阅读说明：本技术 一种铝合金水解产物制备微纳米氧化铝的方法 (Method for preparing micro-nano aluminum oxide from aluminum alloy hydrolysate ) 是由 罗平 黄珍 肖瑶 刘刚元 陈琪 官旭 董仕节 于 2019-12-06 设计创作，主要内容包括：本发明涉及无机物制备技术领域,提供了一种铝合金水解产物制备微纳米氧化铝的方法,包括以下步骤：(1)将铝合金水解产物依次进行干燥和球磨处理,得到球磨产物；(2)将所述球磨产物固液分离后收集固体并干燥,得到微纳米氧化铝；所述步骤(1)中铝合金水解产物包括Al(OH)<Sub>3</Sub>和AlOOH。本发明提供的制备方法相对于已公开的氧化铝制备方法,具有原材料成本低、制备方法流程简单、易于操作等优点,且本发明提供的方法有利于促进铝合金水解制氢领域的发展。(The invention relates to the technical field of inorganic substance preparation, and provides a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate, which comprises the following steps: (1) drying and ball-milling the aluminum alloy hydrolysate in sequence to obtain a ball-milled product; (2) performing solid-liquid separation on the ball-milled product, collecting solids and drying to obtain micro-nano alumina; the aluminum alloy hydrolysate in the step (1) comprises Al (OH) 3 And AlOOH. Compared with the disclosed aluminum oxide preparation method, the preparation method provided by the invention has the advantages of low raw material cost, simple preparation method flow, easiness in operation and the like, and is favorable for promoting the development of the field of hydrogen production by aluminum alloy hydrolysis.)

1. A method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate comprises the following steps:

(1) drying and ball-milling the aluminum alloy hydrolysate in sequence to obtain a ball-milled product;

(2) performing solid-liquid separation on the ball-milled product, collecting solids and drying to obtain micro-nano alumina;

the aluminum alloy hydrolysate in the step (1) comprises Al (OH)₃And/or AlOOH.

2. The method according to claim 1, wherein the method for preparing the aluminum alloy hydrolyzate comprises the steps of:

reacting the hydrolyzed hydrogen-producing aluminum alloy with water, performing solid-liquid separation, and collecting solids to obtain an aluminum alloy hydrolysate;

the preparation method of the aluminum alloy for hydrogen production by hydrolysis comprises the following four parallel technical schemes:

the first method comprises the following steps: the material comprises the following components by mass: 60 to 95 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and Bi₂O₃1～10wt％，SnCl₂1-10 wt%, and performing ball milling to obtain a hydrolysis hydrogen production aluminum alloy;

and the second method comprises the following steps: the material comprises the following components by mass: 70 to 97.5 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, and Bi₂O₃0.5～10wt％，SnCl₂0.5-10 wt%, and performing ball milling to obtain a hydrolysis hydrogen production aluminum alloy;

and the third is that: the material comprises the following components by mass: 60-95 wt% of Al, 0.5-10 wt% of Ga, 0.5-10 wt% of In, 0.5-10 wt% of Sn, 0.5-10 wt% of Bi and 0.5-10 wt% of Sr, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy;

and fourthly: the material comprises the following components by mass: 60 to 97 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and SnCl₂1-10 wt%, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy.

3. The method according to claim 2, wherein the reaction temperature is 0-95 ℃ and the reaction time is 0.5-5 h.

4. The method according to claim 2, wherein the solid-liquid separation comprises centrifugal separation and filtration which are sequentially carried out, the rotation speed of the centrifugal separation is 6000-14000 rpm, and the time of the centrifugal separation is 30-120 s.

5. The method according to claim 1, wherein the drying temperature in the step (1) is 50-90 ℃ and the drying time is 0.5-10 h.

6. The method of claim 1, wherein the ball milling in step (1) is performed in a container made of alumina, the milling balls for ball milling are alumina ceramic balls, the ball milling is wet milling, and the solvent for wet milling is water.

7. The method according to claim 1 or 6, wherein the rotation speed of the ball mill is 250-500 rpm, the ball-to-material ratio is 1-40: 1, the water-to-material mass ratio is 0.5-50: 1, and the time is 1-48 h.

8. The method according to claim 1, wherein the drying temperature in the step (2) is 80-120 ℃, and the drying time is 1-15 h.

Technical Field

The invention relates to the technical field of inorganic matter preparation, in particular to a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate.

Background

Alumina is a material with wide application, has many excellent characteristics of high hardness, corrosion resistance, high temperature resistance, high oxidation resistance and the like, and is widely applied to different fields of aerospace industry, automobile industry, consumer product processing industry, casting/die casting, semiconductor industry and the like. At present, the industrial preparation method of alumina comprises a soda lime sintering method and a bayer method, wherein the soda lime sintering method is to mix and grind bauxite, supplemented soda powder, lime (small stone slag), circulating alkali liquor (namely carbon evaporation mother liquor) and bayer method red mud according to a proportion into qualified raw slurry, spray the raw slurry into a clinker kiln to sinter the raw slurry at a high temperature, the clinker and adjusting solution are crushed and dissolved out in wet grinding, the dissolved solution is separated by the red mud to obtain crude solution, the crude solution is desiliconized and filtered by leaves to obtain sodium aluminate refined solution, the sodium aluminate refined solution is carbonated and decomposed to separate out aluminum hydroxide, and the aluminum hydroxide is roasted to obtain the product alumina. The Bayer process for preparing alumina includes heating caustic soda (NaOH) solution to dissolve out alumina in bauxite to obtain sodium aluminate solution, separating the solution from residue (red mud), lowering temperature, adding aluminum hydroxide as seed crystal, stirring for a long time to decompose sodium aluminate to separate out aluminum hydroxide, washing, and calcining at 950-1200 deg.C to obtain alumina product. Currently, 95 wt% of the world's aluminum companies are producing alumina using the bayer process.

The existing production method of alumina is single, and a new alumina production process needs to be explored and researched.

Disclosure of Invention

The invention provides a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate, which has simple steps and is easy to implement.

The invention provides a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate, which comprises the following steps:

(1) drying and ball-milling the aluminum alloy hydrolysate in sequence to obtain a ball-milled product;

(2) performing solid-liquid separation on the ball-milled product, collecting solids and drying to obtain micro-nano alumina;

the aluminum alloy hydrolysate in the step (1) comprises Al (OH)₃And/or AlOOH.

Preferably, the preparation method of the aluminum alloy hydrolysate comprises the following steps:

reacting the hydrolyzed hydrogen-producing aluminum alloy with water, performing solid-liquid separation, and collecting solids to obtain an aluminum alloy hydrolysate;

the preparation method of the aluminum alloy for hydrogen production by hydrolysis comprises the following three parallel technical schemes:

the first method comprises the following steps: the material comprises the following components by mass: 60 to 95 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and Bi₂O₃1～10wt％，SnCl₂1-10 wt%, and performing ball milling to obtain a hydrolysis hydrogen production aluminum alloy;

and the second method comprises the following steps: the material comprises the following components by mass: 70 to 97.5 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, and Bi₂O₃0.5～10wt％，SnCl₂0.5-10 wt%, and performing ball milling to obtain a hydrolysis hydrogen production aluminum alloy;

and the third is that: the material comprises the following components by mass: 60-95 wt% of Al, 0.5-10 wt% of Ga, 0.5-10 wt% of In, 0.5-10 wt% of Sn, 0.5-10 wt% of Bi and 0.5-10 wt% of Sr, and performing ball milling to obtain a hydrolysis hydrogen production aluminum alloy;

and fourthly: the material comprises the following components by mass: 60 to 97 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and SnCl₂1-10 wt%, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy.

Preferably, the reaction temperature is 0-95 ℃ and the reaction time is 0.5-5 h.

Preferably, the solid-liquid separation comprises centrifugal separation and filtration which are sequentially carried out, the rotating speed of the centrifugal separation is 6000-14000 rpm, and the time of the centrifugal separation is 30-120 s.

Preferably, the drying temperature in the step (1) is 50-90 ℃, and the drying time is 0.5-10 h.

Preferably, the ball milling in the step (1) is performed in a container made of alumina, the milling balls for ball milling are alumina ceramic balls, the ball milling is wet milling, and a solvent for the wet milling is water.

Preferably, the rotation speed of the ball mill is 250-500 rpm, the ball-material ratio is 1-40: 1, the water-material mass ratio is 0.5-50: 1, and the time is 1-48 h.

Preferably, the drying temperature in the step (2) is 80-120 ℃, and the drying time is 1-15 h.

The invention provides a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate, which comprises the following steps: (1) drying and ball-milling the aluminum alloy hydrolysate in sequence to obtain a ball-milled product; (2) performing solid-liquid separation on the ball-milled product, collecting solids and drying to obtain micro-nano alumina; the aluminum alloy hydrolysate in the step (1) comprises Al (OH)₃And/or AlOOH. Compared with the disclosed preparation method of alumina, the preparation method provided by the invention has the following advantages: (1) the raw material is from an aluminum alloy hydrolysate for hydrogen production by hydrolysis, and the cost of the raw material is low; (2) the preparation method has simple flow, does not need expensive equipment and is easy to operate; (3) the invention promotes the development of the aluminum alloy hydrolysis hydrogen production method, and the invention is the secondary utilization of the aluminum alloy hydrolysate for hydrolysis hydrogen production, thereby effectively reducing the preparation cost of the aluminum alloy for hydrolysis hydrogen production and further promoting the development of the aluminum alloy hydrolysis hydrogen production method.

Drawings

FIG. 1 is an XRD pattern of alumina prepared in examples 1-4;

FIG. 2 is a graph showing the distribution of the particle size of alumina prepared in examples 1 to 4.

Detailed Description

The invention provides a method for preparing micro-nano aluminum oxide from an aluminum alloy hydrolysate, which comprises the following steps:

(1) drying and ball-milling the aluminum alloy hydrolysate in sequence to obtain a ball-milled product;

(2) and (3) performing solid-liquid separation on the ball-milled product, collecting the solid and drying to obtain the micro-nano alumina.

In the present invention, the aluminum alloy hydrolyzate includes Al (OH)₃And AlOOH, the aluminum alloyThe method for preparing the hydrolysate preferably comprises the steps of:

and (3) reacting the hydrolyzed hydrogen-producing aluminum alloy with water, performing solid-liquid separation, and collecting solids to obtain an aluminum alloy hydrolysate.

In the invention, the preparation method of the aluminum alloy for hydrogen production by hydrolysis preferably comprises four parallel technical schemes, wherein the first scheme is as follows: the material comprises the following components by mass: 60 to 95 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and Bi₂O₃1～10wt％，SnCl₂1-10 wt%, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy. In the invention, the raw material comprises 60-95 wt% of Al, preferably 70-93 wt%, and more preferably 85-90 wt%; the raw material comprises 0.5-10 wt% of Ga, preferably 1-8 wt%, more preferably 1.5-5 wt%; the raw materials comprise 0.5-10 wt% of In, preferably 1-8 wt%, more preferably 1.5-5 wt%; the raw material comprises 0.5-10 wt% of Sr, preferably 1-8 wt%, and more preferably 1.5-5 wt%; the raw material comprises 1-10 wt% of Bi₂O₃Preferably 1.5 to 8 wt%, more preferably 2 to 5 wt%; the raw material comprises 1-10 wt% of SnCl₂Preferably 1.5 to 8 wt%, more preferably 2 to 5 wt%. In the invention, the ball milling is preferably carried out under the protection of nitrogen or argon, the ball-to-material ratio of the ball milling is preferably 10-20: 1, more preferably 12-18: 1, and most preferably 14-16: 1; the ball milling time is preferably 1-24 h, more preferably 5-20 h, and most preferably 10-15 h; the ball milling is preferably carried out in a ball mill, and the rotation speed of a main shaft of the ball mill is preferably 200-500 r/min, more preferably 300-400 r/min, and most preferably 340-360 r/min. The preparation method of the aluminum alloy for hydrogen production by hydrolysis in the first technical scheme of the invention is the same as that in patent 201610566177.7.

In the invention, the second preparation method of the aluminum alloy for hydrogen production by hydrolysis is preferably as follows: the material comprises the following components by mass: 70 to 97.5 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, and Bi₂O₃0.5～10wt％，SnCl₂0.5-10 wt%, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy. In the invention, the raw material comprises 70-97.5 wt% of Al, preferably 80-95 wt%, and more preferably 85-91 wt%; the raw material comprises 0.5-10 wt% of Ga, preferably 1-8 wt%, more preferably 2-5 wt%; the raw materials comprise 0.5-10 wt% of In, preferably 1-8 wt%, and more preferably 2-5 wt%; the raw material comprises 0.5-10 wt% of Bi₂O₃Preferably 1 to 8 wt%, more preferably 2 to 5 wt%; the raw material comprises 0.5-10 wt% of SnCl₂Preferably 1 to 8 wt%, more preferably 2 to 5 wt%. In the invention, the ball milling is preferably carried out under the protection of nitrogen or argon, the ball-to-material ratio of the ball milling is preferably 10-20: 1, more preferably 12-18: 1, and most preferably 14-16: 1; the ball milling time is preferably 1-24 h, more preferably 5-20 h, and most preferably 10-15 h; the ball milling is preferably carried out in a ball mill, and the rotation speed of a main shaft of the ball mill is preferably 200-500 r/min, more preferably 300-400 r/min, and most preferably 340-360 r/min. The preparation method of the aluminum alloy for hydrogen production by hydrolysis in the second technical scheme of the invention is the same as that in patent 201610564832.5.

In the invention, the third preparation method of the aluminum alloy for hydrogen production by hydrolysis is preferably as follows: 60-95 wt% of Al, 0.5-10 wt% of Ga, 0.5-10 wt% of In, 0.5-10 wt% of Sn, 0.5-10 wt% of Bi and 0.5-10 wt% of Sr, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy. In the invention, the raw material comprises 60-95 wt% of Al, preferably 65-95 wt%, and more preferably 70-90 wt%; the raw material comprises 0.5-10 wt% of Ga, preferably 0.5-4 wt%, more preferably 1-3 wt%; the raw materials comprise 0.5-10 wt% of In, preferably 1-9 wt%, and more preferably 2-8 wt%; the raw material comprises 0.5-10 wt% of Sn, preferably 1-9 wt%, more preferably 2-8 wt%; the raw material comprises 0.5-10 wt% of Bi, preferably 1-9 wt%, and more preferably 2-8 wt%; the raw material comprises 0.5-10 wt% of Sr, preferably 1-9 wt%, and more preferably 2-8 wt%. In the present invention, the purities of Al, Ga, In, Sn, Bi, and Sr are each more than 95 wt%, and more preferably more than 99 wt%. In the invention, the ball milling is preferably carried out under the protection of nitrogen or argon, and the ball-to-material ratio of the ball milling is preferably 5-25: 1, more preferably 8-15: 1; the ball milling time is preferably 1-12 h, and more preferably 2-10 h; the ball milling is preferably carried out in a ball mill, and the rotation speed of a main shaft of the ball mill is preferably 200-450 r/min, and more preferably 250-400 r/min. The preparation method of the aluminum alloy for hydrogen production by hydrolysis in the third technical scheme of the invention is the same as that in patent 201610566177.7.

In the invention, the fourth preparation method of the aluminum alloy for hydrogen production by hydrolysis is preferably as follows: the material comprises the following components by mass: 60 to 97 wt% of Al, 0.5 to 10 wt% of Ga, 0.5 to 10 wt% of In, 0.5 to 10 wt% of Sr, and SnCl₂1-10 wt%, and performing ball milling to obtain the hydrolysis hydrogen production aluminum alloy. In the invention, the raw material comprises 60-97 wt% of Al, preferably 70-93 wt%, and more preferably 85-90 wt%; the raw material comprises 0.5-10 wt% of Ga, preferably 1-8 wt%, more preferably 2-5 wt%; the raw materials comprise 0.5-10 wt% of In, preferably 1-8 wt%, and more preferably 2-5 wt%; the raw material comprises 0.5-10 wt% of Sr, preferably 1-8 wt%, and more preferably 2-5 wt%; the raw material comprises 1-10 wt% of SnCl₂Preferably 2 to 8 wt%, more preferably 3 to 5 wt%. In the invention, the ball milling is preferably carried out under the protection of nitrogen or argon, the ball-to-material ratio of the ball milling is preferably 10-25: 1, more preferably 12-20: 1, and most preferably 14-16: 1; the time of ball milling is preferably 1-24 h, more preferably 5-20 h, most preferably 10-15 h, the ball milling is preferably carried out in a ball mill, the rotation speed of a main shaft of the ball mill is preferably 300-550 r/min, more preferably 350-450 r/min, and most preferably 380-420 r/min. The preparation method of the aluminum alloy for hydrogen production by hydrolysis in the fourth technical scheme of the invention is the same as that in patent 201610564831.0.

After the hydrolysis hydrogen production aluminum alloy is obtained, the hydrolysis hydrogen production aluminum alloy reacts with water. In the invention, the reaction temperature of the aluminum alloy for hydrogen production by hydrolysis and water is preferably 0-95 ℃, more preferably 10-90 ℃, and more preferably 20-80 ℃; the reaction time is preferably 0.5-5 h, more preferably 1-4.5 h, and even more preferably 1.5-4 h. In the present invention, the water is preferably in excess to ensure the completion of the hydrolysis hydrogen-producing aluminum alloy reaction. In the invention, after the aluminum alloy for hydrogen production by hydrolysis is contacted with water, violent reaction immediately occurs, and the reaction temperature and the reaction time are preferably controlled within the range so as to ensure the complete reaction of the aluminum alloy for hydrogen production by hydrolysis.

After the reaction is finished, the obtained reaction liquid is subjected to solid-liquid separation, and the solid is collected to obtain the aluminum alloy hydrolysate. In the invention, the solid-liquid separation preferably comprises centrifugal separation and filtration which are sequentially carried out, the rotating speed of the centrifugal separation is preferably 6000-14000 rpm, more preferably 8000-12000 rpm, more preferably 10000-11000 rpm, and the time of the centrifugal separation is preferably 30-120 s, more preferably 50-100 s, and more preferably 60-80 s. The present invention preferably controls the parameters of the centrifugal separation within the above-mentioned ranges to sufficiently separate the solid and the liquid. The method of collecting the solid by filtration is not particularly required in the present invention, and a method well known to those skilled in the art may be used.

After the aluminum alloy hydrolysate is obtained, the aluminum alloy hydrolysate is dried. In the invention, the drying temperature is preferably 50-90 ℃, more preferably 60-80 ℃, and the drying time is preferably 0.5-10 h, more preferably 1-9 h. The invention fully removes the water in the aluminum alloy hydrolysate through drying treatment.

After drying is finished, the dried aluminum alloy hydrolysate is subjected to ball milling treatment to obtain a ball milling product. In the present invention, the ball milling is preferably performed in an alumina vessel, more preferably in an alumina ceramic vessel; the grinding balls for ball milling are preferably alumina ceramic balls; the ball milling is preferably wet milling, and the solvent for the wet milling is preferably water. In the invention, the rotation speed of the ball mill is preferably 250-500 rpm, more preferably 300-450 rpm, and more preferably 350-400 rpm; the ball-to-material ratio of the ball milling is preferably 1-40: 1, more preferably 5-35: 1, and more preferably 10-30: 1; the water-material mass ratio is preferably 0.5-50: 1, more preferably 10-40: 1, and more preferably 20-30: 1; the ball milling time is preferably 1-48 h, more preferably 10-40 h, and even more preferably 20-30 h. In the ball milling process, the aluminum alloy hydrolysate undergoes reactions shown in formulas (1) to (2):

the invention decomposes the aluminum alloy hydrolysate into aluminum oxide by ball milling treatment.

After the ball milling is finished, the ball milling product is subjected to solid-liquid separation, and then the solid is collected and dried to obtain the micro-nano alumina. The present invention is not particularly limited to the specific embodiment of the solid-liquid separation, and may be carried out in a manner known to those skilled in the art. In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 90-110 ℃; the drying time is preferably 1-15 hours, and more preferably 5-10 hours.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.