CN111111633A - Spherical alumina, preparation method thereof, catalyst carrier and catalyst - Google Patents
Spherical alumina, preparation method thereof, catalyst carrier and catalyst Download PDFInfo
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- CN111111633A CN111111633A CN201911339712.5A CN201911339712A CN111111633A CN 111111633 A CN111111633 A CN 111111633A CN 201911339712 A CN201911339712 A CN 201911339712A CN 111111633 A CN111111633 A CN 111111633A
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- spherical alumina
- alumina
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- alginate
- solution
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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 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000000725 suspension Substances 0.000 claims abstract description 41
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 33
- 229920000615 alginic acid Polymers 0.000 claims abstract description 33
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940072056 alginate Drugs 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 229960001126 alginic acid Drugs 0.000 claims abstract description 13
- 239000000783 alginic acid Substances 0.000 claims abstract description 13
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 13
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 235000010407 ammonium alginate Nutrition 0.000 claims description 4
- 239000000728 ammonium alginate Substances 0.000 claims description 4
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 235000010418 carrageenan Nutrition 0.000 claims description 4
- 239000000679 carrageenan Substances 0.000 claims description 4
- 229920001525 carrageenan Polymers 0.000 claims description 4
- 229940113118 carrageenan Drugs 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 4
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 235000010408 potassium alginate Nutrition 0.000 claims description 3
- 239000000737 potassium alginate Substances 0.000 claims description 3
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 38
- 239000000499 gel Substances 0.000 description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 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 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 wherein Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
- B01J2/08—Gelation of a colloidal solution
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalyst carriers and catalysts, and discloses spherical alumina, a preparation method thereof, a catalyst carrier and a catalyst. The method comprises the following steps: (1) mixing alginic acid and/or alginate with the slurry to prepare a suspension; (2) dropwise adding the suspension into a solution containing metal ions to perform a gel reaction; the slurry contains an alumina precursor and an auxiliary agent; density ρ of the suspension1Is 1 to 1.5g/cm3Viscosity of 100-900 mPa-.And S. The spherical alumina prepared by the method has high sphericity, uniform size, high strength and stable performance.
Description
Technical Field
The invention relates to the technical field of catalyst carriers and catalysts, in particular to spherical alumina, a preparation method thereof, a catalyst carrier and a catalyst.
Background
Activated alumina (gamma-Al)2O3) The catalyst has the advantages of adjustable porous structure, large specific surface area, good adsorption performance, good thermal stability, acidity on the surface and the like, is commonly used as a catalyst carrier in catalytic hydrogenation, dehydrogenation, desulfurization, reforming, cracking and other petrochemical industries, and is one of the most applied carriers in the petrochemical industry. The activated alumina material with different grain size, shape, specific surface area and surface property is prepared according to different purposes, wherein the spherical alumina has the advantages of high rolling property, low bulk density, low abrasion and the like, and has wide application in fixed bed and fluidized bed processes.
At present, the preparation method of the spherical active alumina in industry mainly focuses on the rolling method [ spherical gamma-Al2O3Research on support preparation, Industrial catalysis, 2003, 9, 39-40]Oil (ammonia) column formation [ US 4279779; US 4108971; US4273735]Aqueous phase formation [ CN 104477953A; CN 102718241A; CN106745125B]The method of (1).
The rolling forming method has the advantages of large dust in the production process, high product abrasion and large particle size deviation. The oil (ammonia) column forming and the water phase forming mainly utilize sol to gel in the oil (ammonia) column or the water column to form spherical particles, and the forming operation is simple and the efficiency is high. However, the oil column and oil ammonia column methods require heat aging (the oil phase temperature is as high as 95 ℃ during the operation of the oil column forming method, the energy consumption is high), the aging time is long, and the oil removal treatment is required; the oil ammonia column method also has the problem of discharging irritant gas ammonia, which causes the problems of complex process, high energy consumption, environmental pollution and the like; the oil-ammonia column forming method has an oil-water interface, the surface layer of the sol solution is easy to peel off when the sol solution drops pass through the oil-water interface, an emulsion layer is easy to form at the interface to cause the floating of particles, and the like, and the ammonia is easy to volatilize to cause environmental pollution. The water column forming method mainly utilizes a large amount of free carboxylic acid in alginic acid to quickly form gel when encountering polyvalent metal ions (such as calcium, aluminum, zinc, barium, manganese and the like), and compared with an oil column method and an oil ammonia column method, the water column method has the advantages of simple process, low cost, low energy consumption and easy industrial production.
CN104477953A discloses a method for forming spherical alumina (water column forming method), wherein: uniformly mixing the aluminum gel and the alginate solution to prepare suspension slurry; dripping the suspension slurry into a multivalent metal cation solution to form spherical composite gel particles; taking out the gel particles, drying and roasting to obtain an alumina product; wherein the aluminum gel is alumina hydrogel or nano alumina sol; the weight content of alumina in the suspension slurry is 5-25%, and the content of alginate is 0.3-5%; the polyvalent metal cation solution is a salt solution of aluminum, zinc, calcium, copper, iron, ferrous iron, cobalt, manganese or nickel ions with 0.1 mol/L-saturated concentration. However, the pellets produced by this method are unstable in quality and are liable to crack.
CN106745125B discloses a preparation method (water column forming method) of spherical alumina, wherein, sodium metaaluminate solution is mixed with alginate solution to prepare solution a; dripping or spraying the solution A into an aluminum salt solution through a pinhole to form gel spheres, and further aging until the gel spheres are completely hardened; taking out the gel balls, fully washing the gel balls by using deionized water until the conductivity of washing water is less than 500 mu s/cm, and then soaking the gel balls by using 0.5-10 wt% of urea solution; finally, drying and roasting to obtain spherical alumina; wherein the alginate is sodium alginate, potassium alginate or ammonium alginate; the content of alumina in the solution A is 5-20 wt%, and the content of alginate is 0.3-5 wt%; the aluminum salt is aluminum sulfate, aluminum nitrate or aluminum chloride, and the concentration of aluminum ions in the aluminum salt solution is 0.1-1 mol/L. Adopts sodium metaaluminate solution as raw material, the strong basicity of the sodium metaaluminate solution increases the operation difficulty, and introduces Na as impurity+Resulting in increased production costs.
CN102718241A discloses a method for preparing spherical alumina particles by alginic acid assisted molding (water column molding method). Pseudo-boehmite PB and ammonium alginate are mixed and then added into polyvalent metal ions (Ca) in a dropwise manner2+、Ba2+、Cu2+、Zn2+、Mn2+Etc.) to form gel beads in an aqueous solution. Placing the pellet inSolidifying in acetic acid solution with certain concentration for a period of time, drying and calcining to obtain gamma-Al with the particle size of 2.5-3mm2O3And (4) a small ball. The gamma-Al obtained by the method2O3The content of impurities in the pellet is high (7-10% of polyvalent metal ions), and the pore volume and crushing strength are greatly changed and are respectively 0.27-0.54cm3(iv)/g and 25-110N, uniformity of pore distribution and instability of sphericity in the pellets. In addition, the gel pellets need to be treated in an acetic acid solution with a certain concentration for a period of time, and the acetic acid treatment not only increases the difficulty of the production process and the production cost, but also causes environmental pollution.
The problems of easy cracking, unstable crushing strength, uncontrollable physicochemical properties (such as particle size, sphericity, pore volume, surface acidity and the like) and the like of the active alumina spheres prepared by the alginate-assisted gel method are mainly caused by the factors of poor slurry stability, non-uniform internal structure, rapid evaporation and decomposition of water or organic matters in the processes of gel sphere dehydration and organic matter removal.
Therefore, how to improve the crushing strength and the stability of the product of the spherical alumina prepared by the alginate-assisted gel method needs further research and development.
Disclosure of Invention
The invention aims to solve the problems of unstable quality, easy cracking and unstable sphericity of the prepared spherical alumina in the prior art, and provides the spherical alumina, a preparation method thereof, a catalyst carrier and a catalyst. The method simplifies the production process, reduces the production cost, is easy to realize industrial continuous production, can improve the sphericity of the spherical alumina, has uniform size, high strength and stable performance.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing spherical alumina, the method comprising:
(1) mixing alginic acid and/or alginate with the slurry to prepare a suspension;
(2) dropwise adding the suspension into a solution containing metal ions to perform a gel reaction;
wherein the slurry contains an alumina precursor and an auxiliary agent;
wherein the suspension has a density ρ1Is 1 to 1.5g/cm3The viscosity was 100-900 mPaS.
In a second aspect, the present invention provides a spherical alumina prepared by the method described above.
In a third aspect, the present invention provides a catalyst, wherein the catalyst contains the spherical alumina.
The fourth aspect of the present invention provides a catalyst carrier, wherein the catalyst carrier contains the spherical alumina described above.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) the spherical alumina prepared by the method has high sphericity, uniform size, high strength and stable performance.
(2) Strong acid and strong base are not used in the production process, the production process is simplified, the production cost is reduced, and the industrial continuous production is easy to realize.
(3) In addition, the gel beads are in the presence of Al3+Aging in solution of (2), wherein, Al3+The impurity-metal ions in the gel beads can be replaced, and the purity of the aluminum oxide can be improved; the calcining method of drying in the shade, slow burning at low temperature and multi-stage heating can avoid the cracking of alumina caused by the rapid evaporation and decomposition of water and organic matters in the calcining process and improve the balling rate.
Drawings
FIG. 1 is an optical photograph of spherical alumina prepared in example 1 of the present invention;
FIG. 2 is an optical photograph of spherical alumina prepared in example 2 of the present invention;
FIG. 3 is an optical photograph of spherical alumina prepared in example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of spherical alumina in a first aspect, which comprises the following steps:
(1) mixing alginic acid and/or alginate with the slurry to prepare a suspension;
(2) dropwise adding the suspension into a solution containing metal ions to perform a gel reaction;
wherein the slurry contains an alumina precursor and an auxiliary agent;
wherein the suspension has a density ρ1Is 1 to 1.5g/cm3The viscosity was 100-900 mPaS.
According to the invention, the suspension preferably has a density ρ1Is 1.05-1.24g/cm3The viscosity was 110-540 mPaS. In the present invention, controlling the density and viscosity of the suspension to be within the above ranges has an advantage in that the sphericity of the spherical alumina prepared is high.
According to the invention, the suspension has a density ρ1And the density ρ of the solution containing metal ions2The relationship of (d) may be: rho2＝(0.6-1.5)×ρ1Preferably ρ2＝(0.8-1.25)×ρ1(ii) a Will rho1And rho2The method has the advantages that the curing time of the prepared spherical alumina is proper, the spherical alumina has certain strength when being deposited to the bottom of the cup, the damage in the production process is avoided, and the yield of the final product is improved.
According to the invention, in the step (1), the alginate is one or more of sodium alginate, potassium alginate and ammonium alginate, and is preferably sodium alginate.
According to the invention, the content of alginic acid is 0.5-6 wt% and the content of alginate is 0.5-6 wt% based on the total weight of the slurry; preferably, the content of alginic acid is 1.5-4 wt% and the content of alginate is 1.5-4 wt% based on the total weight of the slurry.
According to the present invention, the alumina precursor contains one or more of hydrated alumina, boehmite and pseudoboehmite, preferably pseudoboehmite.
According to the invention, the auxiliary agent contains one or more of urea, carboxymethyl cellulose, polyacrylamide, sodium polyacrylate, carrageenan and tween 80, and preferably urea and/or polyacrylamide.
According to the invention, the slurry also contains water, and the content of the alumina precursor is 50-150g and the content of the auxiliary agent is 4-14g relative to 150mL of water. In the present invention, specifically, the content of the alumina precursor may be, for example, 50g, 55g, 60g, 65g, 70g, 75g, 80g, 85g, 90g, 95g, 100g, 105g, 110g, 115g, 120g, 125g, 130g, 135g, 140g, 145g, and 150g, and any value in the range of any two of these points. In addition, in the present invention, specifically, the content of the auxiliary may be, for example, any value in a range of 4g, 5g, 6g, 7g, 8g, 9g, 10g, 11g, 12g, 13g, and 14g, and any two of these points.
According to the present invention, in the step (2), the metal ion in the metal ion-containing solution may be Ca2+、Ba2+、Mg2+And Zn2+Preferably Ca2+And/or Mg2+(ii) a For example, in the present invention, the solution containing metal ions may be one or more of calcium nitrate, calcium chloride, barium nitrate, barium chloride, magnesium nitrate, magnesium chloride, zinc nitrate, and zinc chloride.
According to the present invention, the suspension is dropped into a solution containing metal ions to perform a gel reaction, wherein the average particle diameter, specific surface area, pore volume, most probable pore diameter, strength and surface acidity of spherical alumina can be controlled by controlling the diameter of a dropping head and the height of the dropping head to the liquid surface, and in the present invention, the dropping conditions include: the diameter of the dripper is 0.5-5mm, and the height from the dripper to the liquid level is 1.5-15 cm; preferably, the diameter of the dripper is 0.8-3mm, and the height from the dripper to the liquid level is 3-5 cm; in the present invention, specifically, the diameter of the dripper may be, for example, any value in the range of 0.8mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, 2.2mm, 2.3mm, 2.5mm, 2.7mm, 2.8mm, and 3mm and any two of these point values. In the present invention, specifically, the height of the dripper from the liquid surface is 1.5cm, 1.7cm, 1.8cm, 1.9cm, 2cm, 2.3cm, 2.5cm, 2.8cm, 3cm, 3.2cm, 3.5cm, 3.7cm, 4cm, 4.3cm, 4.5cm, 4.7cm, 4.8cm, and 5cm, and any value in the range of any two of these point values.
In the invention, under the conditions defined above, the suspension prepared by mixing alginic acid and/or alginate with the slurry is added dropwise into the solution containing metal ions for gel reaction to form gel particles, and simultaneously, the alumina precursor embedded in the alginic acid and/or alginate particles is subjected to an in-situ sol-gel process under acidic conditions to form a jelly of alginic acid and/or alginate and the alumina precursor.
According to the invention, the method also comprises the step of adding the gel balls obtained in the step (2) to a mixture containing Al3+Aging the solution, draining, transferring to a constant temperature and humidity box, drying in the shade, vibrating, screening, and roasting; wherein said Al is contained3+The solution of (A) may be Al (NO)3)3、AlCl3And Al2 (SO)4)3Preferably Al (NO)3)3(ii) a In the present invention, the Al-containing compound3+The mass concentration of (b) may be 12 to 28 wt%, specifically, for example, may be any value in the range of 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, and 28 wt%, and any two of these points.
In the present invention, the aging conditions may include: aging at 40-90 deg.C for 20min-120 h; preferably, the aging is carried out for 30min-1h at the temperature of 40-55 ℃.
In the present invention, the drying conditions in the shade may include: drying in the shade at 20-50 deg.C and 40-80% RH relative humidity, wherein the drying time in the shade is preferably 32-48 h.
In the invention, the roasting adopts a method of multi-stage heating roasting:
(a) heating to 90-120 deg.C at a heating rate of 0.2-2 deg.C/min, and maintaining at the temperature for 1-8 hr;
(b) heating to 180-240 ℃ at the heating rate of 1-4 ℃/min, and keeping the temperature for 1-6 h;
(c) heating to 350-460 ℃ at a heating rate of 1-5 ℃/min, and keeping the temperature for 2-16 h;
(d) raising the temperature to 550-650 ℃ at a temperature raising rate of 2-5 ℃/min, and keeping the temperature for 30min-4 h.
Preferably, the method for multistage temperature-rising roasting comprises the following steps:
(a) heating to 110-120 ℃ at a heating rate of 1-1.8 ℃/min, and keeping the temperature for 6-7 h;
(b) heating to 230-240 deg.c at 1-2 deg.c/min and maintaining at the temperature for 4-5 hr;
(c) heating to 420-430 ℃ at a heating rate of 1-2 ℃/min, and keeping the temperature for 6-7 h;
(d) the temperature is raised to 600-620 ℃ at the temperature raising rate of 2-3 ℃/min, and the temperature is kept for 3-4 h.
In the invention, the calcining method of drying in the shade, slow burning at low temperature and multi-stage temperature rise can avoid the cracking of alumina caused by the rapid evaporation and decomposition of water and organic matters in the calcining process and improve the balling rate.
According to the invention, the method also comprises the steps of selecting the calcined spherical alumina and packaging.
In a second aspect, the present invention provides a spherical alumina prepared by the method described above.
According to the invention, the average particle diameter of the spherical alumina is 0.5-5mm, and the specific surface area is 180-230m2(ii)/g, strength of 53-120N; preferably, the spherical alumina has an average particle diameter of 1.1-3.5mm and a specific surface area of 181-220m2/g，The intensity is 60-111N.
Specifically, the average particle diameter of the spherical alumina may be, for example, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, 3mm, 3.1mm, 3.2mm, 3.3mm, 3.4mm, 3.5mm, or any value within a range constituted by any two of these point values.
Specifically, the spherical alumina has a specific surface area of 181m2/g、182m2/g、183m2/g、184m2/g、185m2/g、186m2/g、187m2/g、188m2/g、189m2/g、190m2/g、191m2/g、192m2/g、193m2/g、194m2/g、195m2/g、196m2/g、197m2/g、198m2/g、199m2/g、200m2/g、201m2/g、202m2/g、203m2/g、204m2/g、205m2/g、206m2/g、207m2/g、208m2/g、209m2/g、210m2/g、211m2/g、212m2/g、213m2/g、214m2/g、215m2/g、216m2/g、217m2/g、218m2/g、219m2G and 220m2G, and any value in the range of any two of these point values.
Specifically, the strength of the spherical alumina is any value in a range of 60N, 61N, 62N, 63N, 64N, 65N, 66N, 67N, 68N, 69N, 70N, 71N, 72N, 73N, 74N, 75N, 76N, 77N, 78N, 79N, 80N, 81N, 82N, 83N, 84N, 85N, 86N, 87N, 88N, 89N, 90N, 91N, 92N, 93N, 94N, 95N, 96N, 97N, 98N, 99N, 100N, 101N, 102N, 103N, 104N, 105N, 106N, 107N, 108N, 109N, and 110N, and any two of these point values.
In a third aspect, the present invention provides a catalyst, wherein the catalyst contains the spherical alumina.
The fourth aspect of the present invention provides a catalyst carrier, wherein the catalyst carrier contains the spherical alumina described above.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) the average particle size is measured by randomly selecting 50-100 spheres, reading diameter data by a vernier caliper and then taking an average value;
(2) the strength was measured using a universal press, purchased from Hunan Tan instruments Ltd, model XM-50 KN;
(3) the specific surface area and pore volume were measured using ASAP-2460 from Micromeritics.
Example 1
This example is intended to illustrate spherical alumina prepared by the process of the present invention.
(1) Adding 50g of pseudo-boehmite, 6g of urea, 1g of ammonium polyacrylate and 3g of Tween 80 into 150mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 6 wt%, and stirring at the stirring speed of 300 revolutions per minute at 35 ℃ for 0.5h to form uniform alginic acid-pseudo-boehmite suspension;
wherein the density and viscosity of the suspension were measured to be 1.15g/cm, respectively3And 180 mpa.s;
(2) dropping the suspension to a density of 1.12g/cm3Gelling in calcium nitrate solution to form gel balls; wherein the diameter of the dripper is 3mm, and the height from the dripper to the liquid level is 5 cm;
(3) aging the gel spheres in an aluminum nitrate solution (28 mass percent) at 40 ℃ for 15min, draining, transferring to a constant temperature and humidity box, drying in the shade, and drying in the shade at 20 ℃ and 80% humidity for 48 hours; carrying out vibration screening and calcining treatment on the gel balls dried in the shade; wherein, the calcining procedure is as follows: heating to 120 deg.C at 1 deg.C/min, holding for 6 hr, heating to 240 deg.C at 1 deg.C/min, holding for 4 hr, heating to 420 deg.C at 1 deg.C/min, holding for 6 hr, heating to 600 deg.C at 2 deg.C/min, holding for 3 hr, and naturally cooling.
Results the properties of the prepared spherical alumina S1 were tested, and fig. 1 is an average particle diameter of the spherical alumina S2, and the test results are shown in table 1.
Example 2
This example is intended to illustrate spherical alumina prepared by the process of the present invention.
(1) Adding 30g of boehmite and 30g of hydrated alumina, 2g of urea, 1g of ammonium polyacrylate and 1g of carrageenan into 150mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 6 wt%, and stirring at the temperature of 55 ℃ and the stirring speed of 280 revolutions per minute for 1.5 hours to form uniform alginic acid-boehmite-hydrated alumina suspension;
wherein the density and viscosity of the suspension were measured to be 1.16g/cm, respectively3And 240 mpa.s;
(2) dropping the suspension to a density of 1.12g/cm3Gelling in calcium nitrate solution to form gel balls; wherein the diameter of the dripper is 2mm, and the height from the dripper to the liquid level is 5 cm;
(3) aging the gel spheres in an aluminum nitrate solution (28 mass percent) at 55 ℃ for 45min, draining, transferring to a constant temperature and humidity box for drying in the shade, and drying in the shade at 20 ℃ and 80% humidity for 48 hours; carrying out vibration screening and calcining treatment on the gel balls dried in the shade; wherein, the calcining procedure is as follows: heating to 120 deg.C at 1 deg.C/min, holding for 6 hr, heating to 240 deg.C at 1 deg.C/min, holding for 4 hr, heating to 420 deg.C at 1 deg.C/min, holding for 6 hr, heating to 600 deg.C at 2 deg.C/min, holding for 3 hr, and naturally cooling.
Results the properties of the prepared spherical alumina S2 were tested, and fig. 2 is a graph showing the average particle size of the spherical alumina S2, the test results being shown in table 1.
Example 3
This example is intended to illustrate spherical alumina prepared by the process of the present invention.
(1) Taking 75g of pseudo-boehmite, 6g of urea, 0.75g of ammonium acrylate and 0.25g of carrageenan, adding 75mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 3 wt%, and stirring for 1h at the stirring speed of 220 r/min at 45 ℃ to form uniform alginic acid-pseudo-boehmite suspension;
wherein the density and viscosity of the suspension were measured to be 1.24g/cm, respectively3And 540 mpa.s;
(2) dropping the suspension to a density of 1.18g/cm3Gelling in calcium nitrate solution to form gel balls; wherein the diameter of the dripper is 0.8mm, and the height from the dripper to the liquid level is 3 cm;
(3) aging the gel spheres in an aluminum nitrate solution (28 mass percent) at 45 ℃ for 30min, draining, transferring to a constant temperature and humidity box for drying in the shade, and drying in the shade at 20 ℃ and 80% humidity for 32 hours; carrying out vibration screening and calcining treatment on the gel balls dried in the shade; wherein, the calcining procedure is as follows: heating to 120 deg.C at 1 deg.C/min, holding for 6 hr, heating to 240 deg.C at 1 deg.C/min, holding for 6 hr, heating to 420 deg.C at 1 deg.C/min, holding for 10 hr, heating to 600 deg.C at 2 deg.C/min, holding for 3 hr, and naturally cooling.
Results the performance of the prepared spherical alumina S3 was tested, and fig. 3 is a graph showing the average particle size of the spherical alumina S2, the test results being shown in table 1.
Example 4
Spherical alumina was prepared in the same manner as in the examples, except that:
(1) taking 70g of pseudo-boehmite, 4g of urea, 0.75g of ammonium acrylate and 0.25g of carboxymethyl cellulose, adding 150mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 4 wt%, and stirring for 1h at the stirring speed of 220 r/min at 45 ℃ to form uniform alginic acid-pseudo-boehmite suspension;
wherein the density and viscosity of the suspension were measured to be 1.17g/cm, respectively3And 190 mpa.s;
(2) dropping the suspension to a density of 1.18g/cm3Gelling in barium nitrate solution to form gel balls; wherein the diameter of the dripper is 1mm, and the height from the dripper to the liquid level is 3.5 cm;
(3) the gel balls are put into an aluminum chloride solution (28 mass percent).
Results the performance of the prepared spherical alumina S4 was tested as shown in table 1.
Example 5
Spherical alumina was prepared in the same manner as in the examples, except that:
(1) adding 80g of pseudo-boehmite, 3g of urea and 3g of carboxymethyl cellulose into 150mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 3.9 wt%, and stirring for 1h at the stirring speed of 220 r/min at 45 ℃ to form uniform alginic acid-pseudo-boehmite suspension;
wherein the density and viscosity of the suspension were measured to be 1.19g/cm, respectively3And 210 mpa.s;
(2) dropping the suspension to a density of 1.18g/cm3Gelling in magnesium nitrate solution to form gel balls; wherein the diameter of the dripper is 1.5mm, and the height from the dripper to the liquid level is 4 cm;
(3) placing the gel balls on Al2(SO4)3Solution (28% by weight).
Results the performance of the prepared spherical alumina S5 was tested as shown in table 1.
Example 6
Spherical alumina was prepared in the same manner as in the examples, except that:
(1) adding 100g of pseudo-boehmite, 6g of sodium polyacrylate and 6g of carboxymethyl cellulose into 150mL of water for dispersion, adding 100mL of sodium alginate aqueous solution with the mass concentration of 5 wt%, and stirring for 1h at the stirring speed of 220 r/min at 45 ℃ to form uniform alginic acid-pseudo-boehmite suspension;
wherein the density and viscosity of the suspension were measured to be 1.23g/cm, respectively3And 300 mpa.s;
(2) dropping the suspension to a density of 1.18g/cm3Gelling in zinc nitrate solution to form gel balls; wherein the diameter of the dripper is 2.5mm, and the height from the dripper to the liquid level is 4.5 cm;
(3) placing the gel balls in AlCl3Solution (28% by weight).
Results the performance of the prepared spherical alumina S6 was tested as shown in table 1.
Comparative example 1
Alumina pellets produced by Sasol corporation were used.
Results the performance of the alumina pellets produced by Sasol corporation was tested as shown in table 1.
Comparative example 2
Spherical alumina was prepared under the same conditions as in example 1, except that: the suspension had a density and viscosity of 0.9g/cm, respectively3And 90 mpa.s.
Results the properties of the prepared spherical alumina DS2 were tested as shown in table 1.
Comparative example 3
Spherical alumina was prepared under the same conditions as in example 1, except that: the mixture ratio of the density of the suspension and the density of the calcium nitrate is as follows: rho2＝0.5×ρ1。
Results the properties of the prepared spherical alumina DS3 were tested as shown in table 1.
Comparative example 4
Spherical alumina was prepared under the same conditions as in example 1, except that: adding 40g of pseudo-boehmite, 1g of urea, 1g of ammonium polyacrylate and 1g of Tween 80 into 150mL of water for dispersion, and then adding 100mL of sodium alginate aqueous solution with the mass concentration of 12%.
Results the properties of the prepared spherical alumina DS4 were tested as shown in table 1.
TABLE 1
| Sample (I) | Average particle diameter (mm) | Strength (N) | Specific surface area (cm)3/g) |
| S1 | 3.5 | 53 | 215 |
| S2 | 2.3 | 54 | 220 |
| S3 | 1.1 | 111 | 216 |
| S4 | 1.9 | 60 | 215 |
| S5 | 2.1 | 72 | 218 |
| S6 | 3.0 | 81 | 217 |
| DS1 | 1.8 | 40 | 214 |
| DS2 | 1.5 | 41 | 213 |
| DS3 | 1.4 | 45 | 209 |
| DS4 | 1.7 | 46 | 211 |
As can be seen from Table 1 and FIGS. 1 to 3, the spherical aluminas prepared in examples 1 to 6 according to the method of the present invention have high strength, relatively high specific surface area, high sphericity and uniform size.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method for preparing spherical alumina, the method comprising:
(1) mixing alginic acid and/or alginate with the slurry to prepare a suspension;
(2) dropwise adding the suspension into a solution containing metal ions to perform a gel reaction;
wherein the slurry contains an alumina precursor and an auxiliary agent;
wherein the suspension has a density ρ1Is 1 to 1.5g/cm3Viscosity of 100-900 mPa-.S。
2. The method of claim 1, wherein the suspension has a density p1And the placeDensity rho of the solution containing metal ions2The relationship of (1) is: rho2＝(0.6-1.5)×ρ1(ii) a More preferably ρ2＝(0.8-1.25)×ρ1。
3. The method according to claim 1, wherein, in step (1), the alginate is one or more of sodium alginate, potassium alginate and ammonium alginate;
preferably, the content of alginic acid is 0.5 to 6 wt% and the content of alginate is 0.5 to 6 wt% based on the total weight of the slurry;
preferably, the content of alginic acid is 1.5-4 wt% and the content of alginate is 1.5-4 wt% based on the total weight of the slurry.
4. The method of claim 1 or 3, wherein the alumina precursor contains one or more of hydrated alumina, boehmite, and pseudoboehmite;
preferably, the auxiliary agent contains one or more of urea, carboxymethyl cellulose, polyacrylamide, sodium polyacrylate, carrageenan and tween 80;
preferably, the slurry also contains water, and the content of the alumina precursor is 50-150g and the content of the auxiliary agent is 4-14g relative to 150mL of water.
5. The method according to claim 1, wherein, in the step (2), the metal ion in the metal ion-containing solution is Ca2+、Ba2+、Mg2+And Zn2+One or more of;
preferably, the dropping conditions include: the diameter of the dripper is 0.5-5mm, and the height from the dripper to the liquid level is 1.5-15 cm.
6. The method according to any one of claims 1 to 5, wherein the method further comprises subjecting the gel beads obtained in step (2) to a treatment comprising Al3+Aging in the solution, drying in the shade, screening and then performingRoasting treatment;
preferably, the Al-containing component3+The solution of (A) is Al (NO)3)3、AlCl3And Al2(SO4)3One or more of;
preferably, the Al-containing component3+The mass concentration of the solution of (2) is 12 to 28 wt%.
7. The method of claim 6, wherein the aging condition comprises: the temperature is 40-90 ℃, and the time is 20min-120 h;
preferably, the drying in the shade conditions include: the temperature is 20-50 ℃, and the relative humidity is 40-80%;
preferably, the roasting adopts a method of multi-stage heating roasting:
(a) heating to 90-120 ℃ at a heating rate of 0.2-2 ℃/min and keeping for 1-8 h;
(b) heating to 180-240 ℃ at the heating rate of 1-4 ℃/min and keeping for 1-6 h;
(c) heating to 350-460 ℃ at the heating rate of 1-5 ℃/min and keeping for 2-16 h;
(d) raising the temperature to 550-650 ℃ at the temperature raising rate of 2-5 ℃/min and keeping the temperature for 30min-4 h.
8. Spherical alumina prepared by the process of any one of claims 1 to 7.
9. The spherical alumina as claimed in claim 8, wherein the spherical alumina has an average particle diameter of 0.5 to 5mm and a specific surface area of 180-230m2In terms of/g, the strength is 53-120N.
10. A catalyst comprising the spherical alumina according to claim 8 or 9.
11. A catalyst carrier comprising the spherical alumina according to claim 8 or 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020429A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Alumina particles and their preparation method |
| CN116474712A (en) * | 2023-04-03 | 2023-07-25 | 上海化工研究院有限公司 | A kind of molding preparation method of silicon-aluminum composite oxide pellet |
| CN116966889A (en) * | 2023-07-26 | 2023-10-31 | 山西炬华新材料科技有限公司 | A kind of spherical alumina catalyst carrier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542113A (en) * | 1982-04-02 | 1985-09-17 | Condea Chemie Gmbh | Method for preparing spheroidal alumina |
| CN104891539A (en) * | 2015-05-22 | 2015-09-09 | 中国海洋石油总公司 | Chambering method for spherical aluminum oxide particles |
-
2019
- 2019-12-23 CN CN201911339712.5A patent/CN111111633B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542113A (en) * | 1982-04-02 | 1985-09-17 | Condea Chemie Gmbh | Method for preparing spheroidal alumina |
| CN104891539A (en) * | 2015-05-22 | 2015-09-09 | 中国海洋石油总公司 | Chambering method for spherical aluminum oxide particles |
Non-Patent Citations (1)
| Title |
|---|
| 孟广莹等: "水柱成型法制备重整载体", 《无机盐工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020429A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Alumina particles and their preparation method |
| CN116474712A (en) * | 2023-04-03 | 2023-07-25 | 上海化工研究院有限公司 | A kind of molding preparation method of silicon-aluminum composite oxide pellet |
| CN116966889A (en) * | 2023-07-26 | 2023-10-31 | 山西炬华新材料科技有限公司 | A kind of spherical alumina catalyst carrier and preparation method thereof |
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