于 2020-07-15 设计创作，主要内容包括：本发明公开了一种薄带状晶态Nb-Ti-Co氢分离材料,由Nb、Ti、Co为原料,熔炼为母合金后,经熔体旋淬得到非晶态合金,再经退火工艺形成晶态合金,所得材料为薄带状,其合金组织由作为渗氢相,起扩散作用的白色粒状α-Nb相和作为抗氢脆相,起抗氢脆作用的灰色TiCo相组成,两相呈镶嵌分布。其制备方法包括以下步骤：1)母合金的熔炼；2)薄带状非晶态Nb-Ti-Co氢分离材料的制备；3)薄带状晶态Nb-Ti-Co氢分离材料的制备。作为渗氢材料的应用,在673K温度下其氢透率为1-2.5×10<Sup>?8</Sup> molH<Sub>2</Sub>m<Sup>?1</Sup>s<Sup>?1</Sup>Pa<Sup>?1/2</Sup>。在纯氢气氛下其氢通量为14-18ccH<Sub>2</Sub>cm<Sup>?2</Sup>min<Sup>?1</Sup>,抗氢脆时间不少于110h。作为氢分离材料的应用,在氢气和二氧化碳或一氧化碳组成的二元混合气体条件下,有效分离氢气,并且抗氢脆时间不少于30 h。(The invention discloses a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material, which is prepared by smelting Nb, Ti and Co as raw materials into a master alloy, performing melt spinning quenching to obtain an amorphous alloy, and performing an annealing process to form a crystalline alloy, wherein the obtained material is in a thin strip shape, the alloy structure of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material consists of a white granular α -Nb phase serving as a hydrogen permeation phase and a gray TiCo phase serving as a hydrogen embrittlement resistant phase and a hydrogen embrittlement resistant phase, and the two phases are in mosaic distribution1‑2.5×10 −8 molH 2 m −1 s −1 Pa −1/2 . The hydrogen flux is 14-18ccH under pure hydrogen atmosphere 2 cm −2 min −1 The hydrogen embrittlement resistance time is not less than 110 h. The hydrogen is effectively separated under the condition of binary mixed gas consisting of hydrogen and carbon dioxide or carbon monoxide, and the hydrogen embrittlement resistance time is not less than 30 h.)
1. A thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is characterized in that: the material is prepared by melting Nb, Ti and Co into master alloy, performing melt spinning quenching and annealing, wherein the obtained material is thin strip-shaped, has a smooth and continuous surface and a thickness of 55-65 mu m, and the alloy structure of the material consists of a white granular alpha-Nb phase and a gray TiCo phase, wherein the alpha-Nb phase is a hydrogen permeation phase and plays a role in diffusion, and the TiCo phase is a hydrogen embrittlement resistance phase and plays a role in hydrogen embrittlement resistance.
2. The thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material according to claim 1, characterized in that: the diameter distribution range of the alpha-Nb hydrogen permeating phase is 0.25-3.4 mu m, and the hydrogen permeating phase and the hydrogen-resistant brittle phase are in mosaic distribution.
3. The thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material according to claim 1, characterized in that: the hydrogen separation material is subjected to melt spinning to obtain amorphous alloy, and the amorphous alloy is formed by combining with a later-stage annealing process.
4. A preparation method of a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is characterized by comprising the following steps:
step 1) smelting a master alloy, wherein the mass ratio of pure metals Nb, Ti and Co is 30: 35: 35, smelting high-purity Nb, Ti and Co as raw materials to obtain a master alloy;
step 2) preparing a thin strip-shaped amorphous Nb-Ti-Co hydrogen separation material, namely cutting the master alloy obtained in the step 1 into particles by adopting a linear cutting method, heating the particles to a molten state by utilizing magnetic induction, and preparing the thin strip-shaped amorphous Nb-Ti-Co hydrogen separation material by adopting a melt spinning process under a certain condition, wherein a nozzle material of a device used in the melt spinning process is a carbon material;
and 3) preparing the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material, namely annealing the thin strip-shaped amorphous Nb-Ti-Co hydrogen separation material obtained in the step 2 under certain conditions to obtain the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material.
5. The method of claim 4, wherein: the condition parameters of the melt rotary quenching in the step 2 are that the working temperature is 2000 ℃, and the cooling rate of a water cooling device in the device is 130-.
6. The method of claim 4, wherein: the annealing condition of the step 3 is that the annealing temperature is 1000 ℃ and the annealing time is 12 h.
7. The use of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material as a hydrogen permeation material in accordance with claim 1, wherein the hydrogen separation material is sputter-coated with palladium films having a thickness of 185-220nm and a hydrogen permeation rate of 1-2.5 × 10 at 673K−8molH2m−1s−1Pa−1/2。
8. Use of a thin strip-like crystalline Nb-Ti-Co hydrogen separation material as a hydrogen permeable material according to claim 7, characterized in that: 673K, under pure hydrogen atmosphere, its hydrogen flux is 14-18ccH2cm−2min−1The hydrogen embrittlement resistance time is not less than 110 h.
9. Use of a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material according to claim 7 as a hydrogen separation material, characterized in that: at 673K, under the condition of binary gas mixture containing 95% of hydrogen and 5% of carbon dioxide, the hydrogen flux of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is 13-15 ccH2cm−2min−1Is pure hydrogen85-95% of the value, and the hydrogen embrittlement resistance time is not less than 30 h.
10. Use of a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material according to claim 7 as a hydrogen separation material, characterized in that: at 673K, under the condition of binary gas mixture containing 95% of hydrogen and 5% of carbon monoxide, the hydrogen flux of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is 12-14 ccH2cm−2min−1The hydrogen gas value is 85-95% of the pure hydrogen gas value, and the hydrogen embrittlement resistance time is not less than 30 h.
Technical Field
The invention relates to the field of hydrogen purification, in particular to a thin strip-shaped crystalline Nb-Ti-Co hydrogen infiltration material and a preparation method and application thereof.
Background
In recent years, the demand of natural resources is increasing, non-renewable energy sources such as coal, petroleum and natural gas are increasingly deficient, and the natural environment is seriously polluted in the using process. Therefore, renewable energy sources (such as hydrogen energy, solar energy, wind energy, etc.) are receiving widespread attention from society. Among them, hydrogen energy is known as the most concerned energy in the 21 st century because of its many advantages such as high calorific value, no pollution (combustion product is water) and being renewable. The hydrogen as an ideal clean energy source has extremely important application at the present of fossil energy shortage, and the industrially prepared hydrogen often contains certain impurity gases (such as CO and CO)2、H2S), and therefore hydrogen purification is of particular importance.
The membrane separation technology is the most promising hydrogen separation method internationally recognized at present due to the advantages of low energy consumption, simplicity, practicability and the like, membrane materials applied to hydrogen separation mainly comprise a polymer membrane, a carbon membrane, a ceramic membrane, a metal membrane and the like, wherein the metal membrane has outstanding mechanical strength, hydrogen permeability, stability and the like, so the membrane separation technology is widely applied, and the permeation mechanism of the metal membrane is as follows: when a hydrogen pressure difference occurs across the metal film, hydrogen molecules are decomposed into hydrogen atoms at the high-pressure side of the metal film. The hydrogen atoms then dissolve into the metal and pass through the metal film to the low pressure side where they combine to produce H2The molecules are then removed from the metal filmAnd finally, the hydrogen is purified.
The palladium membrane and the palladium alloy membrane have the effect of catalyzing and dissociating hydrogen and have excellent hydrogen embrittlement resistance, but the palladium membrane has low hydrogen permeation rate when being applied to the separation and purification of the hydrogen, and the hydrogen permeation rate is only 1.54 × 10 at 673K-8mol H2m-1s-1Pa-1/2(ii) a In addition, palladium is a noble metal, the raw material cost is extremely high, and a Pd membrane with a thickness of 25 μm is about $4500/m2Severely limiting its large-scale application. Therefore, increasing the hydrogen permeation rate and reducing the raw material cost are problems to be solved urgently.
The prior research finds that the VB group metal Nb has a typical Bcc body-centered cubic structure and has higher hydrogen permeability than Pd under the same condition, and the hydrogen permeability reaches 3.52 × 10-7mol H2m-1s-1Pa-1/2(ii) a Moreover, the raw material of niobium is low in price. Niobium has the above characteristics that can solve the technical problems of palladium membranes, but niobium has a very strong hydrogen solubility. The characteristic determines that the cracking phenomenon is very serious because the hydrogen embrittlement phenomenon is easy to occur when the niobium is used in a single phase, so that the selection of proper elements to form the niobium-based alloy reduces the solubility of hydrogen, and the niobium-based alloy is an effective way for solving the hydrogen embrittlement phenomenon and improving the hydrogen embrittlement resistance.
For example, Hashi et al (Ishikawa K, Seki Y, Kita K, et al. hydropropagation in rapidly sequenced amophorus and crystallized Nb) of the prior art20Ti40Ni40alloyribbons[J]International Journal of Hydrogen Energy, 2011, 36(2):1784-20Ti40Ni40The alloy forms crystalline Nb after 1173K annealing for 10h20Ti40Ni40At 673K, although the alloy has good hydrogen embrittlement resistance, the hydrogen permeability is low and is only 0.48 × 10-8mol H2m-1s-1Pa-1/2。
In addition, the performance of the material is closely related to the preparation process of the material, the current Nb-Ti-Co alloy film is mostly prepared by adopting electric arc melting and combining with the later stage linear cutting technology, and the alloy sample is caused when the alloy is melted by adopting the electric arc melting methodThe product has very high cooling speed (up to 200K/s) in a water-cooled copper crucible, which can cause the nonuniform internal structure of the alloy and has a great deal of defects, and the thickness of an alloy membrane cut by a later linear cutting technology is generally 0.7mm, and the hydrogen permeation flow is lower by 1-5 ccH2cm-2min-1The obtained alloy membrane has limited size, and inevitably causes damage to the alloy structure during the cutting process, thereby affecting the continuity of the hydrogen diffusion channel.
Meanwhile, the prior art shows that (Tokui S, Ishikawa K, Aoki K. microstuctural control by a Rolling-Annealing Technique and Hydrogen Permeability in the Nb-Ti-Ni alloys [ J ]. MRS on line processing Library approach, 2011, 885: 0885-A09-60.) the phase structure of the alloy can be adjusted through an Annealing process, and further the Hydrogen embrittlement resistance of the alloy film is improved.
Therefore, the prior art has the following technical problems:
1) the hydrogen separation alloy membrane prepared by adopting the arc melting method needs to be sliced later and has larger thickness, so that the application range is limited;
2) the partial hydrogen separation alloy membrane has poor hydrogen permeation performance, is easy to hydrogen embrittlement, has short service life and is not suitable for large-scale application;
3) the palladium and the palladium alloy membrane which are widely applied at present have higher manufacturing cost and are not suitable for large-scale application.
Disclosure of Invention
The invention aims to prepare the Nb-Ti-Co hydrogen separation material with good hydrogen permeation performance and better durability; another object is to provide a new process for preparing thin ribbon crystalline Nb-Ti-Co hydrogen separation materials.
Aiming at the technical problems in the prior art, the invention adopts the following principles and methods to solve the problems:
1. the hydrogen separation material is prepared by taking Nb, Ti and Co as raw materials,
the metal niobium has the performances of high temperature resistance, wear resistance, extremely stable chemical property, higher hydrogen permeability and the like;
the metal titanium has the performances of high temperature resistance, corrosion resistance, high strength and the like;
the metal cobalt has good cutting performance;
and the three have better intersolubility.
Therefore, the hydrogen separation material prepared from Nb, Ti and Co has excellent hydrogen permeation performance, hydrogen embrittlement resistance and cutting processability; in addition, the metal raw materials adopted by the invention also have the characteristic of low cost.
2. Compared with an electric arc smelting method, the alloy membrane with a smooth and continuous surface and a thickness of less than 100 mu m can be prepared by adopting a melt rotary quenching process, and can be directly applied to hydrogen separation without complex operations such as later cutting, polishing and the like, so that the damage and damage to the alloy surface are effectively reduced, the hydrogen permeation performance is improved, and the method is very suitable for the production and preparation of industrial large-scale hydrogen separation membranes;
3. because the alloy film prepared by the melt spinning quenching process is an amorphous alloy film, the amorphous alloy film is limited by thermal stability and the like in practical application, and an annealing process is required to be subsequently adopted to convert the alloy film into a crystalline state and adjust the phase structure of the alloy, so that the performances of the alloy film such as permeability, ductility, hardness and the like are improved.
4. Meanwhile, a nozzle adopted in the conventional melt spinning process is made of quartz material, and due to poor heat resistance and stability, the molten Nb-Ti-Co alloy is easy to solidify at the bottom of the nozzle and difficult to spray, and is not suitable for the invention.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is prepared by melting Nb, Ti and Co into master alloy, performing melt spinning quenching and annealing process, wherein the obtained material is thin strip-shaped, has a smooth and continuous surface and a thickness of 55-65 mu m, and the alloy structure of the material consists of a white granular alpha-Nb phase and a gray TiCo phase, wherein the alpha-Nb phase is a hydrogen permeation phase and plays a role in diffusion, and the TiCo phase is a hydrogen embrittlement resistance phase and plays a role in hydrogen embrittlement resistance;
the diameter distribution range of the alpha-Nb hydrogen permeating phase is 0.25-3.4 mu m, and the hydrogen permeating phase and the hydrogen-resistant brittle phase are in mosaic distribution;
the hydrogen separation material is subjected to melt spinning to obtain amorphous alloy, and the amorphous alloy is formed by combining with a later-stage annealing process.
A preparation method of a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material comprises the following steps:
step 1) smelting a master alloy, wherein the mass ratio of pure metals Nb, Ti and Co is 30: 35: 35, smelting high-purity Nb, Ti and Co as raw materials to obtain a master alloy;
step 2) preparing a thin strip-shaped amorphous Nb-Ti-Co hydrogen separation material, namely cutting the master alloy obtained in the
the condition parameters of melt rotary quenching are that the working temperature is 2000 ℃, the rotating speed of a copper roller is 2000r/min, and the cooling rate of a water cooling device in the device is 135 ℃/min;
step 3) preparing a thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material, namely annealing the thin strip-shaped amorphous Nb-Ti-Co hydrogen separation material obtained in the
the annealing treatment condition of the
The application of thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material as hydrogen permeation material is characterized by that the hydrogen separation material is plated with palladium film by means of sputtering method, the thickness of palladium film on two sides is 185-220nm, and its hydrogen permeation rate is 1-2.5 × 10 at 673K temperature−8molH2m− 1s−1Pa−1/2。
673K, under pure hydrogen atmosphere, its hydrogen flux is 14-18ccH2cm−2min−1The hydrogen embrittlement resistance time is not less than 110 h.
673K, at a hydrogen content of 95%,the hydrogen flux of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is 13-15 ccH under the condition of binary gas mixture with 5 percent of carbon dioxide content2cm−2min−1The hydrogen gas value is 85-95% of the pure hydrogen gas value, and the hydrogen embrittlement resistance time is not less than 30 h.
673K, under the condition of binary gas mixture containing 95% hydrogen and 5% carbon monoxide, the hydrogen flux of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is 12-14 ccH2cm−2min−1The hydrogen gas value is 85-95% of the pure hydrogen gas value, and the hydrogen embrittlement resistance time is not less than 30 h.
The thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material prepared by the invention has the advantages that:
1. in the Nb-Ti-Co hydrogen separation material, metal niobium has the performances of high temperature resistance, wear resistance, extremely stable chemical property, higher hydrogen permeability and the like, metal titanium has the performances of high temperature resistance, corrosion resistance, high strength and the like, metal cobalt has good cutting performance, and the three have good intersolubility, so that the Nb-Ti-Co alloy as the hydrogen separation material has excellent hydrogen permeation performance, hydrogen embrittlement resistance and cutting processing performance.
2. Compared with an electric arc smelting method, the alloy membrane with a smooth and continuous surface and a thickness of less than 100 mu m can be prepared by adopting a melt spinning process, the alloy membrane can be directly applied to hydrogen separation without complex operations such as later cutting, polishing and the like, the damage and damage to the alloy surface are effectively reduced, the hydrogen permeation performance is improved, the alloy membrane is very suitable for production and preparation of industrial large-scale hydrogen separation membranes, the phase structure of the alloy is adjusted by a subsequent annealing process, and the properties such as the permeability, ductility and hardness of the alloy membrane are improved.
3. The hydrogen permeability at 673K is 1.68 × 10−8molH2m−1s−1Pa−1/2The hydrogen flux was 15.55cc H under a pure hydrogen atmosphere2cm−2min−13-9 times of other as-cast niobium-based films under the same condition, and the hydrogen embrittlement resistance time in the hydrogen permeation process is not less than 110 h.
4. The price of the prepared thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material is lower than that of a palladium membrane, the average per square meter of the thin strip-shaped crystalline Nb-Ti-Co hydrogen separation material plated with the 200nm palladium membrane is about $ 170, and the per square meter of the Pd membrane with the thickness of 25 mu m costs $ 4500.
Therefore, compared with the prior art, the invention improves the processability, hydrogen brittleness resistance and hydrogen permeability of the hydrogen separation material, reduces the cost and has wide application prospect in the field of hydrogen purification.
Drawings
FIG. 1 is a master alloy after arc melting in example 1;
FIG. 2 shows ribbon-like amorphous Nb prepared by the melt-spinning process of example 130Ti35Co35XRD spectrum (b), amorphous structure (c) and spectrum (d) of the hydrogen separation material;
FIG. 3 is a schematic view showing heating of amorphous Nb in a DSC apparatus in example 130Ti35Co35Alloy thermogram (a) and XRD pattern (b), arrow (b)T A）-（T D) Marking the position corresponding to the heating temperature selection during XRD test;
FIG. 4 shows Nb in example 1 and comparative examples 1, 2 and 330Ti35Co35SEM images of hydrogen separation materials;
FIG. 5 shows the thin strip-shaped crystalline Nb in example 1 and comparative example 130Ti35Co35The embedded graph is the surface appearance of the alloy strip after hydrogen permeation after annealing at 1000 ℃ for 24 hours according to the change rule of hydrogen flux of the hydrogen separation material along with time;
FIG. 6 shows the thin strip-shaped crystalline Nb in example 130Ti35Co35Hydrogen separation materials in different CO or CO2Hydrogen permeation characteristics at feed concentration (a) CO2Or the change curve of thin strip hydrogen permeation flux with time under CO atmosphere, (b) hydrogen permeation performance and CO2A curve relating contents, (c) a curve relating hydrogen permeability to CO content, (d) CO and CO2Linear regression curve between adsorption constant and reciprocal temperature and corresponding change in adsorption enthalpy (Δ)H i)；
FIG. 7 shows the thin ribbon amorphous Nb in example 130Ti35Co35The change rule of the hydrogen flux of the hydrogen separation material along with time, and an inset is the surface appearance after the hydrogen permeation test.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are provided in the accompanying drawings, but are not intended to limit the present invention.
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