阅读说明：本技术 一种铝合金制氢方法以及反应液的用途 (Aluminum alloy hydrogen production method and application of reaction liquid ) 是由 高钱 魏存弟 李永涛 于 2018-05-31 设计创作，主要内容包括：本发明公开了一种铝合金制氢方法,将可水解制氢的铝合金与无机盐的水溶液接触,以进行水解制氢反应,其中,所述反应液为可溶性无机盐的水溶液,所述无机盐为碱金属、碱土金属、锌、铝和锰的卤化物盐中的一种或多种；本发明还提供了上述反应液在与铝合金进行水解制氢反应中的用途。本发明在反应结束后能够实现对合金中稀有金属快速高效地回收利用。(The invention discloses a method for preparing hydrogen from aluminum alloy, which comprises the steps of contacting aluminum alloy capable of preparing hydrogen through hydrolysis with aqueous solution of inorganic salt to perform hydrolysis hydrogen-preparing reaction, wherein the reaction solution is aqueous solution of soluble inorganic salt, and the inorganic salt is one or more of halide salts of alkali metal, alkaline earth metal, zinc, aluminum and manganese; the invention also provides application of the reaction liquid in hydrolysis hydrogen production reaction with aluminum alloy. The method can realize the rapid and efficient recycling of rare metals in the alloy after the reaction is finished.)

1. The method for preparing the hydrogen by the aluminum alloy is characterized in that the aluminum alloy capable of preparing the hydrogen by hydrolysis is contacted with a reaction liquid to perform hydrolysis hydrogen-preparing reaction, wherein the reaction liquid is an aqueous solution of soluble inorganic salt, and the inorganic salt is one or more of halide salt and nitrate of alkali metal, alkaline earth metal, zinc, aluminum and manganese; preferably one or more of halide salts of potassium, sodium, calcium, magnesium, zinc, aluminum, manganese; further preferably one or more of hydrochloride of potassium, sodium, calcium, magnesium, zinc, aluminum and manganese.

2. the method according to claim 1, wherein the concentration of the inorganic salt in the aqueous solution of the inorganic salt is not more than 10mol/L, preferably 0.05 to 5mol/L, and more preferably 0.1 to 1 mol/L.

3. The method according to claim 1 or 2, wherein the aluminum alloy and the reaction solution are subjected to hydrolysis hydrogen production, the liquid-solid ratio is not less than 15L/Kg, preferably 18 to 25L/Kg, and the reaction temperature is 20 to 60 ℃, preferably 30 to 50 ℃.

4. The method according to any one of claims 1 to 3, further comprising subjecting the aqueous solution after the hydrogen production reaction by hydrolysis to solid-liquid separation to obtain a solid-phase metal;

Preferably, the method further comprises the steps of dropwise adding alkali liquor, preferably weak alkali solution, into the liquid obtained by the solid-liquid separation until no precipitate is generated, obtaining precipitate after the separation, and drying the precipitate to obtain the hydrolysate of the aluminum.

5. the method according to any one of claims 1-4, wherein the aluminum alloy is an Al-Ga-In-Sn alloy;

Optionally, the aluminum alloy further comprises an X metal component, and the X metal component is selected from one or more of metal bismuth, zinc, iron, copper, magnesium and titanium.

6. The method of claim 5, wherein the aluminum alloy comprises 80-94 wt% aluminum, 2-5 wt% gallium, 3-16 wt% indium, and tin, wherein the sum of the aluminum, gallium, indium, and tin contents is no less than 90 wt%.

7. The method according to claim 6, wherein the aluminum alloy consists of 80-90 wt% aluminum, 2-5 wt% gallium, 3-15 wt% indium and tin, and not more than 10 wt% of X metal component, preferably the X metal component content is not more than 8 wt%, further preferably not more than 6 wt%, more preferably 0.5-4 wt%.

8. The method of claim 7, wherein the mass ratio of indium to tin in the aluminum alloy is between 1:4 and 3: 1.

9. The application of the reaction liquid in hydrolysis hydrogen production reaction with aluminum alloy is characterized in that the reaction liquid is an aqueous solution of soluble inorganic salt, and the inorganic salt is one or more of halide salt and nitrate of alkali metal, alkaline earth metal, zinc, aluminum and manganese; preferably one or more of halide salts of potassium, sodium, calcium, magnesium, zinc, aluminum, manganese; further preferably one or more of hydrochloride of potassium, sodium, calcium, magnesium, zinc, aluminum and manganese.

Technical Field

the invention relates to a method for producing hydrogen by aluminum-based alloy and application of reaction liquid, in particular to a method for producing hydrogen by reacting the aluminum-based alloy with the reaction liquid instead of water or acid and alkali solution, and quickly recovering unreacted metal or intermetallic compounds after reaction.

Background

Because of the advantages of low price, wide source, high energy density and the like, the aluminum is the first choice for hydrogen production in metal, but because of the high activity, an oxide film is very easy to form in the air, and the aluminum has a certain effect of hindering the reaction. The low-melting-point metal Ga is added into the aluminum base to form alloy, so that the problem of the oxide film on the surface of the aluminum can be effectively solved, and the reaction is obviously promoted. Therefore, the reaction of aluminum-based alloy with water to produce hydrogen becomes the focus of research in recent years, and the hydrogen production mode is suitable for portable application, high in efficiency and simple in operation equipment. Through continuous exploration of researchers In various countries, various aluminum-based alloys capable of continuously reacting with water to release hydrogen are researched, for example, metals such as Ga, In, Sn, Zn, Ti, Fe and the like are added into aluminum to prepare binary, ternary, quaternary, quinary and even more-element alloys, and the hydrogen production performance is improved to different degrees when the alloys react with water.

However, when the aluminum-based alloy reacts with water, only aluminum generally reacts with water to release hydrogen, and other components such as Ga, In, Sn, Zn, Ti, Fe, etc. do not react with water. Therefore, In addition to pure hydrogen gas, the product after reaction is mixed In solution with aluminum hydrolysate and metals such as Ga, In, Sn, Zn, Ti, Fe, etc. which are still present In the form of simple substances or intermetallic compounds, which adds little difficulty to the processing of the product. Ga, In and Sn which do not participate In the reaction are mixed with the aluminum hydrolysis precipitate, so that the Ga, In and Sn are not easy to recover, and In addition, the Ga, In and Sn are all rare metals and are expensive, so that the hydrogen production cost of the aluminum-based alloy is increased. Therefore, it is an urgent need to solve the problem of developing a method for efficiently and rapidly recovering the rare metals which do not participate in the reaction process and simultaneously realizing the continuous, stable and controllable hydrogen production process.

disclosure of Invention

One of the objects of the present invention is to provide a method for producing hydrogen from an aluminum alloy, by which unreacted metal can be recovered quickly and efficiently.

the invention also aims to provide application of the reaction liquid in hydrolysis hydrogen production reaction with aluminum alloy.

In order to realize one aspect of the aim, the invention provides an aluminum alloy hydrogen production method which adopts the following technical scheme:

a method for preparing hydrogen from aluminum alloy comprises the steps of contacting aluminum alloy capable of preparing hydrogen through hydrolysis with a reaction liquid to perform hydrolysis hydrogen-preparing reaction, wherein the reaction liquid is an aqueous solution of soluble inorganic salt, and the inorganic salt is one or more of halide salt and nitrate of alkali metal, alkaline earth metal, zinc, aluminum and manganese; preferably one or more of halide salts of potassium, sodium, calcium, magnesium, zinc, aluminum, manganese; further preferably one or more of hydrochloride of potassium, sodium, calcium, magnesium, zinc, aluminum and manganese.

In the present invention, aluminum alloys that can be hydrolyzed to produce hydrogen are those known in the art, in which aluminum can be directly hydrolyzed with water to produce hydrogen, and are well known in the art. In one embodiment, the aluminum alloy is an Al-Ga-In-Sn alloy commonly used In the art for hydrogen production by hydrolysis, and optionally, the aluminum alloy further comprises an X metal component selected from one or more of metals bismuth, zinc, iron, copper, magnesium and titanium to replace part of gallium, indium and tin, thereby reducing the amount of noble metal used, wherein the content of the replacement metal is not more than 10 wt%, preferably, the content of the X metal component is not more than 8 wt%, and more preferably not more than 6 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt% or 4 wt%. For example, when the X element is zinc, an al (Zn) solid solution and an elemental Zn phase may be further formed in the aluminum alloy.

According to the method of the invention, preferably the aluminium alloy comprises 80 wt% to 94 wt%, such as 82 wt%, 85 wt%, 88 wt%, 90 wt% or 92 wt% aluminium, 2 wt% to 5 wt%, such as 3 wt% or 4 wt% gallium, 3 wt% to 16 wt%, such as 5 wt%, 8 wt%, 10 wt%, 12 wt% or 15 wt% indium and tin, wherein the sum of the aluminium, gallium, indium and tin contents is not less than 90 wt%, such as 95 wt% or 98 wt%.

In one embodiment and at least part of the indium and tin form the metal compound InSn ₄ in the aluminium alloy may typically comprise al (Ga) solid solution, GaInSn ₄ and possibly GaIn ₃ Sn phases, in the present invention the metal compound (intermetallic) InSn ₄ comprises InSn ₄ and GaInSn ₄ further combined with Ga preferably the ratio of the amounts of indium and tin in the aluminium alloy is between 1:4 and 3:1, comprising 1:4 and 3:1, preferably not more than 1:2, further preferably not more than 1:3, such as 1:4, to enhance the hydrolysis reaction with the reaction liquid.

the aluminum alloy can be prepared by the following steps:

(1) Weighing each metal according to the proportion, putting the weighed metals into a furnace protected by nitrogen, heating at the temperature of 700-. Preferably, the purity of each metal used is greater than or equal to 99%.

(2) stirring the sample after heat preservation, pouring the sample into a mold, and cooling, preferably naturally cooling in air. And packaging the cooled alloy, and storing for a long time.

According to the process of the present invention, preferably, the concentration of the inorganic salt in the aqueous solution of the inorganic salt is not more than 10mol/L, preferably 0.05 to 5mol/L, such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 2mol/L, 3mol/L or 4 mol/L. Too high a concentration may hinder the movement of ions, resulting in adverse effects such as a decrease in hydrogen production performance, while too low a concentration may result in the formation of a hydrolysate of precipitated aluminum, thereby failing to effectively achieve the adverse effects of separation of aluminum from unreacted metals or intermetallic compounds.

According to the method of the present invention, preferably, the method further comprises subjecting the aqueous solution after the hydrolysis hydrogen production reaction to solid-liquid separation, and washing to recover the solid phase, i.e. the metal (including the elemental metal and the intermetallic compound) in the alloy which is not subjected to the hydrolysis reaction. In the present invention, because of the effect of the reaction solution, no precipitate is formed after the aluminum in the alloy is hydrolyzed, and therefore the solid phase is a metal which does not participate in the hydrolysis reaction in the aluminum alloy, so that the solid phase is convenient for recycling, preferably, when the aluminum alloy and the reaction solution are subjected to the hydrogen production reaction by hydrolysis, the liquid-solid ratio (the ratio of the volume of the liquid phase to the mass of the solid phase) is not less than 15L/Kg, preferably 18-25L/Kg, such as 20L/Kg, 22L/Kg or 24L/Kg, and the reaction temperature is 20-60 ℃, such as 25 ℃, 35 ℃, 40 ℃, 45 ℃ or 55 ℃, preferably 30-50 ℃.

According to the method of the present invention, preferably, the method further comprises adding alkali liquor, preferably weak alkali solution such as ammonia water, dropwise into the liquid obtained by solid-liquid separation until precipitation does not occur, obtaining precipitate after separation, and drying the precipitate to obtain aluminum hydrolysate so as to further recover aluminum.

The invention also aims to provide the application of the reaction liquid in the hydrolysis hydrogen production reaction with the aluminum alloy.

Compared with the prior art, the invention has the following advantages:

(1) The invention utilizes the aluminum-based alloy to react with the reaction liquid, such as AlX ₃ (X can be F-, C l-, Br-, I-plasma) solution to prepare hydrogen, because the X-in the solution has the function of destroying the oxide film on the surface of the alloy, thereby promoting the hydrogen preparation reaction of the aluminum alloy, and simultaneously, the hydrogen preparation reaction of the aluminum alloy which takes the solution as the reaction liquid can obtain clear transparent liquid, thereby avoiding the adhesion of low-melting-point metal which does not participate in the reaction in the aluminum alloy and solid reaction products, and being convenient for the recovery and the cyclic utilization of noble metal;

In addition, the raw materials of the reaction solution have low cost, wide sources and simple preparation method.

(2) The research shows that the metal compound InSn ₄, such as GaInSn ₄ phase, is more beneficial to breaking an oxide film formed on Al crystal grains and obviously improving the hydrogen production rate, In addition, compared with In ₃ Sn, the consumption can be obviously reduced, the cost is saved, and simultaneously, due to the improvement, a large aluminum block alloy can be used for hydrogen production, excessive treatment is not needed, the energy consumption is reduced, and the preparation process is simplified.

Drawings

FIG. 1 is an X-ray diffraction pattern of a sample of the Al-Ga-In-Sn alloy cyclically synthesized In example 1, indicating that the metallic mesophase present In the alloy is In ₃ Sn;

FIG. 2 is a scanning electron micrograph of the Al-Ga-In-Sn alloy sample cyclically synthesized In example 1, which shows the microstructure and structure of an aluminum alloy ingot;

FIG. 3 is an X-ray diffraction spectrum of boehmite, a by-product obtained in example 1;

FIG. 4 is a graph comparing the hydrogen production rates of the alloy samples of example 1 reacted with different inorganic salt solutions and distilled water;

FIG. 5 is a graph of hydrogen generation rates for the alloy samples of examples 4, 9, 11, 12, and 13 after reaction with different inorganic salt solutions;

FIG. 6 is an X-ray analysis chart of the Al-Ga-In-Sn-Zn quinary alloy prepared In examples 14 to 17.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Unless otherwise specified, the chemical reagents used below were analytical grade.