阅读说明：本技术 一种半固态金属基水解制氢材料及制备方法 (Semi-solid metal-based hydrolysis hydrogen production material and preparation method thereof ) 是由 黄海军 疏达 汪东红 祝国梁 孙宝德 于 2019-08-06 设计创作，主要内容包括：本发明提供了一种半固态金属基水解制氢材料及制备方法,材料具有半固态组织,半固态组织包括金属基体元素的球状或近球状初生相,以及含有活性元素网状的二次凝固组织,其中金属基体元素的球状或近球状初生相均匀弥散分布于含有活性元素网状的二次凝固组织中；金属基体元素与活性元素经预制成坯料,再将坯料经半固态制浆,冷却之后获得半固态金属基水解制氢材料。本发明获得金属基块体水解制氢材料相比同成分其他现有组织的块体材料,产氢速率高出20％-500％,且产率近100％。(The invention provides a semi-solid metal-based hydrolysis hydrogen production material and a preparation method thereof, wherein the material has a semi-solid structure, the semi-solid structure comprises a spherical or near-spherical primary phase of a metal matrix element and a secondary solidification structure containing an active element net, wherein the spherical or near-spherical primary phase of the metal matrix element is uniformly dispersed and distributed in the secondary solidification structure containing the active element net; the metal matrix elements and the active elements are prefabricated into blanks, and then the blanks are subjected to semi-solid pulping and cooling to obtain the semi-solid metal-based hydrogen production material by hydrolysis. Compared with other block materials with the same components and the existing organization, the hydrogen production rate of the metal-based block hydrolysis hydrogen production material obtained by the invention is 20-500% higher, and the yield is nearly 100%.)

1. A semi-solid metal-based hydrolysis hydrogen production material is characterized in that: the material is provided with a semi-solid structure, wherein the semi-solid structure comprises a spherical or near-spherical primary phase of a metal matrix element and a secondary solidification structure containing an active element net, and the spherical or near-spherical primary phase of the metal matrix element is uniformly dispersed in the secondary solidification structure containing the active element net.

2. The semi-solid metal-based hydrolysis hydrogen production material of claim 1, wherein: the metal matrix elements and the active elements are prefabricated into blanks, and the blanks are subjected to semi-solid pulping and cooling to obtain the semi-solid metal-based hydrogen production material.

3. The semi-solid metal-based hydrolysis hydrogen production material of claim 1, wherein: the material comprises the following components in percentage by mass: the metal matrix element is 50-99%, and the active element is 1-50%.

4. The semi-solid metal-based hydrolysis hydrogen production material of claim 1, wherein: the material comprises the following components in percentage by mass: the metal matrix element is 50-80%, the active element is 19-50%, and the refiner is 0-1%.

5. The semi-solid metal-based hydrolysis hydrogen production material according to any one of claims 1-4, wherein: the metal matrix element is one or more of Al, Mg, Zn, Li and Ca.

6. The semi-solid metal-based hydrolysis hydrogen production material according to any one of claims 1-4, wherein: the active element is one or more of metal elements, metal oxides and metal salts.

7. The semi-solid metal-based hydrolysis hydrogen production material of claim 6, wherein: the metal elements are one or more of Ga, In, Sn, Bi, Hg, Cu, Mn, Si, Ni, Cr, V, Ti, Zr and Zn.

8. The semi-solid metal-based hydrolysis hydrogen production material of claim 6, wherein: has one or more of the following characteristics:

-said metal oxide is Bi₂O₃、ZnO、CaO，SnO₂One or more of;

-said metal salt is NaCl, KCl, MgCl₂、ZnCl₂、SnCl₂One or more of (a).

9. A method of preparing the semi-solid metal-based hydrolysis hydrogen production material of any one of claims 1-8, wherein:

firstly, prefabricating metal matrix elements and active elements into alloy blanks;

then the prepared alloy blank is processed by semi-solid pulping and cooling to obtain a semi-solid block hydrolysis hydrogen production material, wherein: the spherical or near-spherical primary phase of the metal matrix element is uniformly dispersed and distributed in the active element-containing reticular secondary solidification structure.

10. The method for preparing the semi-solid metal-based hydrolysis hydrogen production material according to claim 9, wherein the method comprises the following steps: the semi-solid pulping adopts any one of mechanical stirring, electromagnetic stirring, single-roller rotation method, double-roller rotation method, strain-induced activation method, secondary remelting method, ultrasonic vibration method, powder metallurgy method and spray deposition method.

Technical Field

The invention relates to the field of metal materials, in particular to a semi-solid metal-based hydrogen production material by hydrolysis and a preparation method thereof.

Background

Hydrogen energy is considered as a preferred approach for solving carbon emission, but the utilization of hydrogen energy and the development of hydrogen energy are severely restricted due to the development defects in hydrogen production, hydrogen transportation, hydrogen storage and the like. The hydrogen production of metal through hydrolysis reaction is a hydrogen energy acquisition method with prospect, not only has large energy density, large reserve capacity, easy acquisition and low cost, but also has the reaction product which is environment-friendly and can be recycled, and is regarded as a method integrating hydrogen storage, transportation and preparation, and the method has the advantages of: the hydrogen storage and transportation are realized by taking the active metal and the water as carriers, and the generation and the stop of the hydrogen are realized by controlling whether the active metal is contacted with the water, so that the problems that the hydrogen production by using fossil fuel is exhausted, the high-pressure hydrogen storage and the hydrogen transportation are safe and the like in the traditional hydrogen energy utilization process are solved, and the hydrogen production system has the advantage of conveniently producing the hydrogen in real time according to the needs.

The existing metal hydrolysis hydrogen production materials mainly have two types in morphology, namely granular materials and bulk materials. Among them, the block material has attracted more attention because of its simple preparation process, low energy consumption, convenient storage and low cost. However, most of the existing bulk materials are prepared by a manufacturing method.

The Chinese patent with publication number CN108913957A discloses a hydrolysis hydrogen production aluminum alloy and a preparation method and application thereof, the material structure of the hydrolysis hydrogen production aluminum alloy is in a coarse random particle or dendritic crystal structure, so that a block material is hydrolyzed mainly in an integral mode in the hydrolysis hydrogen production process, and due to the coverage of reaction byproducts on a reaction interface and the thickening of a covering layer, the hydrogen production speed is easy to be insufficient, the hydrogen conversion rate is low gradually along with the hydrolysis, and the further development and application of the metal hydrolysis hydrogen production technology are influenced.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a semi-solid metal-based hydrolysis hydrogen production material and a preparation method thereof.

According to a first aspect of the present invention, there is provided a semi-solid metal-based hydrolysis hydrogen production material,

the material is provided with a semi-solid structure, wherein the semi-solid structure comprises a spherical or near-spherical primary phase of a metal matrix element and a secondary solidification structure containing an active element net, and the spherical or near-spherical primary phase of the metal matrix element is uniformly dispersed in the secondary solidification structure containing the active element net.

Preferably, the metal matrix element and the active element are prefabricated into a blank, the blank is subjected to semi-solid pulping, and after cooling, the semi-solid metal-based hydrogen production material is obtained.

Preferably, the material comprises the following components in percentage by mass: the metal matrix element is 50-99%, and the active element is 1-50%.

Preferably, the material consists of the following components in percentage by mass: the metal matrix element is 50-80%, the active element is 19-50%, and the refiner is 0-1%.

Preferably, the metal matrix element is one or more of Al, Mg, Zn, Li, Ca.

Preferably, the active element is one or more of a metal element, a metal oxide and a metal salt.

Preferably, the metal element is one or more of Ga, In, Sn, Bi, Hg, Cu, Mn, Si, Ni, Cr, V, Ti, Zr, Zn.

Preferably, one or more of the following features:

-said metal oxide is Bi₂O₃、ZnO、CaO，SnO₂One or more of;

-said metal salt is NaCl, KCl, MgCl₂、ZnCl₂、SnCl₂One or more of (a).

In a second aspect of the present invention, a method for preparing a semi-solid metal-based hydrolysis hydrogen production material is provided, which comprises:

firstly, prefabricating metal matrix elements and active elements into alloy blanks;

then the prepared alloy blank is processed by semi-solid pulping and cooling to obtain a semi-solid block hydrolysis hydrogen production material, wherein: the spherical or near-spherical primary phase of the metal matrix element is uniformly dispersed and distributed in the active element-containing reticular secondary solidification structure.

Preferably, the semi-solid pulping adopts any one of mechanical stirring, electromagnetic stirring, single-roller rotation method, double-roller rotation method, strain-induced activation method, secondary remelting method, ultrasonic vibration method, powder metallurgy method and spray deposition method.

Preferably, the method further comprises the step of refining the semi-solid tissue, wherein the refining method adopts one or more of chemical method or physical method.

Compared with the prior art, the invention has at least one of the following beneficial effects:

the invention innovatively uses the semi-solid structure for the hydrolysis hydrogen production material, the semi-solid structure gradually disperses along with the hydrolysis, the spherical or near-spherical primary phase of fine metal matrix elements and the secondary solidification structure rich in active element net disperse in the hydrolysis environment to realize high-speed hydrolysis, and the fine structure is easier to realize complete hydrolysis so as to obtain high hydrogen yield.

The metal-based block hydrolysis hydrogen production material can realize continuous high-speed hydrogen production and high hydrogen conversion rate, and compared with other existing organized block materials with the same components, the novel organized metal-based block hydrolysis hydrogen production material provided by the invention has the advantages that the hydrogen production rate is 20-500% higher, and the yield is nearly 100%.

The components of the metal-based block hydrolysis hydrogen production material are further added with a refiner, so that a semi-solid structure is greatly refined, and the hydrolysis hydrogen production rate of the material is greatly improved.

The method can realize the batch production of the hydrogen production material and has the advantage of high productivity.

The preparation method of the invention is different from the ball milling method and the casting method of the existing preparation method of the aluminum-based hydrolysis material, and the material preparation of the invention is carried out by two stages of blank prefabrication and unique semi-solid forming or the two stages are combined into one. The casting method in the first stage is different from the related casting method in material composition and casting process requirements, and the semi-solid forming step in the second stage comprises semi-solid pulping and solidification forming, which is not available in the existing preparation method.

The method can be applied to the field of hydrogen production by hydrolysis or the field of obtaining hydrolysis byproducts of the metal-based block.

Drawings

Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:

FIG. 1 is a texture plot of Al-15 wt.% (GaInSn) in an embodiment of the present invention;

FIG. 2 is a plot of Al-15 wt.% (GaInSn) hydrogen production in accordance with an embodiment of the present invention;

FIG. 3 is a graph of Al-15 wt.% (GaInSn) hydrogen production rate in an embodiment of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.