CN102000574A - Roller flyball method for preparing spherical magnetic alumina carrier - Google Patents
Roller flyball method for preparing spherical magnetic alumina carrier Download PDFInfo
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- CN102000574A CN102000574A CN 201010513924 CN201010513924A CN102000574A CN 102000574 A CN102000574 A CN 102000574A CN 201010513924 CN201010513924 CN 201010513924 CN 201010513924 A CN201010513924 A CN 201010513924A CN 102000574 A CN102000574 A CN 102000574A
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- colloidal sol
- running roller
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- alumina carrier
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Abstract
The invention discloses a roller flyball method for preparing spherical magnetic alumina carrier. The method comprises the following steps: magnetic cores are added in alumina sol, organic amine solution is added to mix evenly, then the mixture is poured out to flow onto the surface of a roller which rotates, the roller surface line speed can be adjusted, the droplets thrown by the roller are treated through oil column moulding, aging, washing, drying and roasting to obtain the spherical magnetic alumina carrier. The method of the invention can be conveniently adjusted to prepare different diameters of spherical magnetic alumina carriers; the spherical shape is good, the distribution of magnetism is uniform, the cost is low, no pollution is caused, the batch production can be realized; and the carrier is suitable for the magnetically stabilized bed technology or the catalysis-separation process and also for the reaction processes such as hydrorefining and selective hydrogenation in the petrochemical engineering field.
Description
Technical field
The present invention relates to a kind of running roller gets rid of ball and prepares spherical magnetic alumina carrier method.
Background technology
Carrier is the important component part of catalyst, and for many industrial catalysts, after the active component decision, the kind of carrier, character have very big influence to catalyst performance.The mechanical power of carrier is with being skeleton as active component, and it can the dispersed activity component and increases the intensity of catalyst.Aluminium oxide have than table and long-pending high, pore structure is abundant and the heat endurance advantages of higher, it is widely used in important courses of reaction such as oxidation, hydrogenation, dehydrogenation, isomerization, disproportionation, polymerization and reformation, is the carrier that has the call in the petrochemical industry.Magnetic catalyst is the catalyst that a class has the magnetic response feature.Magnetic catalyst had both combined the advantage of high catalytic activity in the homogeneous catalysis, had avoided the characteristics of diffusion-restricted in the heterogeneous catalysis process again, had given the magnetic stalling characteristic of catalyst uniqueness simultaneously, had simplified operating process, had reduced running cost.
Magnetic stablizing bed as a kind of novel bed form, have the advantage of fixed bed and fluid bed concurrently.Compare with fluid bed, externally-applied magnetic field can effectively be controlled alternate back-mixing and particle leakage; Compare with fixed bed, magnetic stablizing bedly can use catalyst particle and be unlikely to cause too high pressure drop, voidage can make bed should not produce channel and hot localised points uniformly.In addition, magnetic stablizing bed can also stable operation in the scope of broad, but and bubble crushing improve interphase mass transfer.Magnetic stablizing bed above characteristic makes it have broad application prospects in oil, chemical industry, medicine and other fields.
Spherical catalyst carrier particle has the characteristics even, that fluid resistance is even and stable of filling, good pore structure, big specific area, good physical strength and acid and alkali-resistance stability, and mechanical strength and mobile and can reduce the abrasion that catalyst fluidization produces is arranged preferably, obtained application more and more widely.The preparation side of ball-aluminium oxide mainly contains and rotates in comminution granulation, spray shaping method, the oil method of forming (comprising the oil ammonia column method of forming and oil-drop method) etc.
Rotating comminution granulation is that very thin alumina powder is placed in the rotating disk of inclination, sprays into amount of water with nozzle above dish, by continuous rotation, makes between the material to adhere to each other mutually.When spherolite length arrives a certain size, just overflowing from web becomes finished product.Though this method gained support strength is very high, it is rough and spherolite is big or small inhomogeneous.Because the raw material that this method is used is alumina powder, the physical arrangement of the ball-aluminium oxide that obtains and performance are subjected to the restriction of alumina powder structure and performance, and outstanding behaviours is that aperture and pore volume are less.
Spray drying process is through nozzle atomization with drop, form sphere under capillary effect, after meeting with hot-air, the solvent in the drop is evaporated rapidly, the fine particle aggregate that drop is become have spherical shape and fine flowability, the product particle of gained is less.
The research that oil-drop method prepares ball-aluminium oxide starts from the 1950's, at first aluminium powder or aluminium bits are dissolved in aluminum salt solution or the dilute hydrochloric acid solution and prepare acidic aluminum sol, aluminium colloidal sol is mixed with coagulant, mixed solution enters moulding in the hot oil column after disperseing, wearing out under higher temperature and pressure decomposes coagulant fully again, after washing, dry, ball-aluminium oxide that roasting obtains having certain crystal formation and pore structure.But it is bigger than normal to exist sphere sizes, diameter skewness, output, inefficient shortcoming.
The invention provides a kind of running roller gets rid of ball and prepares spherical magnetic alumina carrier method.We join magnetic nuclear in the aluminium colloidal sol, and add organic amine solution and evenly mix, and pour out the running roller surface that flows to rotation then, adjustable roller wheel surface linear velocity, and the droplet that throws away from running roller obtains spherical magnetic alumina carrier through behind the forming oil column.The present invention can conveniently adjust the spherical magnetic alumina carrier of preparation different size diameter, spherical form is good, magnetic is evenly distributed, low-cost, pollution-free, can produce in batches, carrier is applicable to magnetic stablizing bed technology or catalytic separation process, also is applicable to courses of reaction such as hydrofinishing in the petrochemical industry and selective hydrogenation.
Summary of the invention
The purpose of this invention is to provide a kind of running roller gets rid of ball and prepares spherical magnetic alumina carrier method.
Running roller provided by the present invention gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that its step is:
1) be that mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to subzero 10 to 10 ℃ in the magnetic nuclear adding aluminium colloidal sol of 0.05-100 μ m with average particle size particle size;
2) the organic amine solution of configuration 0.1-5mol/l is cooled to subzero 10 to 10 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs;
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the running roller linear resonance surface velocity is at 0.1-50m/s, the droplet that throws away from running roller passes through 50-120 ℃ of forming oil column 1-120min, isolate the bead of moulding, again through 100-200 ℃ of aging 2-20h, washing back dry 2-20h under 20-200 ℃, then at 300-800 ℃ of roasting 1-12h, obtaining diameter is the spherical magnetic carrier of 0.1-500 μ m.
Among the above-mentioned preparation method:
Said magnetic nuclear is barium ferrite, γ-Fe
2O
3, α-Fe
2O
3, Fe
3O
4, in one or more.
Said magnetic nuclear is 1-50 with the mass ratio of aluminium colloidal sol: 100.
The aluminium element mass content is 1-30% in the said aluminium colloidal sol.
Said organic amine is urea and/or hexamethylenetetramine.
Said step 2) mol ratio of Al and organic amine is 1-10 in the colloidal sol that obtains: 1.
It is 1-100ml/min that said colloidal sol is poured out speed.
The spherical magnetic alumina carrier of preparation different size diameter 0.1-500 μ m can be conveniently adjusted in this invention, spherical form is good, magnetic is evenly distributed, low-cost, pollution-free, can produce in batches, carrier is applicable to magnetic stablizing bed technology or catalytic separation process, also is applicable to courses of reaction such as hydrofinishing in the petrochemical industry and selective hydrogenation.
Description of drawings
Fig. 1 is that running roller gets rid of the schematic diagram that ball prepares spherical magnetic alumina carrier, and 1 for step 2 among the figure) colloidal sol that obtains, 2 are the rotation running roller, 3 is the forming oil column device.
The specific embodiment
Embodiment 1:
1) with average particle size particle size is α-Fe of 0.1 μ m
2O
3Magnetic nuclear adds in the aluminium colloidal sol, and mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to subzero 5 ℃, and magnetic nuclear is 1: 5 with the mass ratio of aluminium colloidal sol, and the aluminium element mass content is 10% in the aluminium colloidal sol.
2) the hexamethylenetetramine solution of configuration 1mol/l is cooled to subzero 5 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs, and the mol ratio of Al and hexamethylenetetramine is 1: 1 in the colloidal sol.
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the speed of pouring out is 20ml/min, the running roller linear resonance surface velocity is at 20m/s, the droplet that throws away from running roller is through 90 ℃ of forming oil column 120min, isolate the bead of moulding, again through 130 ℃ of aging 5h, washing back dry 10h under 80 ℃, at 400 ℃ of roasting 6h, obtaining diameter is the spherical magnetic carrier of 40 μ m then.
This invention can conveniently prepare the spherical magnetic alumina carrier of 40 μ m, spherical form is good, magnetic is evenly distributed, specific area is big, the intensity height, low cost, pollution-free, can produce in batches, carrier is applicable to magnetic stablizing bed technology or catalytic separation process, also is applicable to courses of reaction such as hydrofinishing in the petrochemical industry and selective hydrogenation.
Embodiment 2:
1) with average particle size particle size is α-Fe of 1 μ m
2O
3Magnetic nuclear adds in the aluminium colloidal sol, and mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to subzero 5 ℃, and magnetic nuclear is 1: 2 with the mass ratio of aluminium colloidal sol, and the aluminium element mass content is 7% in the aluminium colloidal sol.
2) the hexamethylenetetramine solution of configuration 0.5mol/l is cooled to subzero 5 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs, and the mol ratio of Al and hexamethylenetetramine is 2.5: 1 in the colloidal sol.
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the speed of pouring out is 40ml/min, the running roller linear resonance surface velocity is at 35m/s, the droplet that throws away from running roller is through 90 ℃ of forming oil column 120min, isolate the bead of moulding, again through 140 ℃ of aging 5h, washing back dry 10h under 80 ℃, at 400 ℃ of roasting 6h, obtaining diameter is the spherical magnetic carrier of 20 μ m then.
This invention can conveniently prepare the spherical magnetic alumina carrier of 20 μ m, spherical form is good, magnetic is evenly distributed, specific area is big, the intensity height, low cost, pollution-free, can produce in batches, carrier is applicable to magnetic stablizing bed technology or catalytic separation process, also is applicable to courses of reaction such as hydrofinishing in the petrochemical industry and selective hydrogenation.
Embodiment 3:
1) with average particle size particle size is γ-Fe of 2 μ m
2O
3Magnetic nuclear adds in the aluminium colloidal sol, and mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to 3 ℃, and magnetic nuclear is 1: 4 with the mass ratio of aluminium colloidal sol, and the aluminium element mass content is 15% in the aluminium colloidal sol.
2) urea liquid of configuration 1mol/l is cooled to 3 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs, and the mol ratio of Al and urea is 5: 1 in the colloidal sol.
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the speed of pouring out is 10ml/min, the running roller linear resonance surface velocity is at 15m/s, the droplet that throws away from running roller is through 95 ℃ of forming oil column 100min, isolate the bead of moulding, again through 140 ℃ of aging 5h, washing back dry 10h under 80 ℃, at 500 ℃ of roasting 6h, obtaining diameter is the spherical magnetic carrier of 200 μ m then.
This invention can conveniently prepare the spherical magnetic alumina carrier of 200 μ m, spherical form is good, magnetic is evenly distributed, specific area is big, the intensity height, low cost, pollution-free, can produce in batches, carrier is applicable to magnetic stablizing bed technology or catalytic separation process, also is applicable to courses of reaction such as hydrofinishing in the petrochemical industry and selective hydrogenation.
Embodiment 4:
1) be that mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to 3 ℃ in the barium ferrite magnetic nuclear adding aluminium colloidal sol of 5 μ m with average particle size particle size, magnetic nuclear is 1: 8 with the mass ratio of aluminium colloidal sol, and the aluminium element mass content is 10% in the aluminium colloidal sol.
2) urea liquid of configuration 1mol/l is cooled to 3 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs, and the mol ratio of Al and urea is 2: 1 in the colloidal sol.
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the speed of pouring out is 80ml/min, the running roller linear resonance surface velocity is at 10m/s, the droplet that throws away from running roller is through 95 ℃ of forming oil column 100min, isolate the bead of moulding, again through 140 ℃ of aging 5h, washing back dry 10h under 80 ℃, at 350 ℃ of roasting 6h, obtaining diameter is the spherical magnetic carrier of 300 μ m then.
This invention can conveniently prepare the spherical magnetic alumina carrier of 300 μ m, and spherical form is good, magnetic is evenly distributed, and specific area is big, the intensity height, and low cost, pollution-free, can produce in batches.
Embodiment 5:
1) with average particle size particle size is α-Fe of 0.1 μ m
2O
3Magnetic nuclear adds in the aluminium colloidal sol, and mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to subzero 5 ℃, and magnetic nuclear is 1: 5 with the mass ratio of aluminium colloidal sol, and the aluminium element mass content is 7% in the aluminium colloidal sol.
2) the hexamethylenetetramine solution of configuration 1mol/l is cooled to subzero 5 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs, and the mol ratio of Al and hexamethylenetetramine is 2: 1 in the colloidal sol.
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the speed of pouring out is 15ml/min, the running roller linear resonance surface velocity is at 40m/s, the droplet that throws away from running roller is through 90 ℃ of forming oil column 120min, isolate the bead of moulding, again through 130 ℃ of aging 5h, washing back dry 10h under 80 ℃, at 500 ℃ of roasting 4h, obtaining diameter is the spherical magnetic carrier of 10 μ m then.
This invention can conveniently prepare the spherical magnetic alumina carrier of 10 μ m, and spherical form is good, magnetic is evenly distributed, and specific area is big, the intensity height, and low cost, pollution-free, can produce in batches.
Claims (7)
1. a running roller gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that its step is:
1) be that mechanical agitation is dispersed in magnetic nuclear in the aluminium colloidal sol, and places refrigerator to be cooled to subzero 10 to 10 ℃ in the magnetic nuclear adding aluminium colloidal sol of 0.05-100 μ m with average particle size particle size;
2) the organic amine solution of configuration 0.1-5mol/l is cooled to subzero 10 to 10 ℃, dropwise joins then in the aluminium colloidal sol that contains magnetic nuclear, evenly stirs;
3) with step 2) colloidal sol that obtains pours out the running roller surface that flows to rotation, the running roller linear resonance surface velocity is at 0.1-50m/s, the droplet that throws away from running roller passes through 50-120 ℃ of forming oil column 1-120min, isolate the bead of moulding, again through 100-200 ℃ of aging 2-20h, washing back dry 2-20h under 20-200 ℃, then at 300-800 ℃ of roasting 1-12h, obtaining diameter is the spherical magnetic carrier of 0.1-500 μ m.
2. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that said magnetic nuclear is barium ferrite, γ-Fe
2O
3, α-Fe
2O
3, Fe
3O
4, in one or more.
3. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that the said magnetic nuclear and the mass ratio of aluminium colloidal sol are 1-50: 100.
4. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that the aluminium element mass content is 1-30% in the said aluminium colloidal sol.
5. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that said organic amine is urea and/or hexamethylenetetramine.
6. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that said step 2) mol ratio of Al and organic amine is 1-10 in the colloidal sol that obtains: 1.
7. running roller according to claim 1 gets rid of ball and prepares spherical magnetic alumina carrier method, it is characterized in that it is 1-100ml/min that said colloidal sol is poured out speed.
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|---|---|---|---|
| CN2010105139243A CN102000574B (en) | 2010-10-12 | 2010-10-12 | Roller flyball method for preparing spherical magnetic alumina carrier |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357392A (en) * | 2012-04-11 | 2013-10-23 | 北京三聚环保新材料股份有限公司 | Method for preparing spheroidal high-sulfur-capacity magnetic iron oxide desulfurizing agent and product thereof |
| CN104667823A (en) * | 2015-01-30 | 2015-06-03 | 北方华锦化学工业集团有限公司 | Special high-viscosity slurry granulating sprayer for production of compound fertilizer |
| CN107233881A (en) * | 2017-05-16 | 2017-10-10 | 北京化工大学 | Microspheroidal silica/alumina base noble metal catalyst and preparation method thereof |
| CN117550629A (en) * | 2023-11-24 | 2024-02-13 | 源求新材料(南通)有限公司 | Preparation method of hollow spherical alumina carrier with controllable particle size |
| CN117550629B (en) * | 2023-11-24 | 2024-05-17 | 源求新材料(南通)有限公司 | Preparation method of hollow spherical alumina carrier with controllable particle size |
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| CN1583270A (en) * | 2004-06-14 | 2005-02-23 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
| CN1785525A (en) * | 2005-11-17 | 2006-06-14 | 南京航空航天大学 | Synthesis technology of magnet carried photocatalyst composite particle, sewage purification method and device |
| WO2007136757A2 (en) * | 2006-05-19 | 2007-11-29 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
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2010
- 2010-10-12 CN CN2010105139243A patent/CN102000574B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583270A (en) * | 2004-06-14 | 2005-02-23 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
| CN1785525A (en) * | 2005-11-17 | 2006-06-14 | 南京航空航天大学 | Synthesis technology of magnet carried photocatalyst composite particle, sewage purification method and device |
| WO2007136757A2 (en) * | 2006-05-19 | 2007-11-29 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357392A (en) * | 2012-04-11 | 2013-10-23 | 北京三聚环保新材料股份有限公司 | Method for preparing spheroidal high-sulfur-capacity magnetic iron oxide desulfurizing agent and product thereof |
| CN103357392B (en) * | 2012-04-11 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | A kind ofly prepare method of spheroidal high-sulfur-capacitymagnetic magnetic iron oxide desulfurizing agent and products thereof |
| CN104667823A (en) * | 2015-01-30 | 2015-06-03 | 北方华锦化学工业集团有限公司 | Special high-viscosity slurry granulating sprayer for production of compound fertilizer |
| CN107233881A (en) * | 2017-05-16 | 2017-10-10 | 北京化工大学 | Microspheroidal silica/alumina base noble metal catalyst and preparation method thereof |
| CN107233881B (en) * | 2017-05-16 | 2019-10-18 | 北京化工大学 | Microspheroidal silica/alumina base noble metal catalyst and preparation method thereof |
| CN117550629A (en) * | 2023-11-24 | 2024-02-13 | 源求新材料(南通)有限公司 | Preparation method of hollow spherical alumina carrier with controllable particle size |
| CN117550629B (en) * | 2023-11-24 | 2024-05-17 | 源求新材料(南通)有限公司 | Preparation method of hollow spherical alumina carrier with controllable particle size |
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