CN111468048A - Preparation method of high-strength gamma-alumina microspheres - Google Patents
Preparation method of high-strength gamma-alumina microspheres Download PDFInfo
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- CN111468048A CN111468048A CN202010283738.9A CN202010283738A CN111468048A CN 111468048 A CN111468048 A CN 111468048A CN 202010283738 A CN202010283738 A CN 202010283738A CN 111468048 A CN111468048 A CN 111468048A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000004005 microsphere Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 79
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000007921 spray Substances 0.000 claims abstract description 49
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 22
- 238000006073 displacement reaction Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000008387 emulsifying waxe Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- FVFJGQJXAWCHIE-UHFFFAOYSA-N [4-(bromomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CBr)C=C1 FVFJGQJXAWCHIE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000001935 peptisation Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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Abstract
The invention discloses a preparation method of high-strength gamma-alumina microspheres, which comprises the following steps: (1) adding the low-sodium and high-viscosity pseudo-boehmite filter cake or dry powder into deionized water, and uniformly mixing to prepare pseudo-boehmite slurry; (2) grinding the prepared pseudo-boehmite slurry; (3) adding an additive into the obtained milled slurry, uniformly stirring, and then adding a nitric acid solution for peptization; then keeping the temperature of the peptized slurry at a constant temperature for spray drying; (4) conveying the gelatinized pseudoboehmite slurry to a spray dryer to obtain a molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained through the processes of cyclone separation and classification; (5) the high-strength gamma-alumina microsphere can be prepared by roasting the pseudo-boehmite microsphere. The prepared gamma-alumina microsphere has low impurity content, good wear resistance, concentrated particle size distribution, high specific surface area and adjustable pore volume, and is a catalyst carrier with excellent performance.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic porous functional materials, and particularly relates to a preparation method of high-strength gamma-alumina microspheres.
Background
Alumina is a very important inorganic porous materialThe material has the characteristics of proper pore structure, proper specific surface, high strength, good thermal stability and the like, and is widely used as an adsorbent and a catalyst carrier. The gamma-alumina is one of a plurality of alumina crystal forms, the shape, the size and the like of the gamma-alumina have great influence on the performance of the gamma-alumina, the spherical gamma-alumina has the characteristics of good mass transfer, uniform distribution, corrosion resistance, high hardness, high strength, high thermal stability, oxidation resistance, large surface area and the like, and the gamma-alumina carrier is low in production cost and easy to obtain, is a catalyst carrier which is most widely used and accounts for about 70 percent of industrial supported catalysts. Thus, gamma-Al2O3Widely used as catalyst carrier, catalyst, adsorbent, etc. and is one new kind of material with wide development foreground. When the gamma-alumina microspheres are used as a catalyst carrier, noble metals need to be loaded, and the wear of the catalyst can cause the loss of noble metal active components on the surface or generate small particles to block a reactor and the like, so that the catalyst carrier is required to have higher wear resistance. The preparation of the gamma-alumina microsphere with high strength and good wear resistance is one of the key performances which must be possessed by the catalyst carrier.
Aiming at the requirement of good wear resistance of a gamma-alumina microsphere as a catalyst carrier or an adsorbent, the invention provides a preparation method of the high-strength gamma-alumina microsphere so as to meet the requirement of the gamma-alumina microsphere carrier in the production of the catalyst and the adsorbent.
Disclosure of Invention
The invention provides a preparation method of high-strength gamma-alumina microspheres aiming at the requirements of gamma-alumina microspheres for producing catalysts, adsorbents and the like.
In order to solve the problems, the invention adopts the technical scheme that:
a preparation method of high-strength gamma-alumina microspheres comprises the following steps:
(1) adding the low-sodium high-viscosity pseudo-boehmite filter cake or dry powder into deionized water to prepare Al2O3Pseudo-boehmite slurry for producing high-strength gamma-alumina microspheres with the mass concentration of 10-35 percent;
(2) preparing in step (1)Al of (2)2O3Grinding the pseudoboehmite slurry with the concentration of 10-35% by adopting grinding equipment, and controlling the granularity D90 of the ground slurry to be 2-40 mu m;
(3) adding an additive into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a nitric acid solution with the mass concentration of 20-98.5% according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to a certain temperature, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a volumetric pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) and (4) roasting the pseudo-boehmite microspheres obtained in the step (4) at a certain temperature for a certain time to prepare the high-strength gamma-alumina microspheres.
Preferably, the low-sodium and high-viscosity pseudo-boehmite filter cake in the step (1) contains Al2O328-34% of Na2The content of O is 0.01 to 0.1 percent, and Al in the low-sodium high-viscosity pseudo-boehmite dry powder2O360-75% of Na2The content of O is 0.01 to 0.1 percent.
Preferably, the milling equipment in step (2) is a colloid mill, an emulsion pump or a ball mill.
Preferably, the additive in step (3) is one or more of ammonium polymethacrylate, polyethylene glycol, ammonium oleate and emulsifying wax; the additive and Al in the milled slurry2O3The mass ratio of (A) to (B) is 0.001 to 0.01.
Preferably, the nitric acid in step (3) and Al in the milled slurry2O3The mass ratio of (A) to (B) is 0.005 to 0.08.
Preferably, the temperature of the sprayed slurry in the step (3) is controlled to be 70-98 ℃.
Preferably, the positive displacement pump in the step (4) is a screw pump or a hose pump, the pressure of the positive displacement pump is controlled to be 0.2-1.5 MPa, and the motor frequency of the positive displacement pump is controlled to be 10-30 Hz.
Preferably, the rotating speed of the atomizer in the step (4) is controlled to be 200-6000 rpm, the hot air temperature at the inlet of the spray tower is controlled to be 350-550 ℃, and the tail gas temperature at the outlet of the spray tower is controlled to be 100-150 ℃.
Preferably, in the step (5), the roasting temperature is 500-750 ℃, and the roasting time is 3-20 hours.
In addition, the invention also claims the high-strength gamma-alumina microspheres prepared by the method.
Compared with the prior art, the invention has the following obvious beneficial effects:
the invention adopts the low-sodium high-viscosity pseudo-boehmite filter cake or dry powder as the raw material, creatively replaces the common low-sodium pseudo-boehmite filter cake as the raw material, reduces the slurrying time of the raw material and can reduce the raw material cost. The material is ground before gelling to promote the peptization effect of the pseudo-boehmite, and the additive is added into the slurry to increase the strength of the product and improve the physical and chemical properties of the product; the gamma-alumina microspheres with low impurity content, high strength, high thermal stability, large oxidation resistance and surface area and good wear resistance are successfully prepared. And by adopting the method, the yield of the single-kettle pseudo-boehmite can be greatly improved, so that the production cost is greatly reduced. The pseudo-boehmite slurry for producing the high-strength gamma-alumina microspheres is directly prepared by adopting the pseudo-boehmite filter cake, and the drying procedure in the pseudo-boehmite production is omitted, and the slurrying time in the slurrying process is shortened, so that the production cost of each ton of gamma-alumina microsphere products is saved by at least 1000 yuan.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
A preparation method of high-strength gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O329.3% of Na2Adding the low-sodium high-viscosity pseudo-boehmite filter cake with the O content of 0.028% and the viscosity of 25 ten thousand mpa.s into deionized water to prepare Al2O3The high-strength gamma-alumina microsphere production pseudo-boehmite slurry with the mass concentration of 15 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the 15% pseudo-boehmite slurry by a colloid mill, and controlling the granularity D90 of the ground slurry to be 10 mu m;
(3) adding a compounding agent additive of polyethylene glycol and emulsifying wax into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a 65% nitric acid solution according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 90 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 680 ℃ for 12h to obtain high-strength gamma-alumina microspheres;
wherein, the additive in the step (3) and Al in the milled slurry2O3Is 0.005;
the nitric acid in the step (3) and Al in the grinded slurry2O3The mass ratio of (A) to (B) is 0.05;
in the step (4), the displacement pump is a hose pump, the pressure of the hose pump is controlled to be 0.5MPa, and the motor frequency of the hose pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 800 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 490 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 120 ℃.
The product prepared in example 1 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.6 | 0.006 | 0.028 | 2.0 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalline phase (%) |
| Results | 136 | 0.83 | 1.0 | 97 |
Wherein, the alumina is determined by a chemical method, the ferric oxide is determined by a spectrophotometer, the ferric oxide is determined by a flame photometer, the crystalline phase is determined by XRD, the specific surface is determined by a BET method, the bulk ratio is determined by a weighing method, and the abrasion index is determined by an intensity meter.
Example 2
A preparation method of high-strength gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O3The content of Na is 32.5%2Adding the low-sodium high-viscosity pseudo-boehmite filter cake with the O content of 0.022% and the viscosity of 26 ten thousand mpa.s into deionized water to prepare Al2O3Pseudo-boehmite slurry for producing high-strength gamma-alumina microspheres with the mass concentration of 25 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the pseudoboehmite slurry with the concentration of 25% by adopting a ball mill, and controlling the granularity D90 of the ground slurry to be 40 mu m;
(3) adding a compounding agent additive of polyethylene glycol and emulsifying wax into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a nitric acid solution with the concentration of 98% according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 95 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 600 ℃ for 18h to obtain high-strength gamma-alumina microspheres;
wherein, the additive in the step (3) and Al in the milled slurry2O3The mass ratio of (A) to (B) is 0.002;
the nitric acid in the step (3) and Al in the grinded slurry2O3The mass ratio of (A) to (B) is 0.03;
in the step (4), the displacement pump is a screw pump, the pressure of the screw pump is controlled to be 0.5MPa, and the motor frequency of the screw pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 3000 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 510 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 120 ℃.
The product prepared in example 2 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.5 | 0.008 | 0.022 | 2.3 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalline phase (%) |
| Results | 132 | 0.87 | 0.8 | 97.3 |
Example 3
A preparation method of high-strength gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O3The content of Na was 69.2%2Adding the low-sodium high-viscosity pseudoboehmite dry powder with the viscosity of 24 ten thousand mpa.s and the O content of 0.030 percent into deionized water to prepare Al2O3The high-strength gamma-alumina microsphere production pseudo-boehmite slurry with the mass concentration of 15 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the 15% pseudo-boehmite slurry by a ball mill, and controlling the granularity D90 of the ground slurry to be 20 mu m;
(3) adding a compounding agent additive of polyethylene glycol and emulsifying wax into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a nitric acid solution with the concentration of 98% according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 93 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 700 ℃ for 6 hours to obtain high-strength gamma-alumina microspheres;
wherein, the additive in the step (3) and Al in the milled slurry2O3Is 0.006;
the nitric acid and the ground slurry in the step (3)Middle Al2O3The mass ratio of (A) to (B) is 0.04;
in the step (4), the displacement pump is a screw pump, the pressure of the screw pump is controlled to be 0.5MPa, and the motor frequency of the screw pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 1000 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 480 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 110 ℃.
The product prepared in example 3 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.6 | 0.008 | 0.030 | 2.8 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalline phase (%) |
| Results | 127 | 0.86 | 1.3 | 97.8 |
Example 4
A preparation method of high-strength gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O3The content of Na is 70.9%2Adding the low-sodium high-viscosity pseudoboehmite dry powder with the O content of 0.026% and the viscosity of 25 ten thousand mpa.s into deionized water to prepare Al2O3Pseudo-boehmite slurry for producing high-strength gamma-alumina microspheres with the mass concentration of 20 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the 20% pseudo-boehmite slurry by a ball mill, and controlling the granularity D90 of the ground slurry to be 30 mu m;
(3) adding a compounding agent additive of polyethylene glycol and emulsifying wax into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a 65% nitric acid solution according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 93 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 680 ℃ for 10 hours to obtain high-strength gamma-alumina microspheres;
wherein, the additive in the step (3) and Al in the milled slurry2O3The mass ratio of (A) to (B) is 0.004;
the nitric acid in the step (3) and Al in the grinded slurry2O3The mass ratio of (A) to (B) is 0.05;
in the step (4), the displacement pump is a screw pump, the pressure of the screw pump is controlled to be 0.5MPa, and the motor frequency of the screw pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 4000 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 500 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 120 ℃.
The product prepared in example 4 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.6 | 0.006 | 0.06 | 2.6 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalPhoto (%) |
| Results | 135 | 0.83 | 1.1 | 97.1 |
Comparative example 1
A preparation method of gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O3The content of Na was 67.5%2Adding low-sodium pseudo-boehmite dry powder with O content of 0.056% and viscosity of 10 ten thousand mpa.s into deionized water to prepare Al2O3The high-strength gamma-alumina microsphere production pseudo-boehmite slurry with the mass concentration of 15 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the 15% pseudo-boehmite slurry by a ball mill, and controlling the granularity D90 of the ground slurry to be 10 mu m;
(3) adding a 65% nitric acid solution into the milled slurry obtained in the step (2) according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 90 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 680 ℃ for 12h to obtain high-strength gamma-alumina microspheres;
wherein, the nitric acid in the step (3) and Al in the grinded slurry2O3The mass ratio of (A) to (B) is 0.05;
in the step (4), the displacement pump is a screw pump, the pressure of the screw pump is controlled to be 0.5MPa, and the motor frequency of the screw pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 800 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 490 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 120 ℃.
The product prepared in comparative example 1 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.7 | 0.007 | 0.058 | 2.0 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalline phase (%) |
| Results | 130 | 0.79 | 4.1 | 96.5 |
Comparative example 2
A preparation method of gamma-alumina microspheres comprises the following steps:
(1) mixing Al2O3The content of Na is 70.8%2Adding low-sodium pseudo-boehmite dry powder with O content of 0.036% and viscosity of 10 ten thousand mpa.s into deionized water to prepare Al2O3Pseudo-boehmite slurry for producing high-strength gamma-alumina microspheres with the mass concentration of 25 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the pseudoboehmite slurry with the concentration of 25% by adopting a ball mill, and controlling the granularity D90 of the ground slurry to be 40 mu m;
(3) adding a nitric acid solution with the concentration of 98% into the milled slurry obtained in the step (2) according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to 90 ℃, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a hose pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) roasting the pseudo-boehmite microspheres obtained in the step (4) at 680 ℃ for 12h to obtain high-strength gamma-alumina microspheres;
wherein, the nitric acid in the step (3) and Al in the grinded slurry2O3The mass ratio of (A) to (B) is 0.05;
in the step (4), the displacement pump is a screw pump, the pressure of the screw pump is controlled to be 0.5MPa, and the motor frequency of the screw pump is controlled to be 20 Hz;
in the step (4), the rotating speed of the atomizer is controlled to be 800 revolutions per minute, the temperature of hot air at the inlet of the spray tower is controlled to be 490 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 120 ℃.
The product prepared in comparative example 2 was analyzed and the results were as follows:
| analysis item | Al2O3(％) | Fe2O3(％) | Na2O(％) | Causticine (%) |
| Results | 99.6 | 0.007 | 0.036 | 2.0 |
| Analysis item | Specific surface area (m)2/g) | Bulk ratio (g/ml) | Abrasion index (%) | Gamma crystalline phase (%) |
| Results | 128 | 0.81 | 3.9 | 97.2 |
Finally, it is to be noted that: the above embodiments do not limit the invention in any way, and it is obvious to those skilled in the art that modifications and improvements can be made on the basis of the present invention. Accordingly, any modification made without departing from the spirit of the invention is within the scope of the claims.
Claims (10)
1. A preparation method of high-strength gamma-alumina microspheres is characterized by comprising the following steps:
(1) adding the low-sodium high-viscosity pseudo-boehmite filter cake or dry powder into deionized water, and uniformly mixing to prepare Al2O3Pseudo-boehmite slurry for producing high-strength gamma-alumina microspheres with the mass concentration of 10-35 percent;
(2) mixing Al prepared in the step (1)2O3Grinding the pseudoboehmite slurry with the concentration of 10-35% by adopting grinding equipment, and controlling the granularity D90 of the ground slurry to be 2-40 mu m;
(3) adding an additive into the milled slurry obtained in the step (2) according to a certain proportion, uniformly stirring, and then adding a nitric acid solution with the mass concentration of 20-98.5% according to a certain proportion to peptize the pseudo-boehmite slurry; then raising the peptized slurry to a certain temperature, keeping the constant temperature for spray drying;
(4) conveying the gelatinized pseudoboehmite slurry obtained in the step (3) to a spray dryer through a volumetric pump, and controlling the rotating speed of an atomizer of a spray tower, the inlet hot air temperature of the spray tower and the outlet tail gas temperature of the spray tower to obtain the molded and dried pseudoboehmite; then the pseudo-boehmite microspheres are obtained after cyclone separation and grading processes;
(5) and (4) roasting the pseudo-boehmite microspheres obtained in the step (4) at a certain temperature for a certain time to prepare the high-strength gamma-alumina microspheres.
2. The method according to claim 1, wherein the low-sodium and high-viscosity substances are used in step (1)Al in pseudo-boehmite filter cake2O328-34% of Na2The content of O is 0.01 to 0.1 percent, and Al in the low-sodium high-viscosity pseudo-boehmite dry powder2O360-75% of Na2The content of O is 0.01 to 0.1 percent; the low sodium and high viscosity pseudoboehmite has a viscosity of more than 20 ten thousand mpa.s.
3. The method of claim 1, wherein the milling device in step (2) is a colloid mill, an emulsion pump or a ball mill.
4. The method according to claim 1, wherein the additive in step (3) is one or more of ammonium polymethacrylate, polyethylene glycol, ammonium oleate and emulsifying wax; the additive and Al in the milled slurry2O3The mass ratio of (A) to (B) is 0.001 to 0.01.
5. The method of claim 1, wherein the nitric acid of step (3) and Al of the milled slurry2O3The mass ratio of (A) to (B) is 0.005 to 0.08.
6. The method according to claim 1, wherein the temperature of the sprayed slurry in the step (3) is controlled to be 70 to 98 ℃.
7. The preparation method according to claim 1, wherein the positive displacement pump in the step (4) is a screw pump or a hose pump, the pressure of the positive displacement pump is controlled to be 0.2-1.5 MPa, and the motor frequency of the positive displacement pump is controlled to be 10-30 Hz.
8. The preparation method according to claim 1, wherein the rotation speed of the atomizer in the step (4) is controlled to be 200-6000 rpm, the temperature of hot air at the inlet of the spray tower is controlled to be 350-550 ℃, and the temperature of tail gas at the outlet of the spray tower is controlled to be 100-150 ℃.
9. The method according to claim 1, wherein the calcination temperature in the step (5) is 500 to 750 ℃, and the calcination time is 3 to 20 hours.
10. High strength gamma-alumina microspheres produced by the process of any one of claims 1 to 9.
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