CN115872424A - High-strength spherical alumina and preparation method thereof - Google Patents
High-strength spherical alumina and preparation method thereof Download PDFInfo
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- CN115872424A CN115872424A CN202211729809.9A CN202211729809A CN115872424A CN 115872424 A CN115872424 A CN 115872424A CN 202211729809 A CN202211729809 A CN 202211729809A CN 115872424 A CN115872424 A CN 115872424A
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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 194
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000003349 gelling agent Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000001935 peptisation Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000007711 solidification Methods 0.000 claims abstract description 11
- 230000008023 solidification Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 41
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- 239000008188 pellet Substances 0.000 claims description 30
- 238000001723 curing Methods 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- 235000013877 carbamide Nutrition 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010687 lubricating oil Substances 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000010692 aromatic oil Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 3
- QFCVQKSWGFVMTB-UHFFFAOYSA-N trihexoxyalumane Chemical compound [Al+3].CCCCCC[O-].CCCCCC[O-].CCCCCC[O-] QFCVQKSWGFVMTB-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 8
- 229960004011 methenamine Drugs 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a spherical alumina and a preparation method thereof, and the method comprises the steps of adding acid liquor into a dispersion system of pseudo-boehmite, peptization auxiliary agent, alumina powder and water to prepare alumina suspension to form stable slurry sol, then adding gelling agent aqueous solution containing the gelling auxiliary agent into the alumina suspension, uniformly stirring to obtain stable alumina slurry, and then dripping the alumina slurry into an assembled oil ammonia column to perform forming solidification, water washing, drying and calcining to obtain the spherical alumina. According to the invention, different functional auxiliaries are added into the aqueous solution of the gelling agent, and the regulation and control of the components and the composition ratio of the oil-ammonia column are matched, so that the stacking density of the alumina spheres can be effectively reduced, the particle size of the prepared spherical alumina is controllable within the range of 1.5-2.0 mm, the mechanical strength reaches more than 50N, and the spherical alumina can be simultaneously used as an active component of a catalyst and a catalyst carrier.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to high-strength spherical alumina and a preparation method thereof.
Background
The alumina can be used as an active component of the catalyst, and can be used as a carrier of the catalyst due to the stable chemical property and the porous structural characteristic, so that the active component can be effectively and uniformly dispersed, the sintering resistance of the active component is improved, and the performance of the catalyst is improved.
At present, the molding methods of millimeter-grade alumina mainly include an extrusion molding method, a rolling ball molding method, an oil column molding method and an oil ammonia column molding method, wherein the oil column molding method and the oil ammonia column molding method are more commonly applied, and the prepared alumina pellets have more excellent physical properties. Compared with the oil column forming method, the oil ammonia column forming method has the advantages of simple process, short production period and relatively low requirement on equipment. The basic principle of the oil ammonia column forming method is that corresponding sol is dripped into an oil ammonia column configured according to requirements, sol particles firstly pass through an oil phase at an upper layer to complete a primary balling process, then enter a water phase at a lower layer, and a gelling process is started. After being solidified in the oil ammonia column for a certain time, the mixture is taken out from the bottom end and is washed, dried, calcined and the like to obtain the finished product of the alumina pellets. The small balls prepared by the oil ammonia column forming method have the characteristics of uniform integral size, good wear resistance and high strength, and are widely applied to the fields of catalyst carriers, adsorbents and the like.
Patent US4542113A discloses a method for preparing alumina pellets, which comprises adding alumina hydrate as raw material into nitric acid solution dissolved with urea, stirring, dripping into a forming device after stirring for a period of time, and controlling the size of liquid drop during dripping to 4-5 mm. In the cylindrical container, 8wt% concentration ammonia water is 70% and contains 0.1% wetting agent, the rest is diesel oil, and the temperature of the oil ammonia column is 20-25 deg.C. The alumina pellets are collected at the bottom of the oil ammonia column, the drying process is divided into two stages of pre-drying at 60 ℃ and drying at 120 ℃, and then the alumina pellets are calcined at 550 ℃ to obtain finished product alumina pellets, wherein the diameter of the pellets is between 2 and 3 mm. The process adopts normal-temperature oil ammonia column molding, the ammonia water ratio is far higher than that of an organic phase, part of produced finished pellets have cracks, the loss of the pellets can be caused in the calcining process, in addition, the existence of the cracks also reduces the strength of the material, and the synthesized alumina slurry has the phenomenon of too fast solidification, so that the residual sizing material can not be fully utilized.
USP4542113 discloses a method for preparing alumina pellets by using solid aluminum hydroxide powder as raw material, which comprises selecting two solid aluminum hydroxide powders with different crystal grain sizes according to requirements, adding water, stirring, and adding dilute nitric acid into the systemA solution and urea, wherein the urea functions to maintain the entire dispersion stable. And then dripping the slurry into an oil ammonia column, and obtaining the finished product of the alumina pellets through subsequent washing, drying and calcining. The alumina pellets prepared by the method have the crushing strength of 150N and the bulk density of 0.66g/cm 3 . The method also introduces that in order to further reduce the bulk density of the alumina pellets, a certain amount of kerosene can be added as a pore-expanding agent. Although the bulk density of the alumina pellets after the pore-expanding agent is added can meet the requirements of the continuous reforming catalyst, the production cost is increased, for example, the consumption of kerosene is large, additional processes are required to be supplemented to recover the kerosene subsequently, the production period is increased, and meanwhile, certain risks also exist during subsequent drying and calcining.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing high-strength spherical alumina, which at least partially solves the problems in the prior art by adding different functional additives and controlling the oil-ammonia column forming process in the alumina slurry preparation process.
The first aspect of the invention provides a preparation method of spherical alumina, which comprises the following steps:
mixing pseudo-boehmite, peptization auxiliary agent, alumina powder and water to prepare mixed slurry, wherein the mass ratio of the pseudo-boehmite to the alumina powder is 1:5 to 5:1;
stirring the mixed slurry, heating, adding acid liquor, and stirring to obtain an alumina suspension;
adding a gelling agent aqueous solution containing a gelling aid into the alumina suspension, and uniformly stirring to obtain alumina slurry;
and dripping the alumina slurry into an oil ammonia column for forming and curing, and then washing, drying and calcining the obtained alumina pellets to obtain the spherical alumina.
Preferably, the solid content of the mixed slurry is 10 to 35wt% based on alumina.
The pseudoboehmite is prepared by hydrolyzing alkyl aluminum salt, and the alkyl aluminum salt is one or more of aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum n-hexoxide and aluminum n-pentoxide.
Preferably, the peptization auxiliary agent is one or more of PMMA, PVB, PEG, CMC, PVP, PVA and CTAB; the addition amount of the peptization auxiliary agent is 1-20 wt% of the content of the alumina in the mixed slurry.
Preferably, the acid solution is one or more of nitric acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, acetic acid, citric acid and tartaric acid; the hydrogen-aluminum ratio in the alumina suspension is controlled to be 0.03-0.1.
Preferably, the gelling agent is one or more of hexamethylenetetramine, urea, ethylenediamine, dilute ammonia water, ammonium carbonate and ammonium bicarbonate; the addition amount of the gelling agent is 10-60 wt% of the content of the alumina in the alumina suspension.
Preferably, the gelling auxiliary agent is one or more of ethanol, isopropanol, n-butanol, n-pentanol, n-hexanol, ethylene glycol, urea, polyvinylpyrrolidone and carboxymethyl cellulose; the addition amount of the gelling auxiliary agent is 5-15 wt% of the content of the alumina in the alumina suspension.
Preferably, in the oil ammonia column forming and curing, the oil ammonia column comprises an oil phase and a water phase, the height ratio of the oil phase to the water phase is 10-150, the height of the oil phase is 2-50 cm, the height of the water phase is 20-200 cm, and the temperature of the oil ammonia column is 50-90 ℃.
Preferably, the oil phase is one or a mixture of more of silicone oil, aromatic oil, diesel oil, terphenyl and lubricating oil; the oil density in the oil phase is 0.5-1.0 g/cm 3 The kinematic viscosity of the oil body is 30-300 cst; the water phase is prepared by compounding an ammonia water solution and a surfactant, wherein the mass fraction of the ammonia water solution is 5-25 wt%, and the mass fraction of the surfactant is 0.5-10.0 wt%.
Preferably, the balling and pre-curing time of the alumina slurry in the oil ammonia column is 2-24 h; the aluminum oxide pellets are washed by water and then solidified in an ammonia water solution, wherein the mass fraction of the ammonia water solution is 5-35 wt%, the solidification pressure is 0.2-3.0 MPa, the solidification temperature is 50-200 ℃, and the solidification time is 2-24 h.
Preferably, the drying temperature is 60-150 ℃, the drying time is 1-48 h, the drying pressure is 0.2-3.0 MPa, and the humidity is 50-80 Rh%; the calcining temperature of the calcining is 550-1200 ℃, and the calcining time is 1-12 h.
The second aspect of the invention also provides spherical alumina which is prepared by adopting the preparation method of the spherical alumina.
According to the preparation method of the spherical alumina, different functional additives are added into the aqueous solution of the gelling agent, and the regulation and control of the components and the composition ratio of the oil ammonia column are matched, so that the bulk density of the spherical alumina can be effectively reduced. In addition, the mechanical strength of the calcined alumina pellets is enhanced to be more than 50N, and the calcined alumina pellets have good abrasion resistance. The prepared spherical alumina has the grain diameter controllable within the range of 1.5-2.0 mm, has good physical and chemical properties, can be used as an active component and a catalyst carrier of a catalyst at the same time, is widely applied to the fields of petrochemical industry or fine chemical industry, and has good market prospect.
Detailed Description
It should be noted that, in the case of no conflict, the features in the following embodiments and examples may be combined with each other; moreover, all other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein without making any creative effort fall within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. In addition, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to or other than one or more of the aspects set forth herein.
The invention provides a preparation method of spherical alumina, which comprises the following steps:
mixing pseudo-boehmite, peptization auxiliary agent, alumina powder and water to prepare mixed slurry;
stirring the mixed slurry, heating, adding acid liquor, and stirring to obtain an alumina suspension;
adding a gelling agent aqueous solution containing a gelling auxiliary agent into the alumina suspension, and uniformly stirring to obtain alumina slurry
And (3) dripping the alumina slurry into an oil ammonia column for forming and curing, and then washing, drying and calcining the obtained alumina pellets to obtain the spherical alumina.
In the forming process, the peptized pseudo-boehmite is not only a component main body of the alumina ball, but also plays a role of a binder and controls the polycondensation and the final size of the alumina ball; the alumina powder has the characteristics of high specific surface, mesoporous morphology, no peptization and the like, is a supporting framework in the drying and roasting process of the alumina ball, and also plays a role in seed crystal and compound solid content; the selected peptization auxiliary agent firstly has good water solubility, hot solubility, colloid chromatography coagulation resistance, colloid thixotropic property improvement and the like, and secondly, the physical morphology of the alumina ball can be finely adjusted through the addition amount of the peptization auxiliary agent.
In the preparation method provided by the invention, the pseudoboehmite is prepared by hydrolyzing an alkyl aluminum salt, and the alkyl aluminum salt is one or more of aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum n-hexoxide and aluminum n-pentoxide. Preferably, the alkyl aluminum salt is aluminum isopropoxide.
In the preparation method provided by the invention, the solid content of the slurry obtained by compounding the pseudoboehmite and the alumina powder is 10-35 wt% in terms of alumina, and the mass ratio of the pseudoboehmite to the alumina powder is 1:5 to 5:1. the solid content of alumina in the alumina suspension is controlled to be 10-35 wt%, so that the problems that alumina balls prepared from too low solid content of alumina are low in strength and deform or break in the drying and calcining processes and alumina slurry is poor in flowability and difficult to form due to too high solid content of alumina can be solved.
In the preparation method provided by the invention, the peptization auxiliary agent is one or more of PMMA, PVB, PEG, CMC, PVP, PVA and CTAB, and the addition amount of the peptization auxiliary agent is 1-20 wt% of the content of alumina in the mixed slurry; one or more of PVP, CMC, PVA and PEG is preferred, and the addition amount is preferably 5-15 wt% of the alumina content in the mixed slurry.
Preferably, the solid content of the alumina suspension is 12-18 wt% calculated by alumina, and the mass ratio of the pseudoboehmite to the alumina powder is 1: 2-2: 1.
in the preparation method provided by the invention, the acid solution is one or more of nitric acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, acetic acid, citric acid and tartaric acid. Preferably, the acid solution is one or more of nitric acid and hydrochloric acid. Adding acid liquor into the alumina suspension and continuously stirring, and reacting the pseudo-boehmite with the acid to obtain smaller colloidal particles, thereby finally obtaining the alumina sol.
The adding amount of the acid solution is controlled by the ratio of the hydrogen in the acid solution to the molar weight of the aluminum in the alumina suspension, so as to obtain the aluminum sol with certain fluidity. In the technical scheme of the invention, the molar weight ratio of the hydrogen to the aluminum is between 0.045 and 0.10, preferably between 0.050 and 0.070.
In the preparation method provided by the invention, the gelling agent is one or more of hexamethylenetetramine, urea, ethylenediamine, dilute ammonia water, ammonium carbonate and ammonium bicarbonate, and the addition amount of the gelling agent is 10-60 wt%, preferably 25-50 wt% of the content of alumina in the alumina suspension.
In the preparation method provided by the invention, the amount of the gelling agent is 30-70 wt%, preferably 40-55 wt% of the mass of the pseudo-boehmite.
In the preparation method provided by the invention, the mass of water in the aqueous solution of the gelling agent is 2-5 times of the mass of the gelling agent, and preferably the mass of water is 3-4 times of the mass of the gelling agent.
In the preparation method provided by the invention, one or more of the gelling auxiliaries ethanol, isopropanol, n-butanol, n-pentanol, n-hexanol, glycol, urea, polyvinylpyrrolidone and carboxymethyl cellulose are added, wherein the addition amount of the gelling auxiliaries is 5-15 wt% of the content of alumina in the alumina suspension; preferably ethanol, urea, carboxymethyl cellulose or isopropanol, preferably in an amount of 6 to 12wt% of the alumina content of the alumina suspension. The selected gelling assistant can promote dispersed colloidal particles to be in a free state, reduce the kinematic viscosity of a system and keep the stability of colloidal dispersion.
In the preparation method provided by the invention, in the oil ammonia column forming and curing, the oil ammonia column comprises an oil phase and a water phase, the height ratio of the oil phase to the water phase is 10-150, the height of the oil phase is 2-50 cm, and the height of the water phase is 20-200 cm; the temperature of the oil ammonia column is 50-90 ℃. After the alumina slurry is dropped into the oil ammonia column, it is quickly contracted into spherical shape in the oil phase, and then it reacts in the ammonia water solution to form gel spheres, and further solidified.
Preferably, the oil phase is one or a mixture of more of silicone oil, aromatic oil, diesel oil, terphenyl and lubricating oil; the oil density in the oil phase is 0.5-1.0 g/cm 3 The kinematic viscosity of the oil body is 30-300 cst. Specifically, the lubricating oil is lubricating oil with different distillation ranges.
Preferably, the water phase is prepared by compounding an ammonia water solution and a surfactant, wherein the mass fraction of the ammonia water solution is 5-25 wt%, and the mass fraction of the surfactant is 0.5-10.0 wt%. The surfactant is anionic, cationic or nonionic surfactant.
In the preparation method provided by the invention, the time for balling and pre-curing the alumina slurry in the oil ammonia column is 2-24 h. In the technical scheme of the invention, the proportion of the oil phase and the water phase can ensure that the alumina has enough time to shrink in the oil phase when being dripped into the oil ammonia column and is fully solidified in the ammonia water solution, thereby preventing deformation when contacting the bottom of the device.
In the preparation method provided by the invention, the alumina pellets are subjected to water washing and then are solidified in an ammonia water solution. In the curing process, the alumina pellets react with ammonia water to fully splice the inner colloidal particles of the alumina pellets and prevent the alumina pellets from deforming or breaking when dried.
In the preparation method provided by the invention, the mass fraction of the ammonia water solution is 5-35 wt%, the curing pressure is 0.2-3.0 MPa, the curing temperature is 50-200 ℃, and the curing time is 2-24 h.
In the preparation method provided by the invention, the drying temperature is 60-150 ℃, the drying time is 1-48 h, the drying pressure is 0.2-3.0 MPa, and the humidity is 50-80 Rh%; the calcining temperature of the calcining is 550-1200 ℃, and the calcining time is 1-12 h.
The alumina slurry prepared by the method has stable quality, uniform slurry distribution and no colloid chromatography phenomenon, can still be used in the preparation process of alumina pellets after being stood for a long time, has moderate overall viscosity, is not adhered and dragged in the dropping ball operation process, and has high slurry utilization rate.
The oil phase used for the oil ammonia column forming of the invention comprises silicone oil, aromatic oil, diesel oil, terphenyl, lubricating oil with different distillation ranges and the like, and the oil phase has the characteristics of unique viscosity, density and the like. After the alumina slurry drops into the oil column, the alumina slurry can pass through the whole oil column within a controlled time and then fall into the water phase to finish solidification, and finally the finished spherical alumina with high mechanical strength is obtained. As a catalyst carrier, the catalyst has simple, controllable and effective preparation process and formula and good industrial prospect.
The preparation method of the spherical alumina can effectively improve the adhesion problem in the alumina gel ball forming process, keep the roundness of the alumina balls not to deform, effectively solve the problem of crack loss of the alumina balls after curing, drying and calcining, and the average mechanical strength of the obtained spherical alumina can reach more than 50N.
Example 1
A preparation method of spherical alumina comprises the following steps:
preparation of alumina suspension: taking pseudo-boehmite powder prepared by hydrolyzing aluminum isopropoxide, peptization auxiliary agent PEG with the mass fraction of 6wt%, deionized water and alumina powder to prepare mixed slurry with the alumina solid content of 15wt%, heating the mixed slurry, uniformly stirring, dropwise adding 0.060M concentrated nitric acid, and stirring to prepare the alumina suspension.
Preparing a gelling agent aqueous solution: preparing HMT (hexamethylene tetramine) solution with the mass fraction of 30wt%, adding 12wt% of gelling auxiliary agent urea, and uniformly stirring to obtain the product.
Preparing alumina slurry: adding the aqueous solution of the gelling agent into the alumina suspension, and uniformly stirring to obtain alumina slurry.
Preparing spherical alumina: dropping the alumina slurry into an oil ammonia column to form a ball, directly taking out the obtained sample from the lower end of an oil ammonia column forming device after pre-curing is completed for 12h, washing with water, and then curing in an ammonia water solution with the mass fraction of 8wt% for 4h, wherein the pressure during curing is 1.2MPa, and the temperature is 120 ℃; drying the cured pellets at 100 ℃ for 24h, and then calcining at 550 ℃ for 3h to obtain the spherical alumina finished product. The oil phase height in the oil ammonia column molding is 20cm, and the temperature of the oil ammonia column is 55 ℃; the water phase height is 90cm, the water-based paint is prepared by compounding an ammonia water solution with the mass fraction of 9wt% and a surfactant, and the mass ratio of the surfactant to the ammonia water solution is 3. The obtained spherical alumina product was subjected to structural analysis, and the structural characteristics are shown in table 1.
Example 2
A preparation method of spherical alumina comprises the following steps:
preparation of alumina suspension: taking pseudo-boehmite powder prepared by hydrolyzing aluminum isopropoxide, 8wt% of peptization assistant CMC, deionized water and alumina powder to prepare mixed slurry with the alumina solid content of 18wt%, heating the mixed slurry, uniformly stirring, dropwise adding 0.055M concentrated nitric acid, and stirring to obtain the alumina suspension.
Preparing a gelling agent aqueous solution: preparing a HMT solution with the mass fraction of 30wt%, adding a gelling auxiliary agent glycol with the mass fraction of 12wt%, and uniformly stirring to obtain the aqueous emulsion.
Preparing alumina slurry: adding the aqueous solution of the gelling agent into the alumina suspension, and uniformly stirring to obtain alumina slurry.
Preparing spherical alumina: dropping the alumina slurry into an oil ammonia column to form balls, directly taking out the obtained sample from the lower end of an oil ammonia column forming device after pre-curing is completed for 10h, washing with water, and curing in an ammonia water solution with the mass fraction of 8wt% for 8h, wherein the pressure during curing is 1.5MPa, and the temperature is 150 ℃. Drying the solidified pellets at 100 ℃ for 24h, and then calcining at 750 ℃ for 3h to obtain the spherical alumina finished product.
The height of an oil phase in the oil ammonia column forming is 30cm, and the temperature of the oil ammonia column is 55 ℃; the water phase height is 100cm, the water-based paint is prepared by compounding 10wt% of ammonia water solution and a surfactant, and the mass ratio of the surfactant to the ammonia water solution is 5. The obtained spherical alumina product was subjected to structural analysis, and the structural characteristics are shown in table 1.
Example 3
A preparation method of spherical alumina comprises the following steps:
preparation of alumina suspension: preparing pseudo-boehmite powder prepared by hydrolyzing aluminum isopropoxide, 8wt% peptization auxiliary agent PVP, deionized water and alumina powder into mixed slurry with the solid content of alumina being 15wt%, heating the mixed slurry, uniformly stirring, dropwise adding 0.060M concentrated nitric acid, and stirring to obtain alumina suspension.
Preparing a gelling agent aqueous solution: preparing a HMT solution with the mass fraction of 30wt%, adding 10wt% of gelling auxiliary agent urea, and uniformly stirring to obtain the product.
Preparing alumina slurry: adding the aqueous solution of the gelling agent into the alumina suspension, and uniformly stirring to obtain alumina slurry.
Preparing spherical alumina: dropping the alumina slurry into an oil ammonia column to form balls, directly taking out the obtained sample from the lower end of an oil ammonia column forming device after pre-curing is completed for 10h, washing with water, and then curing in an ammonia water solution with the mass fraction of 8wt% for 6h, wherein the pressure during curing is 1.2MPa, and the temperature is 150 ℃. Drying the cured pellets at 120 ℃ for 24h, and then calcining at 750 ℃ for 3h to obtain the spherical alumina finished product. The oil phase height in the oil ammonia column molding is 20cm, and the oil ammonia column temperature is 45 ℃; the water phase height is 110cm, the water phase is prepared by compounding 8wt% of ammonia water solution and a surfactant, and the mass ratio of the surfactant to the ammonia water solution is 6. The obtained spherical alumina product was subjected to structural analysis, and the structural characteristics are shown in table 1.
Example 4
A preparation method of spherical alumina comprises the following steps:
preparation of alumina suspension: taking pseudo-boehmite powder prepared by hydrolyzing aluminum isopropoxide, PVA with the mass fraction of 6wt%, deionized water and alumina powder to prepare mixed slurry with the alumina solid content of 15wt%, heating the mixed slurry, uniformly stirring, dropwise adding 0.055M concentrated nitric acid, and stirring to obtain the alumina suspension.
Preparing a gelling agent aqueous solution: preparing a HMT solution with the mass fraction of 30wt%, adding 8wt% of a gelling auxiliary agent ethylenediamine, and uniformly stirring to obtain the product.
Preparing alumina slurry: adding the aqueous solution of the gelling agent into the alumina suspension, and uniformly stirring to obtain alumina slurry.
Preparing spherical alumina: dropping the alumina slurry into an oil ammonia column to form balls, pre-curing for 10h, directly taking out the obtained sample from the lower end of an oil ammonia column forming device, washing with water, and curing for 6h in an ammonia water solution with the mass fraction of 8wt%, wherein the pressure during curing is 1.2MPa, and the temperature is 150 ℃. Drying the solidified pellets at 120 ℃ for 24h, and then calcining at 950 ℃ for 3h to obtain the spherical alumina finished product. The height of an oil phase in the oil ammonia column forming is 30cm, and the temperature of the oil ammonia column is 55 ℃; the water phase height is 120cm, the water-based paint is prepared by compounding 10wt% of ammonia water solution and a surfactant, and the mass ratio of the surfactant to the ammonia water solution is 5. The obtained spherical alumina product was subjected to structural analysis, and the structural characteristics are shown in table 1.
Comparative example 1
The preparation method of the spherical alumina is different from the preparation method of the example 1 in that no peptization auxiliary agent is added in the preparation step of the alumina suspension, and other steps are the same. The structural characteristics of the resulting spherical alumina product are shown in table 1.
Comparative example 2
A method for preparing spherical alumina, which is different from example 2 in that the gelling aid is replaced with an equimolar amount of acetic acid when preparing an aqueous gelling agent solution, and the other steps are the same. The structural characteristics of the obtained spherical alumina are shown in table 1.
Comparative example 3
A preparation method of spherical alumina is different from the embodiment 3 in that in the step of preparing the spherical alumina, a sample is taken out from the lower end of an oil ammonia column device, and is solidified in an ammonia water solution under the conditions of normal temperature and normal pressure after being washed by water, and other steps are the same. The structural characteristics of the obtained spherical alumina are shown in table 1.
Comparative example 4
The preparation method of the spherical alumina is different from the embodiment 4 in that in the step of preparing the spherical alumina, a sample is taken out from the lower end of an oil ammonia column device, and is solidified for 0.5h in an ammonia water solution with the mass fraction of 8wt% after being washed by water, the pressure during solidification is 1.2MPa, the temperature is 150 ℃, and other steps are the same. The structural characteristics of the obtained spherical alumina are shown in table 1.
TABLE 1 physical Properties of the final spherical alumina
| Sample(s) | Specific surface area/m 2 ·g ～1 | Pore volume/cm 3 ·g ～1 | Average pore diameter/nm | Average intensity/N |
| Example 1 | 191 | 0.65 | 10.61 | 75.2 |
| Example 2 | 165 | 0.62 | 12.41 | 73.8 |
| Example 3 | 178 | 0.55 | 11.12 | 80.4 |
| Example 4 | 154 | 0.56 | 13.88 | 84.9 |
| Comparative example 1 | 183 | 0.61 | 12.21 | 41.9 |
| Comparative example 2 | 180 | 0.60 | 11.17 | 47.7 |
| Comparative example 3 | 174 | 0.57 | 13.62 | 38.8 |
| Comparative example 4 | 175 | 0.58 | 12.82 | 32.1 |
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the spherical alumina is characterized by comprising the following steps:
mixing pseudo-boehmite, peptization auxiliary agent, alumina powder and water to prepare mixed slurry, wherein the mass ratio of the pseudo-boehmite to the alumina powder is 1:5 to 5:1;
stirring the mixed slurry, heating, adding acid liquor, and stirring to obtain an alumina suspension;
adding a gelling agent aqueous solution containing a gelling aid into the alumina suspension, and uniformly stirring to obtain alumina slurry;
and (3) dripping the alumina slurry into an oil ammonia column for forming and curing, and then washing, drying and calcining the obtained alumina pellets to obtain the spherical alumina.
2. The method for preparing spherical alumina according to claim 1, wherein the solid content in the mixed slurry is 10 to 35wt% in terms of alumina; the pseudoboehmite is prepared by hydrolyzing alkyl aluminum salt, wherein the alkyl aluminum salt is one or more of aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum n-hexoxide and aluminum n-pentoxide; the peptization auxiliary agent is one or more of PMMA, PVB, PEG, CMC, PVP, PVA and CTAB; the addition amount of the peptization auxiliary agent is 1-20 wt% of the content of the alumina in the mixed slurry.
3. The method for preparing spherical alumina according to claim 1, wherein the acid solution is one or more of nitric acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, acetic acid, citric acid and tartaric acid; the hydrogen-aluminum ratio in the alumina suspension is controlled to be 0.03-0.1.
4. The method for preparing spherical alumina according to claim 1, wherein the gelling agent is one or more of hexamethylenetetramine, urea, ethylenediamine, dilute ammonia, ammonium carbonate and ammonium bicarbonate; the addition amount of the gelling agent is 10-60 wt% of the content of the alumina in the alumina suspension.
5. The method for preparing spherical alumina according to claim 1, wherein the gelling assistant is one or more of ethanol, isopropanol, n-butanol, n-pentanol, n-hexanol, ethylene glycol, urea, polyvinylpyrrolidone and carboxymethylcellulose; the addition amount of the gelling additive is 5-15 wt% of the content of the alumina in the alumina suspension.
6. The method for preparing spherical alumina according to claim 1, wherein in the oil ammonia column forming solidification, the oil ammonia column comprises an oil phase and a water phase, the height ratio of the oil phase to the water phase is 10-150, the height of the oil phase is 2-50 cm, the height of the water phase is 20-200 cm, and the temperature of the oil ammonia column is 50-90 ℃.
7. The method for preparing spherical alumina according to claim 6, wherein the oil phase is a mixture of one or more of silicone oil, aromatic oil, diesel oil, terphenyl and lubricating oil; what is needed isThe oil density in the oil phase is 0.5-1.0 g/cm 3 The kinematic viscosity of the oil body is 30-300 cst; the water phase is prepared by compounding an ammonia water solution and a surfactant, wherein the mass fraction of the ammonia water solution is 5-25 wt%, and the mass fraction of the surfactant is 0.5-10.0 wt%.
8. The method for preparing spherical alumina according to claim 1, wherein in the oil ammonia column molding and curing, the time for the alumina slurry to form spheres in the oil ammonia column is 2 to 24 hours; the aluminum oxide pellets are solidified in an ammonia water solution after being washed by water, wherein the mass fraction of the ammonia water solution is 5-35 wt%, the solidification pressure is 0.2-3.0 MPa, the solidification temperature is 50-200 ℃, and the solidification time is 2-24 h.
9. The method for preparing spherical alumina according to claim 1, wherein the drying temperature is 60-150 ℃, the drying time is 1-48 h, the drying pressure is 0.2-3.0 MPa, and the humidity is 50-80 Rh%; the calcining temperature is 550-1200 ℃, and the calcining time is 1-12 h.
10. Spherical alumina produced by the method for producing spherical alumina according to any one of claims 1 to 9.
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