CN1865147A - Nano alumina and its preparation method - Google Patents
Nano alumina and its preparation method Download PDFInfo
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- CN1865147A CN1865147A CN 200510046481 CN200510046481A CN1865147A CN 1865147 A CN1865147 A CN 1865147A CN 200510046481 CN200510046481 CN 200510046481 CN 200510046481 A CN200510046481 A CN 200510046481A CN 1865147 A CN1865147 A CN 1865147A
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Abstract
This invention discloses a method for producing nanometer alminum dioxide. The procedures comprise: solubilise the melting inorganic aluminium salt in the mixture of hydrocarbon component and surfactantto form the molten salt-in-oil super solubilising colloidal group, which limits the aluminum hydroxide generated by the reaction of molten salt and precipitant in the colloidal group, so as to avoid the increase of aluminum oxide particle size and narrow the particle size distribution range. This invention is characterized of high yield and purity, with low cost of surfactant and hydrocarbon component. Besides, the process is simple and is adapted for industrial mass production.
Description
Technical field
The present invention relates to a kind of nano aluminium oxide and preparation method thereof, relate in particular to a kind of preparation method of mono-dispersed nano gama-alumina.
Background technology
Nano aluminium oxide is that a kind of particle diameter is the ultrafine particle of 1～100nm, have strong volume effect, quantum size effect, surface effects and macro quanta tunnel effect, show a series of excellent properties at light, electricity, thermodynamics and chemical reaction etc. aspect many, be widely used as fine ceramics, matrix material, fluorescent material, wet quick property transmitter, infrared absorbing material and catalytic material.Gama-alumina is the solid support material that is widely used in catalyzer.Gama-alumina is prepared into nanoparticle, and very big change can take place in the character of catalyzer.
The preparation method of nano aluminium oxide can reduce solid phase method, vapor phase process and liquid phase method at present.Liquid phase method has the precipitator method and sol-gel method and phase transfer method.CN1122772A discloses the method for preparing fine-grained alumina with the aluminium alkoxide sol-gel method, and the shortcoming of this method is that the price of raw material is higher.CN1030066C also discloses the method with the hydrolysis of low-carbon (LC) aluminium alcoholates, and the particle diameter of the aluminum oxide that obtains is bigger, and is inhomogeneous.
Summary of the invention
The preparation method of the dispersed nano aluminum oxide that the purpose of this invention is to provide that a kind of cost is low, aluminum oxide purity height and productive rate is high is especially for the preparation method of the dispersed nano level gama-alumina of making support of the catalyst.
The contriver finds through a large amount of experiments, the fusion inorganic aluminate can be solubilized in hydrocarbon component and the water-in-oil-type surfactant mixtures, form the super solubilising nanometer micelle of oil bag melting salt, control reaction with the nanometer micelle, reaction, the weathering process of inorganic aluminate and precipitation agent are all carried out in the nanometer micelle, thereby produce the nano-aluminum hydroxide gel.
Based on above-mentioned design, the present invention prepares the method for nano aluminium oxide, comprises the steps:
(1) hydrocarbon component and VB value are mixed less than 1 tensio-active agent;
(2) the nano-aluminum hydroxide gel is made by one of following method:
Method one: the fused inorganic aluminate slowly joins in the mixture of step (1) gained, is mixed to form even colloid; Add precipitation agent then, under 50～120 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method two: the fused inorganic aluminate is slowly added in the mixture of step (1) gained, be mixed to and form even colloid; In confined conditions, below the ammonia critical temperature, be generally the critical temperature of 30 ℃～ammonia, add precipitation agent liquefied ammonia, under 30～200 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method three: use precipitation agent and inorganic aluminate to mix the post-heating fusion, slowly join in the mixture of step (1) gained, be mixed to and form even colloid; Under airtight condition, resulting mixture is carried out precipitation from homogeneous solution under 70～200 ℃ of temperature, 4～8 hours reaction times, aging then, obtain the nano-aluminum hydroxide gel;
(3) the nano-aluminum hydroxide gel of step (2) gained is carried out roasting after, obtain nano aluminium oxide;
Weight with the resulting mixture of step (2) is benchmark, inorganic aluminate (butt), precipitation agent and water consumption are 60.0wt%～95.0wt%, be preferably 85.0wt%～95.0wt%, the mol ratio of water and aluminium atom is 3～15: 1, be preferably 3～10: 1, the mol ratio of aluminium atom and precipitation agent is 1: 0.9～5, be preferably 1: 1.2～and 3; The consumption of tensio-active agent is 0.1wt%～8.0wt%, better is 0.5wt%～4.0wt%, preferably 0.8wt%～2.0wt%; The consumption of hydrocarbon component is 3.0wt%～32.0wt%, better is 3.0wt%～15.0wt%, preferably 4.0wt%～8.0wt%; Wherein water can add with crystal water and/or free-water form in step (1) and/or step (2).
Among the present invention, the main effect of water is to participate in reaction as a kind of reactant, makes the reaction of aluminium salt and precipitation agent generate aluminium hydroxide.In addition, inorganic aluminate adds entry in melting process, also can play the effect that reduces fusing point.Water can adopt following one or more modes to add: a, add entry in step (1), b, adopt the form of the inorganic aluminate that contains crystal water to add in step (2), c, add entry in the inorganic aluminate melting process.The adding mode of water is not limited to aforesaid way, can adopt the precipitation agent aqueous solution such as method one, can also form at the mixture of inorganic aluminate and step (1) gained in method one, the method two in the even colloidal process and to add or to add after forming even colloid, method three also can form at the mixture of inorganic aluminate and precipitation agent eutectic and step (1) gained in the even colloidal process or behind the even colloid of formation and add or the like.Method one preferably adopts the precipitation agent aqueous solution, and contains the inorganic aluminate of crystal water and/or add entry in the inorganic aluminate melting process; Method two and method three preferably adopt the inorganic aluminate that contains crystal water and/or add entry in the inorganic aluminate melting process.
Used inorganic aluminate comes from anhydrous or contains in aluminum nitrate, aluminum chloride and the Tai-Ace S 150 of crystal water one or more among the present invention.
Tensio-active agent described in the step (1) is the VB value less than 1 water-in-oil-type tensio-active agent, is selected from one or more mixtures of SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride and two sweet esters, ethylene glycol monostearate, glycol ether monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl maleic anhydride polyol ester, hydramine ester emulsifying agent and succimide class emulsifying agent.Relevant VB value notion please refer to " the A Study of Identifying EmulsionType of Surfactant--Volume Balance Value " that this patent people is published in the Journal ofcolloid and interface science fourth phase in 2002.
The employed hydrocarbon component of step (1) is selected from one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables oil, animal oil.Wherein vacuum distillate is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more of the dewaxing of four line distillates or wax-containing distillate, can come from paraffinic base, intermediate base or naphthenic base crude; The decompression slack wax is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more slack waxs that obtain in the four line distillates, as being the second line of distillation slack wax, subtracting three-way slack wax, subtracting four line slack waxs and composition thereof; The residual oil slack wax is frivolous asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil.Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil and the lard.
Can also add cosurfactant in hydrocarbon component and the surfactant mixtures in the step (1), weight with step (2) gained mixture is benchmark, the consumption of cosurfactant is 0wt%～2.0wt%, better is 0.1wt%～1.0wt%, preferably 0.1wt%～0.5wt%.
Described cosurfactant is one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
Among the present invention, in order to obtain purer aluminum oxide, also can be with the nano-aluminum hydroxide gel of step (2) gained through washing Zhiyin ion weight concentration less than 0.5%, and after 5～24 hours, through step (3), obtain nano aluminium oxide again through 80～110 ℃ of oven dry.Described washing generally adopts water washing just can reach requirement, is preferably to adopt washing with alcohol 1-3 time, washes with water again, and water wherein preferably adopts distilled water or deionized water.
Among the present invention, inorganic aluminate is heated to fusion, perhaps the even post-heating of inorganic aluminate and precipitant mix to fused temperature is 50～120 ℃, the hydrocarbon component and the surfactant mixtures of step (1) gained preferably are heated to 30～120 ℃, preferably are heated to melt temperature ± 20 ℃ of inorganic aluminate.
The present invention can adopt different maturing temperatures to handle, thereby obtain dissimilar aluminum oxide as required, is preferably through 350～650 ℃ of roastings 4～10 hours, obtains the nanometer gama-alumina.
Wearing out described in the step (2) generally is to become under the glue temperature and pressure to wear out 0～30 hour, and the digestion time of method one the best is 0.5～3 hour, and the digestion time of method two the best is 0.5～3 hour, and the digestion time of method three the bests is 5～30 hours.
The character of the nanometer gama-alumina of gained of the present invention is as follows: median size 5-100nm is preferably 7-30nm, specific surface 200～400m
2/ g, pore volume 0.2～1.1ml/g, mean pore size 2～30nm.Surface-area among the present invention and pore structure are with U.S. ASAP2400 type low temperature liquid nitrogen absorption instrument, calculate by the BET method.Median size wherein is the mean diameter that records with transmission electron microscope (TEM).
The inventive method prepares the nanometer gama-alumina and has the following advantages:
1, the inventive method is to utilize the character of the high interior phase dispersion system of oil bag melting salt, this system is super solubilising micelle, it is synthetic that the oxyhydroxide that aluminium salt and precipitation agent reaction are generated is limited in carrying out in the micelle original position, thereby avoided the increase of oxide diameter sizes, the nano-aluminum hydroxide gel particle size distribution range that obtains is narrow.
2, the inorganic aluminate consumption is big in the inventive method, the productive rate height of nano-oxide, and the purity height, and used tensio-active agent and hydrocarbon component consumption are little, cost is low.
3, the purity requirement to aluminum oxide is not under the extra high situation, can adopt the direct roasting method, reduces cost.
4, outstanding feature is that system prepares the nanometer gama-alumina under water requirement situation seldom in the inventive method.
5, the inventive method technology is simple, can carry out industrial production in enormous quantities.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the nano aluminium oxide of embodiment 10 gained.
Embodiment
Among the present invention, the concrete preparation method of nano-aluminum hydroxide gel is as follows.
Method one:
A, under normal pressure, inorganic aluminate is heated to fusion, be generally 50～120 ℃, slowly join in the mixture of step (1) gained that is heated to 30～120 ℃ in advance, be mixed to and form even colloid, general mixing time is 1～60 minute, is preferably 5～30 minutes, is preferably 10～20 minutes;
B, in the mixture of steps A, slowly add precipitation agent, under 50～120 ℃ of temperature, be neutralized into glue, aging 0.5～3 hour then, obtain the nano-aluminum hydroxide gel;
Wherein used precipitation agent is one or more in sodium hydroxide, potassium hydroxide, volatile salt, bicarbonate of ammonia and the ammonia, and this precipitation agent adds with aqueous solution form, is preferably the saturated or oversaturated aqueous solution, preferably adopts ammonia, adds with saturated ammoniacal liquor form.
Method two:
A, inorganic aluminate is heated to fusion, is generally 50～120 ℃, slowly adding is heated in 30～120 ℃ the mixture of step (1) gained in advance, be mixed to and form even colloid, general mixing time is 1～60 minute, is preferably 5～30 minutes, is preferably 10～20 minutes;
B, in confined conditions feeds precipitation agent liquefied ammonia below the ammonia critical temperature, be neutralized into glue under 30～200 ℃ of temperature, and constant temperature and pressure is 0.5～3 hour then, obtains the nano-aluminum hydroxide gel.
Method three:
A, use precipitation agent and inorganic aluminate mix post-heating to 50～120 ℃ fusion, slowly join in the mixture of step (1) gained that is heated to 30～120 ℃ in advance, mix to form uniform colloid; Wherein used precipitation agent is one or more in volatile salt, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate, is preferably one or more of urea, hexamethylenetetramine and ammonium citrate.
B, under airtight condition, resulting mixture in the steps A is carried out precipitation from homogeneous solution under 70～200 ℃ of temperature, in 4～8 hours reaction times, aging then 5～30 hours, obtain the nano-aluminum hydroxide gel.
Further the present invention is described in detail below in conjunction with specific embodiment.
Used hydrocarbon component picks up from the general petrochemical works, Lanzhou in the embodiment of the invention, and its character sees Table 1.
The character of table 1 hydrocarbon component
| Condensation point, ℃ | Oil-containing %, wt% | Viscosity (100 ℃), m 2/s | Penetration degree (25 ℃), 1/10mm | |
| Atmosphere 3rd side cut oil | 5 | 90 | 2.01 | / |
| First vacuum side stream | 30 | 80 | 4.98 | / |
| Second line of distillation oil | 35 | 75 | 5.02 | / |
| Subtract three-way pressed oil | 37 | 68 | 5.55 | / |
| Subtract four line oil | 42 | 56 | 8.58 | 46 |
| The second line of distillation slack wax | 50 | 7.5 | 4.82 | 20 |
| Subtract three-way slack wax | 53 | 8.5 | 5.02 | 19 |
| Subtract four line slack waxs | 56.5 | 22 | 6.08 | 25 |
| The residual oil slack wax | 69 | 32.5 | 19.3 | 40 |
| Frivolous asphalt oil | 38 | 72 | 8.82 | / |
The character of embodiment 1～14 products obtained therefrom sees Table 1, table 2 and table 3.Wherein, T-154 is two succimides of hanging, and originates from Jinzhou general petrochemicals factory.OP-4 is polyoxyethylene nonylphenol ether (4).
Embodiment 1
50g is subtracted three-way pressed oil and 10g SP-80 mixing, and 80 ℃ of heating for dissolving mix; The 700g ANN aluminium nitrate nonahydrate is heated to 80 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.Drip 20 ℃ of saturated ammoniacal liquor 240g, aging 3 hours, obtain the nano-aluminum hydroxide gel.Aluminum hydroxide gel promptly gets present embodiment nanometer gama-alumina through 550 ℃ of roastings 8 hours.
Embodiment 2
10g is subtracted four line oil, 20g first vacuum side stream, 2g second line of distillation slack wax, 13g residual oil slack wax, 8gSP-80,2g OP-4 and 2g M-201 mix, 100 ℃ of heating for dissolving mix; The 820g ANN aluminium nitrate nonahydrate is heated to 100 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 30 minutes.In closed reactor, in super solubilising colloid, add 50 ℃ of 123g liquefied ammonia, 180 ℃ of reactions 2 hours, obtain the nano-aluminum hydroxide gel.Aluminum hydroxide gel is through 600 ℃ of roastings 8 hours, i.e. present embodiment nanometer gama-alumina.
Embodiment 3
57g atmosphere 3rd side cut oil, 3g fatty acid monoglyceride, 10g polyisobutenyl toxilic acid glycol ether ester and 1g Yatall MA acid amides are mixed 100 ℃ of heating for dissolving; 613g aluminum chloride, 367g urea and 355g water are mixed and heated to 120 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.Closed reactor, 200 ℃ of reactions 4 hours, wearing out obtained the nano-aluminum hydroxide gel in 10 hours.Aluminum hydroxide gel is through 650 ℃ of roastings 4 hours, i.e. present embodiment nanometer gama-alumina.
Embodiment 4
100g is subtracted three-way pressed oil, 23g subtract four line slack waxs, the frivolous asphalt oil of 53g, 18g polyisobutenyl toxilic acid glycol ether ester and 6g calcium mahogany sulfonate and mix, 80 ℃ of heating for dissolving mix; The 500g Patent alum is heated to 80 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.The 190g volatile salt is dissolved in the 110g water, and adds in the above-mentioned super solubilising colloid, aging 3 hours, obtain the nano-aluminum hydroxide gel.Aluminum hydroxide gel promptly gets present embodiment nanometer gama-alumina through 550 ℃ of roastings 8 hours.
Embodiment 5
With 146g subtract three-way pressed oil, 70g polyisobutenyl toxilic acid triethanolamine ester mixes 100 ℃ of heating for dissolving; 460g nine water aluminum nitrates, 324g ammonium citrate are mixed and heated to 120 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.Closed reactor, 200 ℃ of reactions 4 hours, wearing out obtained the nano-aluminum hydroxide gel in 10 hours.Aluminum hydroxide gel is through 650 ℃ of roastings 4 hours, i.e. present embodiment nanometer gama-alumina.
Embodiment 6
107g is subtracted three-way slack wax, 214g sheep oil, 1gSP-40,3g fatty acid monoglyceride and 1g Yatall MA acid amides mix, 100 ℃ of heating for dissolving mix; 375g ANN aluminium nitrate nonahydrate, 132g aluminum chloride and 50g water are heated to 100 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 30 minutes.In closed reactor, in super solubilising colloid, add 50 ℃ of 117g liquefied ammonia, 180 ℃ of reactions 2 hours, obtain the nano-aluminum hydroxide gel.Aluminum hydroxide gel is through 600 ℃ of roastings 8 hours, i.e. present embodiment nanometer gama-alumina.
Embodiment 7
70g is subtracted four line oil, 110g peanut oil, 15g polyisobutenyl toxilic acid glycol ether ester and 30gT-154 to mix 100 ℃ of heating for dissolving; 270g ANN aluminium nitrate nonahydrate, 284g Patent alum and 221g hexamethylenetetramine are mixed and heated to 120 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.Closed reactor, 200 ℃ of reactions 4 hours, wearing out obtained the nano-aluminum hydroxide gel in 10 hours.Aluminum hydroxide gel is through 650 ℃ of roastings 4 hours, i.e. present embodiment nanometer gama-alumina.
Embodiment 8
The nano-aluminum hydroxide gel that obtains by embodiment 1, with the 200ml washing with alcohol once, with 200ml distilled water wash three times, through 100 ℃ of oven dry, 250 ℃ of roastings 2 hours, 550 ℃ of roastings 8 hours, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 9
By the nano-aluminum hydroxide gel that embodiment 2 obtains, use the method for embodiment 9, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 10
By the nano-aluminum hydroxide gel that embodiment 3 obtains, use the method for embodiment 9, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 11
By the nano-aluminum hydroxide gel that embodiment 4 obtains, use embodiment 9 methods, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 12
By the nano-aluminum hydroxide gel that embodiment 5 obtains, use embodiment 9 methods, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 13
By the nano-aluminum hydroxide gel that embodiment 6 obtains, use embodiment 9 methods, i.e. the nanometer gama-alumina of present embodiment.
Embodiment 14
By the nano-aluminum hydroxide gel that embodiment 7 obtains, use embodiment 9 methods, i.e. the nanometer gama-alumina of present embodiment.
The composition of table 2 embodiment 1～4 and performance
| Product property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Median size (nm) | 80 | 70 | 88 | 97 |
| BET specific surface (m 2/g) | 240 | 325 | 245 | 300 |
| Pore volume (ml/g) | 0.38 | 0.49 | 0.25 | 0.35 |
| Mean pore size () | 42 | 36 | 29 | 33 |
The composition of table 3 embodiment 5～7 and performance
| Product property | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Median size (nm) | 85 | 95 | 75 |
| BET specific surface (m 2/g) | 210 | 310 | 340 |
| Pore volume (ml/g) | 0.35 | 0.3 | 0.25 |
| Mean pore size () | 45 | 30 | 37 |
The character of table 4 embodiment 8～14 gained aluminum oxide
| Embodiment | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| Median size (nm) | 35 | 30 | 24 | 25 | 33 | 22 | 35 |
| BET specific surface (m 2/g) | 260 | 350 | 280 | 230 | 260 | 310 | 340 |
| Pore volume (ml/g) | 0.58 | 0.89 | 0.65 | 0.75 | 0.66 | 1.00 | 0.95 |
| Mean pore size () | 120 | 150 | 80 | 75 | 110 | 150 | 142 |
Claims (24)
1, a kind of preparation method of nano aluminium oxide comprises the steps:
(1) hydrocarbon component and VB value are mixed less than 1 tensio-active agent;
(2) the nano-aluminum hydroxide gel is made by one of following method:
Method one: the fused inorganic aluminate slowly joins in the mixture of step (1) gained, is mixed to form even colloid; Add precipitation agent then, under 50～120 ℃ of temperature, be neutralized into glue, aging 0～30 hour then, obtain the nano-aluminum hydroxide gel;
Method two: the fused inorganic aluminate is slowly added in the mixture of step (1) gained, be mixed to and form even colloid; In confined conditions, below the ammonia critical temperature, feed precipitation agent liquefied ammonia, under 30～200 ℃ of temperature, be neutralized into glue, aging 0～30 hour then, obtain the nano-aluminum hydroxide gel;
Method three: use precipitation agent and inorganic aluminate to mix the post-heating fusion, slowly join in the mixture of step (1) gained, be mixed to and form even colloid; Under airtight condition, resulting mixture is carried out precipitation from homogeneous solution be neutralized into glue under 70～200 ℃ of temperature, gelation time 4～8 hours aging 0～30 hour then, obtains the nano-aluminum hydroxide gel;
(3) the nano-aluminum hydroxide gel of step (2) gained is carried out roasting after, obtain nano aluminium oxide;
Wherein water adds with crystal water and/or free-water form in step (1) and/or step (2);
Weight with the resulting mixture of step (2) is benchmark, and inorganic aluminate (butt), precipitation agent and water consumption are 60wt%～95wt%, and the mol ratio of water and aluminium atom is 3～15: 1, and the mol ratio of aluminium atom and precipitation agent is 1: 0.9～5; The consumption of tensio-active agent is 0.1wt%～8wt%; The consumption of hydrocarbon component is 3wt%～32wt%.
2, preparation method according to claim 1, it is characterized in that the weight with the resulting mixture of step (2) is benchmark, the consumption of inorganic aluminate (butt), precipitation agent and water is 85wt%～95wt%, the mol ratio of water and aluminium atom is 3～10: 1, and the content of tensio-active agent is 0.5wt%～4wt%; The consumption of hydrocarbon component is 3wt%～15wt%.
3, preparation method according to claim 1 is characterized in that with the resulting mixture of step (2) be benchmark, and the content of tensio-active agent is 0.8wt%～2wt%; The consumption of hydrocarbon component is 4wt%～8wt%.
4, preparation method according to claim 1, it is characterized in that described hydromining adds with following one or more modes: a, in step (1), add entry, b, in step (2), adopt the form of the inorganic aluminate contain crystal water to add, c, in the inorganic aluminate melting process, add entry, d, form with the mixture of step (1) gained and to add in the even colloidal process or after forming even colloid, to add.
5, preparation method according to claim 1 is characterized in that described water, and method one is to adopt the precipitation agent aqueous solution, and contains the inorganic aluminate of crystal water and/or add entry in the inorganic aluminate melting process; Method two and method three are to adopt to contain the inorganic aluminate of crystal water and/or add entry in the inorganic aluminate melting process.
6, preparation method according to claim 1 is characterized in that used inorganic aluminate in the step (2) comes from anhydrous or contains in aluminum nitrate, aluminum chloride and the Tai-Ace S 150 of crystal water one or more.
7, preparation method according to claim 1 is characterized in that the tensio-active agent described in the step (1) is selected from one or more mixtures of SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride and two sweet esters, ethylene glycol monostearate, glycol ether monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl toxilic acid polyol ester, polyisobutenyl toxilic acid hydramine ester emulsifying agent and succimide class emulsifying agent.
8, preparation method according to claim 1 is characterized in that the employed hydrocarbon component of step (1) is selected from one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables oil, animal oil.
9, preparation method according to claim 8 is characterized in that described vacuum distillate is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more of the dewaxing of four line distillates or wax-containing distillate; The decompression slack wax is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more slack waxs that obtain in the four line distillates; The residual oil slack wax is frivolous asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil; Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil and the lard.
10, preparation method according to claim 1 is characterized in that in the step (2), and method one used precipitation agent is one or more in sodium hydroxide, potassium hydroxide, volatile salt, bicarbonate of ammonia and the ammonia, adds with aqueous solution form; Method three used precipitation agents are one or more in volatile salt, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate.
11, preparation method according to claim 1 is characterized in that in the step (2), and method one used precipitation agent adds with saturated or supersaturated aqueous solution form; Method three used precipitation agents are one or more of urea, hexamethylenetetramine and lemon acid amide.
12, preparation method according to claim 9 is characterized in that in the step (2) that method one used precipitation agent is an ammonia, adds with saturated ammoniacal liquor form.
13, preparation method according to claim 1, it is characterized in that adding cosurfactant in middle hydrocarbon component of step (1) and the surfactant mixtures, weight with step (2) gained mixture is benchmark, and the consumption of cosurfactant is 0.1wt%～2.0wt%.
14, preparation method according to claim 13 is characterized in that the weight with the resulting mixture of step (2) is benchmark, and the consumption of cosurfactant is 0.2wt%～1.5wt%.
15, preparation method according to claim 13 is characterized in that described cosurfactant is one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
16, preparation method according to claim 1, it is characterized in that the nano-aluminum hydroxide gel of step (2) gained through washing Zhiyin ion weight concentration less than 0.5%, and through 80～110 ℃ the oven dry 5～24 hours after, through step (3), obtain nano aluminium oxide again.
17, preparation method according to claim 14 is characterized in that described washing is to adopt organic solvent washing 0-3 time earlier, washes with water again, and wherein used solvent is ethanol or acetone.
18, preparation method according to claim 1 is characterized in that in the step (2), the melt temperature of inorganic aluminate is 50～120 ℃ in method one and the method two, and the melt temperature of inorganic aluminate and precipitation agent is 50～120 ℃ in the method three.
19, preparation method according to claim 1 is characterized in that step (1) gained hydrocarbon component and surfactant mixtures are heated to 30～120 ℃.
20, preparation method according to claim 19 is characterized in that step (1) gained hydrocarbon component and surfactant mixtures are heated to melt temperature ± 20 ℃ of inorganic aluminate or inorganic aluminate and precipitation agent.
21, preparation method according to claim 1 is characterized in that in the step (2), the digestion time of method one is 0.5～3 hour, and the digestion time of method two is 0.5～3 hour, and the digestion time of method three is 5～30 hours.
22,, it is characterized in that the described roasting condition of step (3) is:, obtain the nanometer gama-alumina through 350～650 ℃ of roastings 4～10 hours according to claim 1 or 14 described preparation methods.
23, preparation method according to claim 22 is characterized in that the character of gained nanometer gama-alumina is as follows: median size 5-100nm, specific surface 200～400m
2/ g, pore volume 0.2～1.1ml/g, mean pore size 2～30nm.
24, preparation method according to claim 23, it is characterized in that the character of gained nanometer gama-alumina is as follows: median size is 7-30nm.
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