CN103449493A - Low-cost nano aluminum oxide film preparation method and nano aluminum oxide film - Google Patents
Low-cost nano aluminum oxide film preparation method and nano aluminum oxide film Download PDFInfo
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- CN103449493A CN103449493A CN2013100142667A CN201310014266A CN103449493A CN 103449493 A CN103449493 A CN 103449493A CN 2013100142667 A CN2013100142667 A CN 2013100142667A CN 201310014266 A CN201310014266 A CN 201310014266A CN 103449493 A CN103449493 A CN 103449493A
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Abstract
The invention discloses a low-cost nano aluminum oxide powder preparation method which comprises the following steps: 1. preparing an aluminum ammonium sulfate crystal from an aluminum oxide spent catalyst or aluminum scrap turnings; 2. dissolving aluminum ammonium sulfate in water, taking aqua ammonia, dropwisely adding the aluminum ammonium sulfate solution into the aqua ammonia while stirring to obtain a precipitate, filtering, adding a hydrochloric acid solution, heating in a water bath while stirring, sufficiently reacting, adding polyvinyl alcohol, and cooling to room temperature to obtain a boehmite sol; and 3. immersing a pretreated support base into the boehmite sol, slowly lifting, drying at room temperature, transferring into a furnace, heating to 550 DEG C, keeping for 2 hours, and carrying out furnace cooling to obtain the nano aluminum oxide film on the support base. By using waste as the raw material, the preparation method disclosed by the invention has the advantages of cost saving, simple production technique and not need of adding complex equipment, and can easily implement industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of nano aluminium oxide film, refer in particular to a kind of preparation method of the film of nano aluminium oxide cheaply and the nano aluminium oxide film prepared according to this preparation method.
Background technology
Mould material and membrane technique are one of current the most popular new and high technologies in the world.In many-sides such as the energy, electronics, petrochemical complex, medical and health, foodstuffs industry, environment protection and people's lives, all need sepn process miscellaneous (removing, make with extra care, purifying etc. of for example separation of material, purification, pollution).Traditional sepn process energy consumption is high, efficiency is low, often can accomplish energy-conservation, efficient, environmental friendliness after using membrane technique instead.In the situation that world today's energy shortage, water resources are nervous, environmental pollution is day by day serious, membrane separation technique has been deep into many fields of productive life.Become and promoted national many important industry development, the quality of improving the people's livelihood, control the important means of environmental pollution.Under this background, the film industry of advanced country in the world has developed into the huge industry of the output value.
Early stage mould material be take organic membrane as main.But due to the organic membrane poor heat resistance, use after stain to be difficult for processing, rise with the industry of the mineral membranes such as aluminium oxide nano film in recent years.The E.I.Du Pont Company of the U.S., U.S Filter company, Canadian Alcan company have all organized the production of nano aluminium oxide film.According to estimates, within 2004, comprise that the output value of the ceramic membrane of nano aluminium oxide film will be over 1,000,000,000 dollars.Membrane separation technique was developed the 1950's, and along with the development of membrane technique, its Application Areas constantly enlarges, and present international membrane technique industry begins to take shape.2004, the market sales revenue of world's separatory membrane reached 10,000,000,000 dollars, and annual growth reaches 15%.The aluminum oxide of take is greater than 12% as main mineral membrane accounts for the market share.International membrane technique meeting is once classified special topic as by " the strategic role that membrane process is played the part of in most industry of 21 century " and is set off a discussion, and thinks that it is that one of new and high technology of development is arranged mid-term 21 century most.Mineral membrane as 21 century high-temperature gas extremely likely separate and chemical industry novel reactor material and receive people's concern.The national " 863 " plan is also listed the research of " inorganic separation catalytic film " among national hi-tech development plan in.
It is raw material that at present aluminum oxide film production adopts the alkoxide of aluminium more, and technological line is relatively ripe, and shortcoming is that alkoxide is expensive and be difficult to preparation, and cost is higher.For above-mentioned reasons, seriously hinder application and the popularization of alumina-ceramic filter membrane, also limited scale and the process of its industrialization.Existing borolon film mostly adopts sol-gel method, existing commercial γ-Al
2o
3ultra-filtration membrane adopts this method to prepare just.The method is as Al (OC with organo-aluminium compound
3h
7)
3, Al (OC
4h
9)
3or metal inorganic salt is as AlCl
3for starting raw material, by hydrolysis, form stable sol.Then impregnant sol on porous supporting body, under the effect of capillary attraction or drying, sol layer changes dissolved glue film into, obtains inorganic porous membrane after thermal treatment.Key in film-forming process is the integrity of controlling diaphragm, avoids the generation of pin hole and defects i.e.cracks.
For the above-mentioned defect of prior art, be necessary to design a kind of new nano aluminium oxide method for manufacturing thin film, thereby the nano aluminium oxide film preparation reduce costs and can suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the film of nano aluminium oxide cheaply and the nano aluminium oxide film prepared by this preparation method, and this preparation method utilizes industrial waste or the cheap intermediate product nano alumina powder jointed film that raw material production meets the requirements as an alternative.
Solving the technical scheme that technical problem of the present invention adopts is: a kind of nano alumina powder jointed preparation method cheaply is provided, and it comprises the following steps:
Step 1, take the aluminum oxide spent catalyst as raw material, by aluminum oxide spent catalyst grind into powder, according to alumina content and monoammonium sulfate mol ratio, it is 1:6～take at 1: 10 sample, divide and add for 3 ~ 5 times in the monoammonium sulfate of melting, react 0.5～1 hour, being dissolved in water after cooling obtains the first solution;
Perhaps, the aluminium scrap car of take bits are raw material, by aluminium scrap car bits, according to aluminium content and monoammonium sulfate mol ratio, are that 1:3～1:6 takes sample, divide and add for 3 ~ 5 times in the saturated solution of monoammonium sulfate, place 8 ~ 15 hours, allow it fully react and obtain the second solution;
By reacted described the first solution or the second solution filter, get filtrate, the filtrate heating is concentrated, and then recrystallization 3～5 times, pulverize it and dry, and obtains ammonium aluminum sulfate crystal;
Step 2, the exsiccated ammonium alum obtained in step 1 is soluble in water, and get ammonia soln, drip aluminum ammonium sulfate solution to ammonia soln while stirring, be precipitated thing, then filter, fully wash to neutrality with deionized water, then this throw out is transferred in flask, add again hydrochloric acid soln, and heat in water-bath, rapid stirring, fully add polyvinyl alcohol after reaction more simultaneously, continue to stir, then be cooled to room temperature and obtain boehmite sol;
Step 3, support substrate is placed in to sodium hydroxide solution boils, then be washed till neutrality with distilled water; Use again HNO
3solution boils, and with distilled water, is washed till neutrality, then it is proceeded in stove and calcines with the surperficial organism that burnouts; After pre-treatment, support substrate is immersed in the boehmite sol in step 2, then slowly mention, be placed in humidity and be the atmosphere drying at room temperature 24 ~ 36 hours of 60-80% left and right, move into again in stove and be heated to 550 ℃ and keep furnace cooling after 2 hours, can on this support substrate, obtain the nano aluminium oxide film.
Preferably, in step 2, rate of addition is controlled at 1 ~ 2mL/min.
Preferably, in step 2, before filtering, this throw out also will the condition that be 50 ℃ in temperature under ageing 2 hours.
Preferably, in step 2, the concentration of hydrochloric acid soln is 1.0mol/L, and the temperature in water-bath is 85 ℃, reacts after 1 hour and adds polyvinyl alcohol, and the time of continuing to stir is 6～12 hours.
Preferably, in step 3, the concentration of sodium hydroxide solution is 1mol/L, HNO
3the concentration of solution is 1mol/L.
Preferably, in step 3, be fired to 600 ℃ and keep 1h with the surperficial organism that burnouts in retort furnace.
Preferably, in step 3, the time of immersing in the boehmite sol in step 2 is 5 ~ 9 seconds.
Preferably, in step 3, the temperature rise rate while being heated to 550 ℃ is 10 ℃/minute.
Preferably, in step 3, described support substrate is selected from a kind of in metallic matrix, alloy substrate, aluminum oxide, plastics.
Solving another technical scheme that technical problem of the present invention adopts is: a kind of nano aluminium oxide film prepared according to above-described preparation method is provided.
Compared with prior art, preparation method of the present invention has following several advantage:
1, because raw material is waste material and easily acquisition, not only saved cost, and improved physical environment.2, preparation method's of the present invention production technique is simple, without adding complex apparatus.3, be easy to suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is the schema that the embodiment of the present invention prepares the nano aluminium oxide film.
The DSC graphic representation that Fig. 2 is dissolved glue film.
The TG graphic representation that Fig. 3 is dissolved glue film.
The XRD spectra that Fig. 4 is dissolved glue film.
Fig. 5 is that dissolved glue film is calcined to the XRD spectra after 550 ℃.
Fig. 6 is the stereoscan photograph of dissolved glue film (a) and calcining rear oxidation aluminium film (b).
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The aluminium waste that contains of mechanical industry processing for the present invention, the circulation fluid of producing with alum, can be used as waste nano aluminium oxide film with the cheap raw materials such as circulation fluid of alumina producer, this is with regard to the preparation cost of decrease nano aluminium oxide film, and the range of application that enlarges aluminum oxide film has been created condition.
As shown in Figure 1, Fig. 1 is a kind of nano aluminium oxide film preparation schema of the present invention.This preparation method comprises the steps:
Step 1, containing the selection of aluminium waste:
Have two kinds to be easy to obtain containing aluminium waste:
(1) the aluminum oxide spent catalyst of petroleum chemical industry (kind had is salic more than 50%, and more than year output kiloton, major part can not be utilized and bury processing).
(2) aluminium alloy processing industry aluminium scrap car bits (the annual thousands of tons of of this kind, Shanghai waste material, make waste material with 2000 yuan per ton and process at present, wherein contains aluminium more than 90%).
Take the aluminum oxide spent catalyst as raw material: spent catalyst is pulverized, and is 1:6～take sample at 1: 10 according to alumina content and monoammonium sulfate mol ratio, considers several times in the monoammonium sulfate that adds melting, reacts 0.5～1 hour, is dissolved in water after cooling;
The aluminium scrap car of take bits are raw material: aluminium scrap car bits are taken to sample according to aluminium content and monoammonium sulfate mol ratio as 1:3～1:6, consider several times in the saturated solution that adds monoammonium sulfate, placement is spent the night (8 ~ 15 hours), allows it fully react;
By reacted solution filter, get filtrate, the filtrate heating is concentrated, and then recrystallization 3～5 times, pulverize it and dry, and obtains ammonium aluminum sulfate crystal.
The preparation of step 2, boehmite sol: take the 0.03mol exsiccated ammonium alum and be dissolved in about 100mL water, get 2mol/L ammonia soln 165mL, drip aluminum ammonium sulfate solution to ammonia soln while stirring, rate of addition is controlled at 1-2mL/min, be precipitated thing, be 50 ℃ in temperature and place 2 hours (ageing 2h); Again the gained throw out is filtered, with deionized water, fully wash to neutrality, again above-mentioned throw out is transferred in flask, the hydrochloric acid soln that adds 10mL1.0mol/L, in temperature, be to heat in 85 ℃ of water-baths, rapid stirring, add polyvinyl alcohol after 1h simultaneously, continue to stir 6～12h, be cooled to room temperature and obtain boehmite sol.
Step 3, nano aluminium oxide film preparation process: the sodium hydroxide solution that the alumina-supported matrix is placed in to 1mol/L boils 0.5h, with distilled water, is washed till neutrality; Use again the HNO of 1mol/L
3solution boils 30min, with distilled water, is washed till neutrality, then it is proceeded in retort furnace and is fired to 600 ℃ and keep 1h with the surperficial organism that burnouts; After pre-treatment, the alumina-supported matrix is immersed 5-9 second in the above-mentioned stable transparent boehmite sol prepared, with certain pull rate, mention, the atmosphere drying at room temperature that to be placed in humidity be 60% ~ 80% left and right 24 ~ 36 hours, move in retort furnace temperature rise rate with 10 ℃/min and be warming up to 550 ℃ and keep furnace cooling after 2 hours, on this alumina-supported matrix, form the nano aluminium oxide film.
If prepare thicker aluminum oxide film, can repeat above step 2 and step 3.
This support substrate can be selected from a kind of in metallic matrix, alloy substrate, aluminum oxide, plastics.In an embodiment of the present invention, this support substrate is selected from aluminum oxide.
The sign of nano aluminium oxide film prepared by the present invention:
1, scanning electronic microscope (SEM), 3 D video microscope (3D Rotational Microscopy) are analyzed.
The pattern of surface particle and pore size are studied with daily output JSM-6700F awkward silence at a meeting emission scan electron microscope, and the defects such as surface crack are that 20-800 HIROX KH-2700 3 D video microscope is doubly observed by magnification.
2, differential scanning calorimetric analysis (DSC)
By dissolved glue film at the upper TG-DSC curve of measuring of Netzsch STA-429 thermal analyzer (German Netzsch company produce), still air atmosphere, temperature rise rate is 10 ℃/min, range 100 μ V.
3, X-ray diffraction analysis (XRD)
Adopt the D of Rigaku company max-2550 type X-ray diffractometer (XRD) (condition determination is
40KV, 100mA Scanspeed:2deg/min) crystal formation of mensuration film after calcining.
Fig. 2 and Fig. 3 are respectively DSC, the TG curve of boehmite sol film.Being converted into pellumina from the boehmite sol film is that the final step of film-forming process is also one of step of most critical, in this work, with DSC and TG, joins together to investigate this process.Dsc analysis shows that this process has three endotherm(ic)peaks (Fig. 2).First peak (100 ℃) is corresponding to the evaporation of moisture in gel, and second peak (300 ℃) is relevant with the transformation of aluminum oxide crystal formation, and the 3rd peak (approximately 500 ℃) becomes γ-Al corresponding to gel conversion
2o
3the heat absorbed during structure.Can find out (Fig. 3) from the TG curve, sample starts just constantly weightless (dehydration) from room temperature, until reach basic constant weight 550 ℃ the time.In experiment, select this temperature as calcining temperature.
X-ray diffraction analysis after dissolved glue film and calcining
Fig. 4 is the X-ray powder diffraction style (XRD) of dissolved glue film, find the data of this product with the standard diffracting spectrum data of γ-AlOOH, conform to (orthohormbic structure JCPDS21-1307,
).The XRD peak of product is sharp shape diffraction peak, illustrates that its crystallinity is good, does not find any other impurity diffraction peak in sample.Fig. 5 is the XRD figure spectrum after 550 ℃ of calcinings of boehmite film sample.As can be seen from the figure, but all diffraction peaks all index turn to Emission in Cubic γ-Al
2o
3(spacer: Fd3m (227) γ-Al
2o
3jCPDS29-63,
).
High power sem analysis after dissolved glue film and calcining
The SEM photo that Fig. 6 is dissolved glue film and calcining rear oxidation aluminium film, wherein, (a) be γ-AlOOH dissolved glue film, is (b) 550 ℃ of γ-Al that calcining forms
2o
3film, the boehmite particle mainly be take microscler crystal grain as main, and size of particles is more even, evenly gel is grain formation more uniform film and pore structure, the aperture of take below 10nm is as main, and particle is greatly about the 20nm left and right.γ-the Al formed after 550 ℃ of roastings
2o
3film microstructure and the boehmite sol film of film are basically identical, but hole slightly has change large.According to the two dimensional image analysis technology, tentatively calculate to such an extent that porosity is 49% left and right.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a nano alumina powder jointed preparation method cheaply, is characterized in that, it comprises the following steps:
Step 1, take the aluminum oxide spent catalyst as raw material, by aluminum oxide spent catalyst grind into powder, according to alumina content and monoammonium sulfate mol ratio, it is 1:6～take at 1: 10 sample, divide and add for 3 ~ 5 times in the monoammonium sulfate of melting, react 0.5～1 hour, being dissolved in water after cooling obtains the first solution;
Perhaps, the aluminium scrap car of take bits are raw material, by aluminium scrap car bits, according to aluminium content and monoammonium sulfate mol ratio, are that 1:3～1:6 takes sample, divide and add for 3 ~ 5 times in the saturated solution of monoammonium sulfate, place 8 ~ 15 hours, allow it fully react and obtain the second solution;
By reacted described the first solution or the second solution filter, get filtrate, the filtrate heating is concentrated, and then recrystallization 3～5 times, pulverize it and dry, and obtains ammonium aluminum sulfate crystal;
Step 2, the exsiccated ammonium alum obtained in step 1 is soluble in water, and get ammonia soln, drip aluminum ammonium sulfate solution to ammonia soln while stirring, be precipitated thing, then filter, fully wash to neutrality with deionized water, then this throw out is transferred in flask, add again hydrochloric acid soln, and heat in water-bath, rapid stirring, fully add polyvinyl alcohol after reaction more simultaneously, continue to stir, then be cooled to room temperature and obtain boehmite sol;
Step 3, support substrate is placed in to sodium hydroxide solution boils, then be washed till neutrality with distilled water; Use again HNO
3solution boils, and with distilled water, is washed till neutrality, then it is proceeded in stove and calcines with the surperficial organism that burnouts; After pre-treatment, support substrate is immersed in the boehmite sol in step 2, then slowly mention, be placed in humidity and be the atmosphere drying at room temperature 24 ~ 36 hours of 60-80% left and right, move into again in stove and be heated to 550 ℃ and keep furnace cooling after 2 hours, can on this support substrate, obtain the nano aluminium oxide film.
2. preparation method according to claim 1, is characterized in that, in step 2, rate of addition is controlled at 1 ~ 2mL/min.
3. preparation method according to claim 1, is characterized in that, in step 2, before filtering, this throw out also will the condition that be 50 ℃ in temperature under ageing 2 hours.
4. preparation method according to claim 1, is characterized in that, in step 2, the concentration of hydrochloric acid soln is 1.0mol/L, and the temperature in water-bath is 85 ℃, reacts after 1 hour and add polyvinyl alcohol, and the time of continuing to stir is 6～12 hours.
5. preparation method according to claim 1, is characterized in that, in step 3, the concentration of sodium hydroxide solution is 1mol/L, HNO
3the concentration of solution is 1mol/L.
6. preparation method according to claim 1, is characterized in that, in step 3, is fired to 600 ℃ and keep 1h with the surperficial organism that burnouts in retort furnace.
7. preparation method according to claim 1, is characterized in that, in step 3, the time of immersing in the boehmite sol in step 2 is 5 ~ 9 seconds.
8. preparation method according to claim 1, is characterized in that, in step 3, the temperature rise rate while being heated to 550 ℃ is 10 ℃/minute.
9. preparation method according to claim 1, is characterized in that, in step 3, described support substrate is selected from a kind of in metallic matrix, alloy substrate, aluminum oxide, plastics.
10. the nano aluminium oxide film prepared according to the described preparation method of claim 1 to 9 any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130004A (en) * | 2014-07-07 | 2014-11-05 | 山东理工大学 | Preparation method of high-strength block-shaped porous alumina nano-ceramic |
| CN105643480A (en) * | 2016-01-14 | 2016-06-08 | 洛阳三睿宝纳米科技有限公司 | Nano fiber oilstone |
| CN106731890A (en) * | 2016-12-26 | 2017-05-31 | 华北电力大学 | A kind of inoranic membrane and preparation method for trapping vapor in coal steam-electric plant smoke |
| CN109734110A (en) * | 2019-02-28 | 2019-05-10 | 潍坊工商职业学院 | A kind of alumina powder preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055459A1 (en) * | 1980-12-29 | 1982-07-07 | Rikuun Electric co. | Process for producing oxides using chemical vapour deposition |
| JPH09286613A (en) * | 1996-04-19 | 1997-11-04 | Nippon Steel Chem Co Ltd | Production of high purity alumina and mullite for electronic material |
| CN1696060A (en) * | 2005-03-24 | 2005-11-16 | 上海大学 | Method for preparing Nano powder of alumina from industrial waste |
-
2013
- 2013-01-15 CN CN2013100142667A patent/CN103449493A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055459A1 (en) * | 1980-12-29 | 1982-07-07 | Rikuun Electric co. | Process for producing oxides using chemical vapour deposition |
| JPH09286613A (en) * | 1996-04-19 | 1997-11-04 | Nippon Steel Chem Co Ltd | Production of high purity alumina and mullite for electronic material |
| CN1696060A (en) * | 2005-03-24 | 2005-11-16 | 上海大学 | Method for preparing Nano powder of alumina from industrial waste |
Non-Patent Citations (1)
| Title |
|---|
| 张良苗: "AlOOH核壳、空心球的控制合成与组装及Al2O3纳米粉体、薄膜的廉价制备", 《上海大学博士学位论文》, 21 August 2009 (2009-08-21) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130004A (en) * | 2014-07-07 | 2014-11-05 | 山东理工大学 | Preparation method of high-strength block-shaped porous alumina nano-ceramic |
| CN104130004B (en) * | 2014-07-07 | 2015-10-07 | 山东理工大学 | The preparation method of the block porous aluminum oxide nano pottery of high strength |
| CN105643480A (en) * | 2016-01-14 | 2016-06-08 | 洛阳三睿宝纳米科技有限公司 | Nano fiber oilstone |
| CN106731890A (en) * | 2016-12-26 | 2017-05-31 | 华北电力大学 | A kind of inoranic membrane and preparation method for trapping vapor in coal steam-electric plant smoke |
| CN106731890B (en) * | 2016-12-26 | 2023-08-18 | 华北电力大学 | Inorganic film for capturing water vapor in flue gas of thermal power plant and preparation method |
| CN109734110A (en) * | 2019-02-28 | 2019-05-10 | 潍坊工商职业学院 | A kind of alumina powder preparation method |
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Application publication date: 20131218 |