CN103055786A - Alumina ball, preparation method of aluminum ball, and supergravity reactor - Google Patents
Alumina ball, preparation method of aluminum ball, and supergravity reactor Download PDFInfo
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- CN103055786A CN103055786A CN2011103264313A CN201110326431A CN103055786A CN 103055786 A CN103055786 A CN 103055786A CN 2011103264313 A CN2011103264313 A CN 2011103264313A CN 201110326431 A CN201110326431 A CN 201110326431A CN 103055786 A CN103055786 A CN 103055786A
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- charging aperture
- housing
- ammoniacal liquor
- alumina
- supergravity reactor
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 45
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 41
- 230000000694 effects Effects 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 230000002093 peripheral effect Effects 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims description 39
- 239000003921 oil Substances 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 230000036541 health Effects 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000008157 edible vegetable oil Substances 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a supergravity reactor. The supergravity reactor comprises a housing and a dispersing mechanism, wherein the dispersing mechanism is positioned in the housing and is connected with a driving motor through a hollow shaft; through holes are densely distributed in the outer peripheral surface of the dispersing mechanism; a first feed port is formed in the hollow shaft, and the hollow shaft is communicated with the interior of the dispersing mechanism; a second feed port is formed in the sidewall of the housing; and an outlet is formed in the bottom of the housing. The invention also provides a preparation method of an aluminum ball. The method comprises the following steps of: (i) contacting alumina powder with an acidic water solution to obtain gel; (ii) dispersing the gel to form balls in forming oil under the effect of supergravity, and then transferring the balls into ammonia water under the effect of gravity so as to obtain formed aluminum balls; and (iii) separating the formed alumina balls from the ammonia water. The invention also provides the alumina ball manufactured by using the method provided by the invention. According to the preparation method, the grain size of each alumina ball can be adjusted by adjusting the dimensions of the through holes in the dispersing mechanism.
Description
Technical field
The present invention relates to preparation method and the alumina balls obtained by this method of a kind of supergravity reactor, a kind of alumina balls.
Background technology
When aluminium oxide was used for catalytic reaction as catalyst or catalyst carrier, its shape had a great impact catalytic reaction.The aluminium oxide of industrial application has bar shaped, column, cellular and spherical etc., wherein ball-aluminium oxide owing to being in contact with one another with point between the particle, is piled up evenly as fixed bde catalyst or catalyst carrier use the time, eliminate bed resistance, greatly improved mass transfer and catalytic effect; During as fluid catalyst or catalyst carrier use, but spheric catalyst decrease wear rate.Be applied widely in the processes such as hydrogenation reaction in hydrofinishing, selective hydrogenation and the fine chemistry industry of ball-aluminium oxide in petrochemical industry.
Therefore, the ball-aluminium oxide that the prepared sizes distribution is concentrated, sphericity is high has great importance for petrochemical industry and field of fine chemical.
Summary of the invention
The purpose of this invention is to provide a kind of granularity controlled and distribute to concentrate, preparation method and the alumina balls obtained by this method of alumina balls that sphericity is high, and the supergravity reactor that is applicable to the method.
The invention provides a kind of supergravity reactor, it is characterized in that, this supergravity reactor comprises housing and the decentralized institution that is connected this housing and is connected with drive motors by hollow shaft, be densely covered with through hole on the outer peripheral face of described decentralized institution, offer the internal communication of the first charging aperture and hollow shaft and decentralized institution on the described hollow shaft, be provided with the second charging aperture on the sidewall of described housing and the bottom is provided with outlet.
The present invention also provides a kind of preparation method of alumina balls, it is characterized in that, the method may further comprise the steps, and (i) alumina powder is contacted with acidic aqueous solution, obtains colloidal sol; (ii) make described colloidal sol in moulding oil, disperse balling-up under the hypergravity effect, then under Action of Gravity Field, enter in the ammoniacal liquor, obtain the alumina balls of moulding; (iii) from ammoniacal liquor, separate the alumina balls of described moulding, and carry out health, drying and roasting.
In addition, the present invention also provides the alumina balls that made by above-mentioned method.
Method of the present invention can be passed through the particle diameter of the size adjustment alumina balls of the through hole on the adjusting decentralized institution, and the particle diameter distribution homogeneous of the alumina balls that make, good sphericity.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification, is used from explanation the present invention with the following specific embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the schematic diagram of the supergravity reactor in one embodiment of the present invention.
Description of reference numerals
1 supergravity reactor, 2 housings, 3 hollow shafts
4 drive motors, 5 decentralized institutions, 6 through holes
9 outlets of 7 first charging apertures, 8 second charging apertures
10 the 3rd charging apertures
The specific embodiment
The invention provides a kind of supergravity reactor, it is characterized in that, as shown in Figure 1, this supergravity reactor 1 comprises housing 2 and the decentralized institution 5 that is connected this housing 2 and is connected with drive motors 4 by hollow shaft 3, be densely covered with through hole 6 on the outer peripheral face of described decentralized institution 5, offer the internal communication of the first charging aperture 7 and hollow shaft 3 and decentralized institution 5 on the described hollow shaft 3, be provided with the second charging aperture 8 and bottom on the sidewall of described housing 2 and be provided with outlet 9.Wherein, described outlet 9 both can be used as the material liquid outlet, also can be used as the discharging opening of product.
According to the present invention, when described supergravity reactor 1 is interior when needing to add two kinds of different material liquids, preferably different material liquids is added by different charging apertures, therefore, preferably, on the sidewall of housing 2, below the second charging aperture 8, also be provided with the 3rd charging aperture 10.
There is no particular limitation in the position that the present invention offers for described the second charging aperture 8 and the 3rd charging aperture 10, and those skilled in the art can select the suitable position of offering according to the volume of required different material liquid.Preferably, the position that described the second charging aperture 8 is offered is positioned on the described decentralized institution 5, and the position that described the 3rd charging aperture 10 is offered is positioned under the described decentralized institution 5.The position that described the second charging aperture 8 is offered is positioned at and refers on the described decentralized institution 5 that position that the second charging aperture 8 is offered is higher than the peak of decentralized institution 5, similarly, the position offered of described the 3rd charging aperture 10 is positioned at and refers under the described decentralized institution 5 that position that the 3rd charging aperture 10 is offered is lower than the minimum point of decentralized institution 5.
Among the present invention, described decentralized institution 5 is used for holding the material to be disperseed from hollow shaft 3, and under the driving effect of drive motors 4, rotates with hollow shaft 3, and material to be disperseed is escaped and enter in the housing 2 by the through hole 6 on the outer peripheral face.Therefore, described decentralized institution 5 can be the various structures that can realize above-mentioned functions, for example can be the cavity that is distributed with through hole on various upper end open, lower end closed and the outer peripheral face.
In the present invention, in the situation that do not do opposite explanation, the dimensional orientation of supergravity reactor 1 when the state of use as described in the noun of locality of use typically refers to such as " upper and lower ".
The present invention also provides a kind of preparation method of alumina balls, it is characterized in that, the method may further comprise the steps,
(i) alumina powder is contacted with acidic aqueous solution, obtain colloidal sol;
(ii) make described colloidal sol in moulding oil, disperse balling-up under the hypergravity effect, then under Action of Gravity Field, enter in the ammoniacal liquor, obtain the alumina balls of moulding;
(iii) from ammoniacal liquor, separate the alumina balls of described moulding, and carry out health, drying and roasting.
The present invention does not have special requirement to the realization of described hypergravity, and usually, hypergravity all produces by the effect simulation Elevated Gravity of centrifugal force field.Preferably, obtain hypergravity by above-mentioned supergravity reactor, namely method of the present invention is preferably carried out in above-mentioned supergravity reactor.
Studies show that, adding an amount of silica in aluminium oxide can produce a very large impact the character of aluminium oxide.Add after the silicon, its surface acidity, specific area all improve a lot, and be very favourable to a lot of polymerizations and hydrogenation reaction.Therefore, in the step (i), preferably, described contact is carried out in the presence of Ludox.
The addition of described Ludox can change in very wide scope, can determine according to needed silicone content the addition of Ludox, and usually, in the described colloidal sol, in oxide, the weight ratio of silicon and aluminium is 1: 2-99.
According to the present invention, preferably, in the step (ii), the time that described colloidal sol is in the moulding oil needs only so that colloidal sol can form spherical by capillary effect in moulding oil, determining of the height of moulding oil is relevant with many factors, especially and the interrelation of particle size of the alumina balls of required preparation, and preferably, for the preparation average particulate diameter be the alumina balls of 0.1-3mm, the oil reservoir height of described moulding oil is preferably 200-250mm.
According to the present invention, the time that the colloidal sol of dispersion balling-up is in the ammoniacal liquor needs only so that disperse the colloidal sol of balling-up fully to solidify at the effect lower surface of ammoniacal liquor, those skilled in the art can order about in this purpose water layer height and the ammonia concn of the suitable ammoniacal liquor of lower selection, described ammonia concn is preferably the 8-15 % by weight, most preferably is 9.91-11.06 % by weight (corresponding density d
415=0.960～0.954); With aforementioned similar, the water layer height of described ammoniacal liquor is relevant with many factors, usually, is the alumina balls of 0.1-3mm for the preparation particle diameter, and the water layer height of ammoniacal liquor is preferably 1-10m, more preferably 2-8m.
According to the present invention, described method also preferably includes, and in step (ii), is the surfactant solution of 0.1-1.0 % by weight to the lasting implantation concentration in the interface of ammoniacal liquor and moulding oil, be preferably the 0.4-0.6 % by weight, most preferably be the surfactant solution of 0.5 % by weight.The injection of surfactant solution is in order to cushion the capillary difference between moulding oil and the ammoniacal liquor, avoids the colloidal sol of described dispersion balling-up to enter that shape after the ammoniacal liquor changes and the sphericity that affects final alumina balls.Therefore, the injection rate of described surfactant solution needs so that be full of surfactant solution on the interface between ammoniacal liquor and the moulding oil.Preferably, take the area at the interface of every square metre of ammoniacal liquor and moulding oil as benchmark, the injection rate of described surfactant solution is more than the per minute 3L, is preferably 3L-10L.In actual applications, the area at the interface of described ammoniacal liquor and moulding oil can calculate by the sectional area of equipment.The present inventor's discovery, the surfactant solution that adds the amount in the above-mentioned preferable range can make the sphericity of the alumina balls that obtain higher.
Among the present invention, described surfactant solution can be for the aqueous solution of the various surfactants of this area routine, such as anion surfactant (stearic acid, dodecyl sodium sulfate, neopelex etc.); Cationic surfactant (quaternary ammonium compound etc.); Zwitterionic surfactant (lecithin, amino acid pattern, betaine etc.); And non-ionic surface active agent (fatty glyceride, the aliphatic acid sorb is smooth, polysorbate etc.).Preferably, surfactant described in the present invention is neopelex or dodecyl sodium sulfate.
According to the present invention, the weight ratio of described alumina powder and acidic aqueous solution can be the ratio of this area routine, and preferably, in the step (i), the weight ratio of described alumina powder and acidic aqueous solution is 1: 2-3; More preferably 1: 2.4-2.8.In the colloidal sol that contains Ludox, with respect to the 100kg aluminium oxide, the content of water is preferably 200-250kg, more preferably 240-245kg.Wherein, described alumina powder is preferably aluminum oxide dry glue powder.Described alumina powder can be commercially available.
According to the present invention, provide acid acid can be various types of acid of this area routine in the described acidic aqueous solution, be preferably nitric acid and acetic acid, and with respect to the 100kg aluminium oxide, preferably, the content of acetic acid and nitric acid is respectively 5-10kg and 1-2kg in the described colloidal sol, more preferably 6-8kg and 1.2-1.8kg.
According to the present invention, preferably, before described method also is included in and disperses after the contact colloidal sol is vacuumized and wear out, the present inventor finds, through after vacuumizing successively and wearing out, bubble in the colloidal sol is drawn out of, and its peptization is more abundant, thereby makes the sphericity of the alumina balls that make and uniform particle diameter better.Concrete, the described condition that vacuumizes preferably includes, and vacuum be-0.05MPa is to-0.1MPa, be preferably-0.07MPa extremely-0.09MPa; The described time is 1-30 minute, is preferably 5-10 minute.Described aging condition preferably includes, and temperature is 5-50 ℃, is preferably 10-40 ℃, and the time is 5-120 minute, is preferably 20-100 minute.
According to the present invention, in the step (ii), described moulding oil can be the various moulding oil of this area routine, is preferably at least a in aviation kerosine, bobbin oil, pumping fluid, lathe oil and the edible oil, more preferably aviation kerosine or pumping fluid most preferably are aviation kerosine.Described moulding oil can be by commercially available.
According to the present invention, in the step (iii), the condition of described health can be for well known to a person skilled in the art various health-preserving conditions, and preferably, the condition of described health comprises: temperature is 60-70 ℃, and the time is 10-24 hour.
According to the present invention, in the step (iii), the condition of described drying and roasting can be for well known to a person skilled in the art various dryings and roasting condition, as, dry condition can comprise: temperature is 80-120 ℃, and the time is 8-16 hour; The condition of roasting can comprise: temperature is 400-1000 ℃, and the time is 2-10 hour.
According to the present invention, preferably, in the step (iii), the programming rate of described roasting is below 200 ℃/hour, is preferably below 50 ℃/hour; The present inventor's discovery, the programming rate of roasting are to prevent below 200 ℃/hour that alumina balls from fried ball phenomenon occuring in roasting process.
The present invention also provides the alumina balls that made by said method.The particle diameter of alumina balls can be regulated arbitrarily, usually, can be 0.1-3mm, is preferably 0.3-1.2mm.Because the particle diameter that the particle diameter of the size adjustment alumina balls of method of the present invention by through hole, the method have determined alumina balls is homogeneous comparatively.
Among the present invention, described alumina balls can be the pure alumina ball, also can be for containing the alumina balls of other components.For example, in preparation process, behind the adding Ludox, can make the silicon-containing alumina ball.
Below, in conjunction with accompanying drawing of the present invention, the process of carrying out the method for the invention in supergravity reactor 1 is described in detail.
Use supergravity reactor 1 as shown in Figure 1, at first, ammoniacal liquor is added in the housing 2 of supergravity reactor 1 from the 3rd charging aperture 10, then moulding oil is added in the housing 2 of supergravity reactor 1 from the second charging aperture 8, form respectively ammoniacal liquor layer and moulding oil reservoir.Start drive motors 4, make it pass through hollow shaft 3 and drive decentralized institution 5 rotations.Make described colloidal sol by the first charging aperture 7 in hollow shaft 3 enters decentralized institution 5, and make it under the hypergravity effect, via through holes 6 disperses to enter in the moulding oil reservoir, described colloidal sol in moulding oil by capillary effect englobement, then enter in the ammoniacal liquor layer by Action of Gravity Field, make the colloidal sol surface cure of englobement, the alumina balls after the curing are discharged continuously by outlet 9, then carry out follow-up health, drying and roasting process.
The rotating speed of described rotation can be regulated according to required dispersion effect; Usually, the rotating speed of decentralized institution 5 is 100-3000 rev/min, is preferably 500-2500 rev/min, most preferably is 500-2000 rev/min.
Below will describe the present invention by embodiment.In following examples, the alumina balls grain diameter records by particle size analyzer, and described particle diameter is the average diameter of particle; Ludox, aluminum oxide dry glue powder are commercially available product; Ammoniacal liquor, nitric acid and acetic acid are technical grade.
All use supergravity reactor 1 as shown in Figure 1 to carry out the preparation of alumina balls among the embodiment.Wherein, the housing 2 of supergravity reactor 1 is tubular, and height is 2400mm, and sectional area is 0.16m
2The minimum point of decentralized institution 5 is 2150mm apart from the distance of the bottom of supergravity reactor 1, and decentralized institution is cylindric and highly for 50mm, barrel is formed with through hole 6 all around; The second charging aperture is 2300mm apart from the distance of the bottom of supergravity reactor 1; The 3rd charging aperture is 2050mm apart from the distance of the bottom of supergravity reactor 1.
Embodiment 1
Use supergravity reactor 1 as shown in Figure 1; The aperture of through hole 6 is 0.8mm.
(1) ammoniacal liquor (concentration is 10 % by weight) is added in the housing 2 of supergravity reactor 1 from the 3rd charging aperture 10, then aviation kerosine is added in the housing 2 of supergravity reactor 1 from the second charging aperture 8, and form respectively the high ammoniacal liquor layer of 2000mm and the high moulding oil reservoir of 220mm.Start drive motors 4, make it pass through hollow shaft 3 and drive decentralized institution 5 High Rotation Speeds, the rotating speed of decentralized institution 5 is 1000 rev/mins.
(2) water, nitric acid, acetic acid, Ludox and aluminum oxide dry glue powder are fully mixed, obtain the sial mixed sols, in the sial mixed sols, with respect to the aluminium oxide of 100kg, the amount of nitric acid is 1.5kg, and the amount of acetic acid is 7kg, the amount of water is 240kg, and in oxide, the amount of Ludox is 20kg; Then, described sial mixed sols is vacuumized successively and wears out, the vacuum that vacuumizes is-0.08MPa, and the time is 8 minutes, and aging temperature is 25 ℃, and the time is 60 minutes.
(3) make vacuumize and wear out after the sial mixed sols by the first charging aperture 7 in hollow shaft 3 enters decentralized institution 5, and make it under the hypergravity effect, via through holes 6 disperses to enter in the moulding oil reservoir, forms the silicon-containing alumina ball; Then enter in the ammoniacal liquor layer by Action of Gravity Field, meanwhile, continue to inject the neopelex solution of 0.5 % by weight at the interface of moulding oil and ammoniacal liquor, injection rate is 0.5L/min, the silicon-containing alumina ball that obtains is discharged continuously by outlet 9, then carry out health, drying and roasting process, obtain product P 1.
The condition of described health comprises that temperature is 65 ℃, and the time is 18 hours; The condition of described drying comprises that temperature is 100 ℃, and the time is 12 hours; The condition of described roasting comprises that temperature is 800 ℃, and the time is 5 hours, and programming rate is 50 ℃/hour.Fried ball phenomenon does not occur in the silicon-containing alumina ball in the roasting process.
The test result of product P 1 is listed in the table 1.
Embodiment 2
Use supergravity reactor 1 as shown in Figure 1; The aperture of through hole 6 is 0.5mm.
(1) ammoniacal liquor (concentration is 9.91 % by weight) is added in the housing 2 of supergravity reactor 1 from the 3rd charging aperture 10, then pumping fluid is added in the housing 2 of supergravity reactor 1 from the second charging aperture 8, and form respectively the high ammoniacal liquor layer of 2000mm and the high moulding oil reservoir of 200mm.Start drive motors 4, make it pass through hollow shaft 3 and drive decentralized institution 5 High Rotation Speeds, the rotating speed of decentralized institution 5 is 500 rev/mins.
(2) water, nitric acid, acetic acid, Ludox and aluminum oxide dry glue powder are fully mixed, obtain the sial mixed sols, in the sial mixed sols, with respect to the aluminium oxide of 100kg, the amount of nitric acid is 1.2kg, and the amount of acetic acid is 8kg, the amount of water is 242kg, and in oxide, the amount of Ludox is 10kg; Then, described sial mixed sols is vacuumized and wears out, the vacuum that vacuumizes is-0.07MPa, and the time is 10 minutes, and aging temperature is 15 ℃, and the time is 100 minutes; Vacuumize and wear out after the viscosity of sial mixed sols be 20-50 drops/sec.
(3) make vacuumize and wear out after the sial mixed sols by the first charging aperture 7 in hollow shaft 3 enters decentralized institution 5, and make it under the hypergravity effect, via through holes 6 disperses to enter in the moulding oil reservoir, forms the silicon-containing alumina ball; Then enter in the ammoniacal liquor layer by Action of Gravity Field, meanwhile, continue to inject the neopelex solution of 0.5 % by weight at the interface of moulding oil and ammoniacal liquor, injection rate is 0.5L/min; Silicon-containing alumina ball after the curing that obtains is discharged continuously by outlet 9, then carries out health, drying and roasting process, obtains product P 2.The test result of product P 2 is listed in the table 1.
The condition of described health comprises that temperature is 70 ℃, and the time is 10 hours; The condition of described drying comprises that temperature is 120 ℃, and the time is 8 hours; The condition of described roasting comprises that temperature is 500 ℃, and the time is 10 hours, and programming rate is 50 ℃/hour.Fried ball phenomenon does not occur in the silicon-containing alumina ball in the roasting process.
Embodiment 3
Use supergravity reactor 1 as shown in Figure 1; The aperture of through hole 6 is 1.2mm.
(1) ammoniacal liquor (concentration is 11.06 % by weight) is added in the housing 2 of supergravity reactor 1 from the 3rd charging aperture 10, then aviation kerosine is added in the housing 2 of supergravity reactor 1 from the second charging aperture 8, and form respectively the high ammoniacal liquor layer of 2000mm and the high moulding oil reservoir of 250mm.Start drive motors 4, make it pass through hollow shaft 3 and drive decentralized institution 5 High Rotation Speeds, the rotating speed of decentralized institution 5 is 2000 rev/mins.
(2) water, nitric acid, acetic acid, Ludox and aluminum oxide dry glue powder are fully mixed, obtain the sial mixed sols, in the sial mixed sols, with respect to the aluminium oxide of 100kg, the amount of nitric acid is 1.8kg, and the amount of acetic acid is 6kg, the amount of water is 245kg, and in oxide, the amount of Ludox is 5kg; Then, described sial mixed sols is vacuumized and wears out, the vacuum that vacuumizes is-0.09MPa, and the time is 5 minutes, and aging temperature is 35 ℃, and the time is 20 minutes; Vacuumize and wear out after the viscosity of sial mixed sols be 20-50 drops/sec.
(3) make vacuumize and wear out after the sial mixed sols by the first charging aperture 7 in hollow shaft 3 enters decentralized institution 5, and make it under the hypergravity effect, via through holes 6 disperses to enter in the moulding oil reservoir, forms the silicon-containing alumina ball; Then enter in the ammoniacal liquor layer by Action of Gravity Field, meanwhile, continue to inject the SDS solution of 0.5 % by weight at the interface of moulding oil and ammoniacal liquor, injection rate is 0.5L/min; Silicon-containing alumina ball after the curing that obtains is discharged continuously by outlet 9, then carries out health, drying and roasting process, obtains product P 3.The test result of product P 3 is listed in the table 1.
The condition of described health comprises that temperature is 60 ℃, and the time is 24 hours; The condition of described drying comprises that temperature is 80 ℃, and the time is 16 hours; The condition of described roasting comprises that temperature is 1000 ℃, and the time is 2 hours, and programming rate is 50 ℃/hour.Fried ball phenomenon does not occur in the silicon-containing alumina ball in the roasting process.
Embodiment 4
Method according to embodiment 1 prepares silicon-containing alumina ball P4, and different is not inject neopelex solution.The test result of P4 is listed in the table 1.
Embodiment 5
Method according to embodiment 1 prepares silicon-containing alumina ball P5, and different is, the roasting programming rate is 250 ℃/hour, and in roasting process, approximately fried ball phenomenon appears in 30% silicon-containing alumina ball.The test result of P5 is listed in the table 1, and wherein, average grain diameter refers to not explode the average particulate diameter of the part of ball.
Embodiment 6
Method according to embodiment 1 prepares silicon-containing alumina ball P6, and different is, does not vacuumize and wears out.Approximately fried ball phenomenon appears in 10% silicon-containing alumina ball.The test result of P6 is listed in the table 1, and wherein, average grain diameter refers to not explode the average particulate diameter of the part of ball.
Table 1
| Outward appearance (range estimation) | Average grain diameter, mm | Uniform particle diameter (range estimation) | |
| Embodiment 1, product P 1 | Ball | 0.65 | Good |
| Embodiment 2, product P 2 | Ball | 0.43 | Good |
| Embodiment 3, product P 3 | Ball | 1.00 | Good |
| Embodiment 4, product P 4 | Oblate spheroid | 0.65 | Good |
| Embodiment 5, product P 5 | Ball | 0.65 | Good |
| Embodiment 6, product P 6 | Ball | 0.65 | Good |
As can be seen from Table 1, preferred embodiment of the present invention, namely the particle diameter of the alumina balls prepared of embodiment 1-3 is controlled, and the range estimation uniform particle diameter, the good sphericity of outward appearance.
Can find out from the result of embodiment 1 and embodiment 4, do not add the product P 4 that the embodiment 4 of surfactant solution obtains and be oblate spheroid, this is because moulding oil and ammoniacal liquor surface tension difference are larger, disperse the colloidal sol of balling-up that distortion has occured when entering ammoniacal liquor, illustrate that simultaneously at ammoniacal liquor and moulding oil content interface injection surfactant solution be preferred embodiment of the present invention.
Can find out from the result of embodiment 1 and embodiment 5, programming rate is too fast in the roasting process easily causes exploding in a large number ball, and therefore, the roasting programming rate is to be preferred embodiment of the present invention below 200 ℃.
Can find out from the result of embodiment 1 and embodiment 6, do not vacuumize and the embodiment 6 that wears out in the silicon-containing alumina product that obtains in roasting process, burst in a large number, illustrate that colloidal sol is vacuumized and wears out is preferred embodiment of the present invention.
In addition, also can carry out any combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. supergravity reactor, it is characterized in that, this supergravity reactor (1) comprises housing (2) and the decentralized institution (5) that is connected this housing (2) and is connected with drive motors (4) by hollow shaft (3), be densely covered with through hole (6) on the outer peripheral face of described decentralized institution (5), offer the internal communication of the first charging aperture (7) and hollow shaft (3) and decentralized institution (5) on the described hollow shaft (3), be provided with the second charging aperture (8) and bottom on the sidewall of described housing (2) and be provided with outlet (9).
2. supergravity reactor according to claim 1 wherein, on the sidewall of housing (2), also is provided with the 3rd charging aperture (10) in the below of the second charging aperture (8).
3. supergravity reactor according to claim 2, wherein, the position that described the second charging aperture (8) is offered is positioned on the described decentralized institution (5), and the position that described the 3rd charging aperture (10) is offered is positioned under the described decentralized institution (5).
4. the preparation method of alumina balls is characterized in that, the method may further comprise the steps,
(i) alumina powder is contacted with acidic aqueous solution, obtain colloidal sol;
(ii) make described colloidal sol in moulding oil, disperse balling-up under the hypergravity effect, then under Action of Gravity Field, enter in the ammoniacal liquor, obtain the alumina balls of moulding;
(iii) from ammoniacal liquor, separate the alumina balls of described moulding, and carry out health, drying and roasting.
5. method according to claim 4, wherein, in the step (i), described contact is carried out in the presence of Ludox.
6. method according to claim 5, wherein, in the described colloidal sol, in oxide, the weight ratio of silicon and aluminium is 1: 2-99.
7. method according to claim 4, wherein, described method also comprises, in step (ii), continuing implantation concentration to the interface of ammoniacal liquor and moulding oil is the surfactant solution of 0.1-1.0 % by weight, take the area at the interface of every square metre of ammoniacal liquor and moulding oil as benchmark, the injection rate of described surfactant solution is more than the per minute 3L.
8. the described method of any one according to claim 4-7, wherein, in the step (i), the weight ratio of described alumina powder and acidic aqueous solution is 1: 2-3.
9. method according to claim 8, wherein, it is nitric acid and acetic acid that acid acid is provided in the described acidic aqueous solution, and with respect to the 100kg aluminium oxide, the content of acetic acid and nitric acid is respectively 5-10kg and 1-2kg in the described colloidal sol.
10. the described method of any one according to claim 4-7 wherein, before described method also is included in and disperses after the contact vacuumizes colloidal sol and wears out, and the described condition that vacuumizes comprises, vacuum is-0.05MPa extremely-0.1MPa; Time is 1-30 minute, and described aging condition comprises, temperature is 5-50 ℃, and the time is 5-120 minute.
11. the described method of any one according to claim 4-7, wherein, in the step (ii), the concentration of described ammoniacal liquor is the 8-15 % by weight.
12. the described method of any one according to claim 4-7, wherein, in the step (ii), described moulding oil is at least a in aviation kerosine, bobbin oil, pumping fluid, lathe oil and the edible oil.
13. the described method of any one according to claim 4-7, wherein, in the step (iii), the programming rate of described roasting is below 200 ℃/hour.
14. the alumina balls that made by the described method of any one among the claim 4-13.
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| CN104492407A (en) * | 2014-12-25 | 2015-04-08 | 江苏晶晶新材料有限公司 | Preparation method of long-chain alkane dehydrogenation catalyst carrier with large pore volume and low specific surface area |
| CN110871111A (en) * | 2018-08-31 | 2020-03-10 | 中国石油化工股份有限公司 | A kind of ball-forming device and preparation method of spherical carrier |
| CN112427007A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of activated alumina ball adsorbent |
| CN112429755A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of water treatment active alumina ball |
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| CN103990416B (en) | 2016-03-02 |
| CN103055786B (en) | 2015-01-21 |
| CN103990416A (en) | 2014-08-20 |
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