CN105293545A - Method for manufacturing nanometer alumina by using precipitate generated from aluminum-air battery discharge - Google Patents
Method for manufacturing nanometer alumina by using precipitate generated from aluminum-air battery discharge Download PDFInfo
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Abstract
The present invention discloses a method for manufacturing nanometer alumina by using precipitate generated from aluminum-air battery discharge. The method comprises: 1) washing precipitate generated from aluminum-air battery discharge with water to achieve a neutral state, filtering, and drying to obtain a precipitate; 2) heating the precipitate and a sulfuric acid aqueous solution, dissolving, and filtering to obtain an aluminum sulfate aqueous solution; 3) adding ammonium sulfate to the aluminum sulfate aqueous solution, dissolving, evaporating the water to obtain an ammonium aluminum sulfate oversaturation solution, and cooling to a room temperature to obtain an ammonium aluminum sulfate crystal; and 4) calcining the ammonium aluminum sulfate crystal, and cooling to a room temperature to obtain the nanometer alumina. According to the present invention, the purity of the manufactured nanometer alumina is high, and the particle size distribution is uniform; the waste utilization is achieved; the aluminum-air battery operating cost is reduced; the technology has characteristics of simple process, energy saving, and environmental protection; the manufactured nanometer alumina material has high purity and uniform particle size; and the waste utilization is achieved, and the aluminum-air battery operating cost is substantially reduced.
Description
Technical field
The invention belongs to energy technology field, particularly a kind of Yi Lv ?the throw out that generates of gas battery electric discharge be that raw material manufactures the method for nano aluminium oxide.
Technical background
Lv ?gas battery be a kind of take aluminium alloy as negative pole, air electrode is positive pole, neutrality or alkaline aqueous solution are electrolytic solution metal fuel battery.Lv ? externally export electric energy by the oxygen consumed in aluminium alloy negative pole and air in gas battery operational process.Along with the carrying out of discharge process, Lv ?gas battery electrolytic solution in generate throw out.At present, there is no Yi Lv ?the throw out that generates of gas battery electric discharge be that raw material manufactures the relevant report of nano aluminium oxide.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of Yi Lv ?the throw out that generates of gas battery electric discharge be that raw material manufactures the method for nano aluminium oxide.
Technical scheme of the present invention is summarized as follows:
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1) with distilled water repeatedly clean Lv ?the throw out that generates of gas battery electric discharge, make the water after cleaning for neutral, filter, dry, obtain throw out;
2) step 1 is taken) throw out that obtains puts into container, then adds in container by aqueous sulfuric acid, heats and stir to make precipitate dissolves, and filter, obtain aluminum sulfate aqueous solution; Bright sulfur acid weight in described aqueous sulfuric acid and sedimentary weight ratio control in the scope of 2 ~ 6:1;
3) undertaken by the one of following three kinds of modes:
Mode one: ammonium sulfate is added step 2) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtain exsiccated ammonium alum supersaturated solution, be down to room temperature, have exsiccated ammonium alum crystallization, be separated, dry, obtain ammonium aluminum sulfate crystal; Described ammonium sulfate and step 2) described sedimentary weight ratio controls within the scope of 3 ~ 1:1;
Mode two: by step 2) to join pH be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, be separated, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3;
Mode three: by pH be 9 ammonium carbonate solution join step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3;
4) by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium calcined by a step calcination method or two step calcination methods, and cool to room temperature, obtains nano aluminium oxide.
Step 3) mode one is preferably: ammonium sulfate is added the step 2 of adding dispersion agent in advance) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtain exsiccated ammonium alum supersaturated solution, be down to room temperature, have exsiccated ammonium alum crystallization, be separated, drying, obtains ammonium aluminum sulfate crystal; Described ammonium sulfate and step 2) described sedimentary weight ratio controls in the scope of 3 ~ 1:1; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
Step 3) mode two is preferably: by step 2) to join the pH adding dispersion agent in advance be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, be separated, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in ammonium carbonate solution is 1 × 10
?5~ 1mol/L.
Step 3) mode two is preferably: the step 2 of dispersion agent will be added in advance) to join pH be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, be separated, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
Step 3) mode three is preferably: the ammonium carbonate solution being 9 by the pH adding dispersion agent in advance joins step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in ammonium carbonate solution is 1 × 10
?5~ 1mol/L.
Step 3) mode three is preferably: by pH be 9 ammonium carbonate solution join the step 2 of adding dispersion agent in advance under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
Dispersion agent is polyoxyethylene glycol, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, sorbitan ester, sucrose fatty ester, alkylol amide, polyacrylamide, Sodium dodecylbenzene sulfonate, oil acyloxy ethyl sulfonic acid sodium, N-oleoyl N-methyl Sodium taurine salt, Aerosol OT, sodium dibutyl naphthalene sulfonate, stearic acid, dispersant B YK2010, methacrylic ester, polyacrylamide, polyethylene polyamine, N, N ?dimethylamino propylamine, 18 amino propylamine, diethylethanolamine, dispersion agent Disuper (core chemistry), cetyl trimethylammonium bromide, sodium lauryl sulphate or linear alkylbenzene sulphonic acid (LAS).
Step 4) be preferably: by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out cleaning, dry, calcined by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Or by step 3) after the ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out ball milling or grinding, calcined by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Or by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out cleaning, ball milling or grinding, after drying, undertaken calcining by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Clean-out system for the cleaning of aluminium carbonate ammonium is distilled water, alcohol or acetone, and the clean-out system for ammonium aluminum sulfate crystal cleaning is alcohol or acetone;
The condition of a described step calcination method is: be heated to 800-1500 DEG C of insulation 30-240 minute, be cooled to room temperature.
The condition of described two step calcination methods is: be heated to 300-700 DEG C of insulation and be cooled to room temperature after 30-180 minute, reheats 800-1500 DEG C of insulation afterwards and is cooled to room temperature after 30-240 minutes.
Advantage of the present invention: the purity 1) manufacturing nano aluminium oxide is high, even particle size distribution; 2) simple, the energy-saving and environmental protection of preparation process; 3) utilization of waste material is realized; 4) reduce Lv ?gas battery running cost.Not only purity is high, uniform particle sizes for the nano alumina material adopting the technology of the present invention to manufacture, and realizes utilization of waste material, greatly reduce Lv ?gas battery running cost.
Accompanying drawing explanation
Fig. 1 prepares α-Al for calcining exsiccated ammonium alum
2o
3the X-ray diffraction spectrogram of nano material.
Fig. 2 prepares α-Al for calcining exsiccated ammonium alum
2o
3the transmission electron microscope photo of nano material.
Fig. 3 prepares α-Al for calcining aluminium carbonate ammonium
2o
3the transmission electron microscope photo of nano material.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1: Yi Lv ?the throw out that generates of gas battery electric discharge manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
1) by appropriate Lv ?gas battery electric discharge generate throw out put into container, add distilled water fully stir rear leave standstill, the supernatant liquid in rear removal container to be precipitated; Afterwards, again in container, add distilled water, leave standstill after fully stirring, after to be precipitated, remove the supernatant liquid in container again; Repeatedly repeat aforesaid operations, until the pH value of supernatant liquid is close to neutral, cleaning terminates, and removes supernatant liquid, filters, dry, obtains throw out;
2) 16 grams of steps 1 are taken) throw out that obtains puts into container, then adds in container by 200ml aqueous sulfuric acid (wherein containing bright sulfur acid 72 grams), heat and stir to make precipitate dissolves, and filtration, obtains aluminum sulfate aqueous solution; Adding bright sulfur acid and step 1) ratio of described sedimentary weight is 4.5:1
3) 26 grams of ammonium sulfate are added step 2) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtain exsiccated ammonium alum supersaturated solution, be down to room temperature, have exsiccated ammonium alum crystallization, filter, dry, obtain ammonium aluminum sulfate crystal.Adding ammonium sulfate and step 2) described sedimentary weight ratio is 1.6:1;
4) by step 3) ammonium aluminum sulfate crystal that obtains puts into electric furnace, and be heated to 1200 DEG C of insulations after 60 minutes, cool to room temperature, prepares α-Al
2o
3nano material.See Fig. 1 and Fig. 2.
In Fig. 1, a is the α-Al of preparation
2o
3the X-ray diffraction spectrum of nano material, in Fig. 1, b is α-Al
2o
3standard powder X-ray diffraction spectrum.XRD diffraction analysis confirms that product is α-Al
2o
3.Fig. 2 is preparation α-Al
2o
3the transmission electron microscope photo of nano material.
In the present embodiment, by step 3) put into electric furnace after the ammonium aluminum sulfate crystal drying prepared, be warming up to 800-1500 DEG C of different temperature appropriate time and calcine, the nano alumina material of different crystal forms can be prepared.Select higher calcining temperature, α-Al can be prepared
2o
3nano material; Select calcining temperature placed in the middle, β-Al can be prepared
2o
3nano material; Select calcining temperature on the low side, γ-Al can be prepared
2o
3nano material.
In the present embodiment, by step 3) the dry ammonium aluminum sulfate crystal prepared puts into electric furnace, and be warming up to 1000 DEG C of insulations cool to room temperature after 120 minutes, prepare β-Al
2o
3nano material.
In the present embodiment, by step 3) the dry ammonium aluminum sulfate crystal prepared puts into electric furnace, and be warming up to 800 DEG C of insulations cool to room temperature after 240 minutes, prepare γ-Al
2o
3nano material.
In the present embodiment, rate-determining steps 2) middle bright sulfur acid is with sedimentary weight ratio in the scope of 2 ~ 6:1, and the same the present embodiment of other step, can obtain the nano aluminium oxide that the detected result of detected result and the present embodiment is close.
In the present embodiment, rate-determining steps 3) in the ratio of ammonium sulfate and sedimentary weight in the scope of 3 ~ 1:1, the same the present embodiment of other step, can obtain the nano aluminium oxide that the detected result of detected result and the present embodiment is close.
Embodiment 2
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
1) with embodiment 1 step 1);
2) 3 grams of steps 1 are taken) throw out that obtains puts into container, then adds in container by aqueous sulfuric acid (wherein containing bright sulfur acid 16 grams), heat and stir to make precipitate dissolves, and filtration, obtains aluminum sulfate aqueous solution; Adding bright sulfur acid is 5.3:1 with the ratio of sedimentary weight
3) 9 grams of volatile salts are put into beaker, add 100ml distilled water, after stirring makes it dissolve, with ammoniacal liquor, pH value is adjusted to 9 and obtains ammonium carbonate solution, by step 2) under agitation to join pH be in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generate white precipitate, filter, drying, obtains aluminium carbonate ammonium; Adding volatile salt and step 2) ratio of described sedimentary weight is 3:1;
4) by step 3) the aluminium carbonate ammonium that obtains puts into electric furnace, and be warming up to 1400 DEG C of insulations and calcine for 30 minutes, cool to room temperature, prepares α-Al
2o
3nano alumina material, is shown in Fig. 3.
In the present embodiment, by step 3) the aluminium carbonate ammonium prepared puts into electric furnace, and be warming up to 800-1500 DEG C of different temperature reasonable time and calcine, the nano alumina material of different crystal forms can be prepared.In the temperature range of 800-1500 DEG C, calcining temperature is high, can prepare α-Al
2o
3nano material; Calcining temperature is placed in the middle, can prepare β-Al
2o
3nano material; Calcining temperature is low, can prepare γ-Al
2o
3nano material.
In the present embodiment, by step 3) put into electric furnace after the aluminium carbonate ammonium drying prepared, be warming up to 1100 DEG C of insulations cool to room temperature after 30 minutes, prepare β-Al
2o
3nano material.
In the present embodiment, by step 3) put into electric furnace after the aluminium carbonate ammonium drying prepared, be warming up to 900 DEG C of insulations cool to room temperature after 30 minutes, prepare γ-Al
2o
3nano material.
In the present embodiment, rate-determining steps 2) middle bright sulfur acid is with sedimentary weight ratio in the scope of 2 ~ 6:1, and the same the present embodiment of other step, can obtain the nano aluminium oxide that the detected result of detected result and the present embodiment is close.
In the present embodiment, rate-determining steps 3) in the ratio of volatile salt and sedimentary weight in the scope of 4 ~ 9:3, the same the present embodiment of other step, can obtain the nano aluminium oxide that the detected result of detected result and the present embodiment is close.
Embodiment 3
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
1), 2) with 1 of embodiment 2), 2);
3) by pH be 9 ammonium carbonate solution (volatile salt is 9 grams) join step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, centrifugation, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) weight ratio of described throw out (3 grams) controls as 3:1;
4) by step 3) the aluminium carbonate ammonium that obtains puts into electric furnace, and be warming up to 1200 DEG C of insulations and calcine for 120 minutes, cool to room temperature, prepares α-Al
2o
3nano alumina material.
Embodiment 4
Yi Lv ?gas battery electric discharge generate throw out and manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
Step 1), 2), 3) with the step 1 of embodiment 1), 2), 3);
4) by step 3) ammonium aluminum sulfate crystal that obtains puts into ball grinder, with the rotating speed ball milling of per minute 500 turns after 3 hours, puts into electric furnace, and be warming up to 1300 DEG C of insulations cool to room temperature after 50 minutes, obtain α-Al
2o
3nano material;
α-Al prepared by the present embodiment
2o
3the particle diameter ratio of nano material is more even without what grind.Change the β-Al that calcining temperature is prepared
2o
3with γ-Al
2o
3the particle diameter of nano material is also than more even without what grind.
In the present embodiment, by embodiment 1 through step 1), 2), 3) after the ammonium aluminum sulfate crystal prepared puts into ball grinder, add suitable alcohols in ball grinder after, carry out aforesaid grinding operation again.After exsiccated ammonium alum after grinding and the mixture of alcohol being carried out the alcohol that drying treatment removes wherein, then put into electric furnace and carry out follow-up calcining, prepare α-Al
2o
3nano material.
α-Al prepared by the present embodiment
2o
3the particle diameter ratio of nano material is more even without what grind.Change the β-Al that calcining temperature is prepared
2o
3with γ-Al
2o
3the particle diameter of nano material is also than more even without what grind.
In the present embodiment, also the alcohol added in the present embodiment in ball grinder can be replaced to acetone.
Embodiment 5
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
Step 1), 2), 3) with the step 1 of embodiment 2), 2), 3);
4) by step 3) the aluminium carbonate ammonium that obtains puts into ball grinder, and take out after 2 hours with the rotating speed ball milling of per minute 600 turns and put into electric furnace, be warming up to 1500 DEG C of insulations and calcine for 30 minutes, cool to room temperature, prepares α-Al
2o
3nano alumina material.
α-Al prepared by the present embodiment
2o
3the particle diameter ratio of nano material is more even without what grind.Change the β-Al that calcining temperature is prepared
2o
3with γ-Al
2o
3the particle diameter of nano material is also than more even without what grind.
In the present embodiment, by step 3) after the aluminium carbonate ammonium that obtains puts into ball grinder, add suitable alcohols in ball grinder after, carry out aforesaid grinding operation again.After aluminium carbonate ammonium after grinding and the mixture of alcohol being carried out the alcohol that drying treatment removes wherein, then put into electric furnace and carry out follow-up calcining, prepare α-Al
2o
3nano material.α-Al prepared by the present embodiment
2o
3the particle diameter ratio of nano material is more even without what grind.Change the β-Al that calcining temperature is prepared
2o
3with γ-Al
2o
3the particle diameter of nano material is also than more even without what grind.
In the present embodiment, also the alcohol added in ball grinder can be replaced to distilled water or acetone.
Embodiment 6
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture nano aluminium oxide (α-Al
2o
3) method, comprise the steps:
Step 1), 2) with embodiment 1 step 1), 2);
3) ammonium sulfate is added the step 2 of adding Macrogol 2000 in advance) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtain exsiccated ammonium alum supersaturated solution, be down to room temperature, have exsiccated ammonium alum crystallization, filtering separation, drying, obtains ammonium aluminum sulfate crystal, ammonium sulfate and step 2) described sedimentary weight ratio is 1.6:1; The concentration of Macrogol 2000 in aluminum sulfate aqueous solution is 1 × 10
?5mol/L;
4) by step 3) ammonium aluminum sulfate crystal that obtains is heated to 700 DEG C of insulations and is cooled to room temperature after 30 minutes, reheat 1200 DEG C of insulations afterwards and be cooled to room temperature after 150 minutes, obtain α-Al
2o
3.
Be that 1mol/L substitutes 1 × 10 of the present embodiment by the concentration of Macrogol 2000 in aluminum sulfate aqueous solution
?5mol/L, the same the present embodiment of other step, prepares nano aluminium oxide.
Also polyoxyethylene octylphenol ether can be used, polyoxyethylene nonylphenol ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate (AE), sorbitan ester, sucrose fatty ester, alkylol amide, polyacrylamide, Sodium dodecylbenzene sulfonate, oil acyloxy ethyl sulfonic acid sodium, N-oleoyl N-methyl Sodium taurine salt, Aerosol OT, sodium dibutyl naphthalene sulfonate, stearic acid, dispersant B YK2010 (Shanghai turtle power chemical industry), methyl acrylic ester, polyacrylamide, polyethylene polyamine, N, N ?dimethylamino propylamine, 18 amino propylamine, diethylethanolamine, dispersion agent Disuper (core chemistry), cetyl trimethylammonium bromide, sodium lauryl sulphate, linear alkylbenzene sulphonic acid (LAS), fatty amine salt, ethanolamine salt, polyethylene polyamines salt, quaternary ammonium salt or non-ion fluorin carbon surface active agent replace the Macrogol 2000 in the present embodiment, the same the present embodiment of other step, obtain nano aluminium oxide.
Embodiment 7
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1)-2) with embodiment 2 step 1)-2);
3) by pH be 9 ammonium carbonate solution join the step 2 of adding sodium lauryl sulphate in advance under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, centrifugation, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio is at 3:1; The concentration of sodium lauryl sulphate in aluminum sulfate aqueous solution is 1 × 10
?5mol/L.
4) with embodiment 2 step 4).
In the present embodiment, rate-determining steps 3) in the ratio of volatile salt and sedimentary weight in the scope of 4 ~ 9:3, the same the present embodiment of other step, can obtain the nano aluminium oxide that the detected result of detected result and the present embodiment is close.
Be that 1mol/L substitutes 1 × 10 of the present embodiment by the concentration of sodium lauryl sulphate in aluminum sulfate aqueous solution
?5mol/L, the same the present embodiment of other step, prepares nano aluminium oxide.
Also polyoxyethylene octylphenol ether can be used, polyoxyethylene nonylphenol ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate (AE), sorbitan ester, sucrose fatty ester, alkylol amide, polyacrylamide, Sodium dodecylbenzene sulfonate, oil acyloxy ethyl sulfonic acid sodium, N-oleoyl N-methyl Sodium taurine salt, Aerosol OT, sodium dibutyl naphthalene sulfonate, stearic acid, dispersant B YK2010 (Shanghai turtle power chemical industry), methyl acrylic ester, polyacrylamide, polyethylene polyamine, N, N ?dimethylamino propylamine, 18 amino propylamine, polyoxyethylene glycol, diethylethanolamine, dispersion agent Disuper (core chemistry), cetyl trimethylammonium bromide, , linear alkylbenzene sulphonic acid (LAS), fatty amine salt, ethanolamine salt, polyethylene polyamines salt, quaternary ammonium salt or non-ion fluorin carbon surface active agent replace the sodium lauryl sulphate in the present embodiment, the same the present embodiment of other step, obtain nano aluminium oxide.
Embodiment 8
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1)-2) with embodiment 2 step 1)-2);
3) by step 2) to join the pH adding Soxylat A 25-7 in advance be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, filtering separation, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 1) described sedimentary weight ratio controls at 3:1; Soxylat A 25-7 is 1 × 10 in the concentration of ammonium carbonate solution
?5mol/L;
4) with embodiment 2 step 4).
Be that 1mol/L substitutes 1 × 10 of the present embodiment by the concentration of Soxylat A 25-7 in ammonium carbonate solution
?5mol/L, the same the present embodiment of other step, prepares nano aluminium oxide.
Embodiment 9
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1)-2) with embodiment 2 step 1)-2);
3) step 2 of polyoxyethylene nonylphenol ether being added in advance) to join pH be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, centrifugation, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls at 3:1.The concentration of polyoxyethylene nonylphenol ether in aluminum sulfate aqueous solution is 1 × 10
?5.
4) with embodiment 2 step 4).
Be that 1mol/L substitutes 1 × 10 of the present embodiment by the concentration of polyoxyethylene nonylphenol ether in aluminum sulfate aqueous solution
?5mol/L, the same the present embodiment of other step, prepares nano aluminium oxide.
Embodiment 10
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1)-2) with embodiment 2 step 1)-2);
3) ammonium carbonate solution being 9 by the pH adding diethylethanolamine in advance joins step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, filter, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls at 3:1.The concentration of diethylethanolamine in ammonium carbonate solution is 1 × 10
?5mol/L;
4) with embodiment 2 step 4).
Be that 1mol/L substitutes 1 × 10 of the present embodiment by the concentration of diethylethanolamine in ammonium carbonate solution
?5mol/L, the same the present embodiment of other step, prepares nano aluminium oxide.
Embodiment 11
Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, comprise the steps:
1)-2) with embodiment 2 step 1)-2);
3) by pH be 9 ammonium carbonate solution join the step 2 of adding high-carbon fatty alcohol polyoxyethylene ether in advance under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, filter or centrifugation, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 1) described sedimentary weight ratio controls in the scope of 3:1; The concentration of high-carbon fatty alcohol polyoxyethylene ether in aluminum sulfate aqueous solution is 1 × 10
?5mol/L.
4) by step 3) the aluminium carbonate ammonium that obtains calcined by two step calcination methods, the condition of two step calcination methods is: be heated to 300 DEG C of insulations and be cooled to room temperature after 180 minutes, reheat 800 DEG C of insulations afterwards and be cooled to room temperature after 240 minutes, obtain nano aluminium oxide.
Also can be that 700 DEG C of insulations were cooled to room temperature after 30 minutes by the condition of two step calcination methods, reheat the condition of the two step calcination methods of 1500 DEG C of insulations, 30 minutes alternative the present embodiment afterwards, other same the present embodiment, prepares nano aluminium oxide.
1 × 10 of the present embodiment is substituted with 1mol/L
?5mol/L, other same the present embodiment, prepares nano aluminium oxide.
Claims (10)
1. Yi Lv ?the throw out that generates of gas battery electric discharge manufacture the method for nano aluminium oxide, it is characterized in that comprising the steps:
1) with distilled water repeatedly clean Lv ?the throw out that generates of gas battery electric discharge, make the water after cleaning for neutral, dry, obtain throw out;
2) step 1 is taken) throw out that obtains puts into container, then adds in container by aqueous sulfuric acid, heats and stir to make precipitate dissolves, and filter, obtain aluminum sulfate aqueous solution; Bright sulfur acid weight in described aqueous sulfuric acid and sedimentary weight ratio control in the scope of 2 ~ 6:1;
3) undertaken by the one of following three kinds of modes:
Mode one: ammonium sulfate is added step 2) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtain exsiccated ammonium alum supersaturated solution, be down to room temperature, have exsiccated ammonium alum crystallization, be separated, dry, obtain ammonium aluminum sulfate crystal; Described ammonium sulfate and step 2) described sedimentary weight ratio controls within the scope of 3 ~ 1:1;
Mode two: by step 2) to join pH be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generates precipitation, be separated, dry, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3;
Mode three: by pH be 9 ammonium carbonate solution join step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, dry, obtain aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3;
4) by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium calcined by a step calcination method or two step calcination methods, and cool to room temperature, obtains nano aluminium oxide.
2. method according to claim 1, it is characterized in that described step 3) mode one is: ammonium sulfate is added the step 2 of adding dispersion agent in advance) in the aluminum sulfate aqueous solution that obtains, be stirred to dissolve, heating evaporation moisture content, obtains exsiccated ammonium alum supersaturated solution, is down to room temperature, there is exsiccated ammonium alum crystallization, be separated, dry, obtain ammonium aluminum sulfate crystal; Described ammonium sulfate and step 2) described sedimentary weight ratio controls in the scope of 3 ~ 1:1; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
3. method according to claim 1, it is characterized in that described step 3) mode two is: by step 2) to join the pH adding dispersion agent in advance be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, drying, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in ammonium carbonate solution is 1 × 10
?5~ 1mol/L.
4. method according to claim 1, it is characterized in that described step 3) mode two is: the step 2 of dispersion agent will be added in advance) to join pH be under agitation in the ammonium carbonate solution of 9 for the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, drying, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
5. method according to claim 1, it is characterized in that described step 3) mode three is: the ammonium carbonate solution being 9 by the pH adding dispersion agent in advance joins step 2 under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, drying, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in ammonium carbonate solution is 1 × 10
?5~ 1mol/L.
6. method according to claim 1, it is characterized in that described step 3) mode three is: by pH be 9 ammonium carbonate solution join the step 2 of adding dispersion agent in advance under agitation) in the aluminum sulfate aqueous solution that obtains, generate precipitation, be separated, drying, obtains aluminium carbonate ammonium; Described volatile salt and step 2) described sedimentary weight ratio controls in the scope of 4 ~ 9:3; The concentration of dispersion agent in aluminum sulfate aqueous solution is 1 × 10
?5~ 1mol/L.
7. according to the method one of claim 2 ~ 6 Suo Shu, it is characterized in that described dispersion agent is polyoxyethylene glycol, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, sorbitan ester, sucrose fatty ester, alkylol amide, polyacrylamide, Sodium dodecylbenzene sulfonate, oil acyloxy ethyl sulfonic acid sodium, N-oleoyl N-methyl Sodium taurine salt, Aerosol OT, sodium dibutyl naphthalene sulfonate, stearic acid, dispersant B YK2010, methacrylic ester, polyacrylamide, polyethylene polyamine, N, N ?dimethylamino propylamine, 18 amino propylamine, diethylethanolamine, dispersion agent Disuper, cetyl trimethylammonium bromide, sodium lauryl sulphate or linear alkylbenzene sulphonic acid.
8. method according to claim 1, it is characterized in that described step 4) be: by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out cleaning, dry, calcined by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Or by step 3) after the ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out ball milling or grinding, calcined by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Or by step 3) ammonium aluminum sulfate crystal that obtains or aluminium carbonate ammonium carry out cleaning, ball milling or grinding, after drying, calcined by a step calcination method or two step calcination methods, cool to room temperature, obtains nano aluminium oxide;
Clean-out system for the cleaning of aluminium carbonate ammonium is distilled water, alcohol or acetone, and the clean-out system for ammonium aluminum sulfate crystal cleaning is alcohol or acetone.
9. the method according to claim 1 or 8, is characterized in that the condition of a described step calcination method is: be heated to 800-1500 DEG C of insulation 30-240 minute, be cooled to room temperature.
10. the method according to claim 1 or 8, is characterized in that the condition of described two step calcination methods is: be heated to 300-700 DEG C of insulation and be cooled to room temperature after 30-180 minute, reheats 800-1500 DEG C of insulation afterwards and is cooled to room temperature after 30-240 minutes.
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