CN116037217A - Alumina carrier and preparation method and application thereof - Google Patents
Alumina carrier and preparation method and application thereof Download PDFInfo
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- CN116037217A CN116037217A CN202111260257.7A CN202111260257A CN116037217A CN 116037217 A CN116037217 A CN 116037217A CN 202111260257 A CN202111260257 A CN 202111260257A CN 116037217 A CN116037217 A CN 116037217A
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- Prior art keywords
- groups
- powder
- alumina carrier
- alumina
- acid
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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 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 117
- 239000011148 porous material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000002210 silicon-based material Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 150000004684 trihydrates Chemical class 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000002909 rare earth metal compounds Chemical class 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 16
- 241000219782 Sesbania Species 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- UOCIZHQMWNPGEN-UHFFFAOYSA-N dialuminum;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[O-2].[Al+3].[Al+3] UOCIZHQMWNPGEN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B01J35/635—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/613—
-
- B01J35/643—
-
- 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
Abstract
The invention provides an alumina carrier and a preparation method thereof. In the preparation process of the alumina carrier, a certain amount of alpha-Al is added 2 O 3 Powder, alpha-Al used 2 O 3 The particle size, impurity content and the like of the powder are required to meet certain conditions, and the preparationThe obtained alumina carrier has the advantages of low bulk density, high water absorption, large pore volume and large average pore diameter. The active metal can be more uniformly distributed on the surface of the alumina carrier due to the increase of the pore volume and the water absorption rate of the alumina carrier, and the diffusion of reactants and products is facilitated and the reactivity and the selectivity are improved due to the increase of the average pore diameter.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an alumina carrier, and a preparation method and application thereof.
Background
The alumina carrier is widely applied in the petrochemical industry field, such as alkyne selective hydrogenation catalyst carrier, pyrolysis gasoline hydrogenation catalyst carrier, ethylene oxide catalyst carrier prepared by ethylene oxidation, etc. The requirements of different application fields on the alumina carrier are different, and the pore diameter is larger and the acidity is stronger; some of the materials need to have good thermal stability and gradient acidity. Alumina carrier has the advantages of large specific surface area, rich pore structure, high heat stability, etc. especially microporous structure with the features required in catalytic reaction, such as diffusion performance and surface acidity. 8 kinds of alumina in different crystal forms may be obtained through different preparation process and roasting temperature. The properties of the various crystalline forms of alumina are different, and the macroscopic and microscopic structural properties (such as density, pore volume, pore size distribution, etc.) of the same crystalline form of alumina also vary greatly.
The industrial alumina carrier generally adopts pseudo-boehmite powder, quick deoxidized aluminum powder and the like as raw materials, and uses compression molding, extrusion molding, rotational molding and other methods to process the alumina into shapes such as spheres, tooth spheres, bars and the like and certain sizes according to the use requirements. The physical properties of the raw material pseudo-boehmite powder, the selection of forming parameters and the selection of forming aids can influence the physical properties of the final alumina carrier, thereby influencing the performance of the prepared catalyst. The physical properties of the alumina carrier can be adjusted by optimizing the alumina powder refining process and the alumina forming method, and more related researches are developed.
Chinese patent CN103816940a discloses a method for preparing alumina carrier, which uses alumina trihydrate or surge bauxite with wide source and low price as main raw material, alumina sol as binder, and adding fluoride, alkaline earth metal compound and silicide, etc., and through kneading-extrusion-forming, roasting temperature and heating rate are controlled to obtain catalyst carrier with high strength and large specific surface area.
Chinese patent CN106669850a discloses a preparation method of alumina carrier, which uses chloroaluminate modified pseudo-boehmite as raw material, and adds boric acid or phosphoric acid compound, alkyl chloride and binder, and then extrusion-forming-drying and roasting are carried out after uniform mixing to obtain macroporous alumina carrier. The carrier prepared by the method has larger pore diameter and pore volume and double pore distribution.
Chinese patent CN106669850a discloses a method for preparing alumina carrier, which uses alumina powder and glass bead as raw materials, kaolin as binder, resin as pore-forming agent, and after vacuum pugging, the alumina carrier is obtained by isostatic pressing to form spherical blank and roasting. The prepared carrier has the characteristics of high strength, high water absorption, high heat conductivity coefficient and the like.
In the prior art, the preparation process is longer and complicated, more auxiliary agents are added, the production cost is high, and the physical properties of different batches of the prepared alumina carrier are not stable enough. The development and preparation method is still needed, the carrier performance is stable, and the alumina carrier can be used for preparing various catalysts.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an alumina carrier and a preparation method thereof. In the preparation process of the alumina carrier, a certain amount of alpha-Al is added 2 O 3 Powder, alpha-Al used 2 O 3 The particle size, impurity content and the like of the powder are required to meet certain conditions, so that the bulk density of the prepared alumina carrier is reduced, the water absorption rate is obviously increased, the pore volume is increased, the average pore diameter is increased, and the comprehensive performance is better. The alumina carrier is used for preparing the catalyst, is favorable for uniformly distributing metal active components,diffusion of reactants and products. In particular for preparing selective hydrogenation catalysts, the product produced can diffuse faster due to the increase of the average pore diameter, avoiding excessive hydrogenation.
One of the objects of the present invention is to provide an alumina carrier having a water absorption of 40 to 70%, a pore volume of 0.6 to 0.9ml/g and a most probable pore diameter of 0.100 to 0.300. Mu.m; preferably, the alumina carrier has water absorption of 50-65%, pore volume of 0.63-0.8 ml/g and most probable pore diameter of 0.120-0.250 μm.
Preferably, the specific surface area of the alumina carrier is 5-120 m 2 Per gram, bulk density of 0.3-0.9 g/ml, strength of 20-200 Nm; preferably, the specific surface area of the alumina carrier is 20-100 m 2 Per gram, bulk density of 0.5-0.8 g/ml and strength of 30-100 Nm.
The shape of the alumina carrier includes, but is not limited to, powder, granule, sphere, sheet, tooth sphere, bar, or clover.
The alumina carrier also contains 0.01-1wt% of alkali metal element, alkaline earth metal element and/or rare earth metal element, wherein the alkali metal element is at least one of Na, K and Li; the alkaline earth metal element is at least one selected from Mg and Ca; the rare earth metal element is selected from at least one of La, ce, pr, Y, preferably selected from at least one of La and Ce. The metal elements can further improve the performances of the alumina carrier such as strength, specific surface area, pore volume and the like.
The second object of the present invention is to provide a method for preparing the alumina carrier, comprising the steps of powder mixing, kneading molding, drying and roasting, preferably, specifically comprising the steps of:
step 1, uniformly mixing components including alumina powder and auxiliary agents to obtain powder to be kneaded;
step 2, adding an acidic aqueous solution into the powder to be kneaded for kneading and molding;
and step 3, drying and roasting the kneaded product to obtain the alumina carrier.
In particular, the method comprises the steps of,
in the step 1, the alumina powder comprises pseudo-boehmite powder and alpha-Al 2 O 3 Powder, and optionally alumina trihydrate powder and/or fast deoxidized aluminum powder;
wherein the pseudo-boehmite powder can be common pseudo-boehmite, preferably the specific surface area of the pseudo-boehmite powder is 200-300 m 2 Per gram, pore volume of 0.5-1.2 ml/g and bulk density of 0.2-0.4 g/ml;
the alpha-Al 2 O 3 The powder can be obtained by roasting high-purity aluminum hydroxide at a temperature of above 1300deg.C, and fluorine-containing compound can be added during roasting to form flaky alumina particles 2 O 3 The F content in the powder is not more than 0.1%; the alpha-Al 2 O 3 The powder can also be obtained by roasting pseudo-boehmite powder used for molding, and the roasting temperature is higher than 1300 ℃. Preferably, the alpha-Al 2 O 3 The powder is obtained by roasting pseudo-boehmite powder. The alpha-Al 2 O 3 alpha-Al in the powder 2 O 3 The content is more than 95%, the particle diameter of the powder is 2-100 mu m, and the mass content of Na, fe and Si is less than 0.1%;
in the step 1, the alpha-Al 2 O 3 The powder is 5-30wt%, preferably 5-20wt% of the total weight of the alumina powder;
the aluminum oxide trihydrate and the aluminum oxide rapid deoxidization can be prepared from common components, for example, aluminum oxide trihydrate powder can be at least one of gibbsite, bayerite and nordstranite, and the aluminum oxide rapid deoxidization powder is prepared by rapid dehydration of aluminum hydroxide, wherein the mass content of Na and Fe is less than 0.1%; the weight of the alumina powder body of the trihydrate accounts for 0-10% of the total weight of the alumina powder body; the mass of the rapid deoxidized aluminum powder accounts for 0-10% of the total mass of the aluminum oxide powder.
In the step 1, the auxiliary agent is at least one selected from silicon-containing compounds and forming pore-forming auxiliary agents;
wherein the silicon-containing compound is selected from water-insoluble silicon-containing compounds, preferably at least one of dry silica gel, nano silica and silicon carbide; wherein, the average grain diameter of the nanometer silicon oxide and the dry silica gel is preferably less than 120nm;
the Si element in the silicon-containing compound is 0 to 1.35 percent of the total weight of the alumina powder, preferably 0 to 0.9 percent;
the shaping pore-forming auxiliary agent is at least one of natural organic matters, high molecular polymers and decomposable alkaline compounds, preferably at least one of sesbania powder, starch, methyl cellulose, hydroxypropyl methyl cellulose, sodium hydroxymethyl cellulose, polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol, polyacrylate acrylic acid, urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate; one skilled in the art can empirically select one or more shaping pore-forming additives in an amount of 0 to 20%, preferably 0 to 10% of the total mass of the alumina carrier.
The powder mixing in the step 1 can be carried out in a special mixer, or the powder can be added into a kneader and then dry mixed for a certain time without adding solution. The time required for mixing can be determined empirically by those skilled in the art. Powder mixing is an important step of carrier preparation, and uniform powder mixing can be ensured by optimizing a mixer structure, prolonging mixing time and other methods.
In the step 2:
the acid in the acidic aqueous solution is at least one selected from organic acid, inorganic acid and acidic salt compounds, preferably at least one selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and ammonium dihydrogen phosphate, and more preferably at least one selected from nitric acid, acetic acid, oxalic acid and citric acid;
the mass percentage concentration of the acid in the acidic aqueous solution is 0.1-10%, preferably 0.1-5%;
the weight ratio of the acidic aqueous solution to the powder to be kneaded is 0.5-5: 1, preferably 0.6 to 2:1, a step of; the amount of acid in the acidic aqueous solution can be adjusted by those skilled in the art based on the plasticity of the kneaded dough and the specific surface area, strength, bulk density and the like of the carrier after high-temperature firing.
In the step 2, a soluble auxiliary agent is further added to the acidic aqueous solution, preferably, the soluble auxiliary agent is at least one selected from alkali metal compounds, alkaline earth metal compounds and rare earth metal compounds; wherein the alkali metal compound is selected from inorganic salt compounds of metals Na, K and Li, preferably at least one selected from nitrate and chloride of metals Na, K and Li; the alkaline earth metal compound is selected from inorganic salt compounds of metal Mg and Ca, preferably at least one of nitrate and chloride of metal Mg and Ca; the rare earth metal compound is selected from at least one of soluble rare earth metal salt compounds, preferably selected from nitrate and chloride of La, ce, pr, Y, more preferably selected from nitrate and chloride of La and Ce; the metal in the soluble auxiliary agent accounts for 0 to 1.35 percent, preferably 0 to 0.9 percent of the total usage of the alumina powder in terms of the mass percent of metal elements.
In the step 2, the step of kneading and forming is to add the acid aqueous solution containing the soluble auxiliary agent into the uniformly mixed powder, continuously mix and knead, react part of the alumina powder with acid to form a plastic blank, and extrude and form the blank into the required shape and size. The kneading molding time, extrusion molding pressure, and the like are related to the size of the apparatus used, the composition of the alumina powder, the composition of the acid solution, and the like, and can be determined empirically by one skilled in the art.
The step 3 is a drying and roasting step, namely, the moisture in the green body is dried, kneaded and formed, the solid phase reaction is generated in the high-temperature roasting process, alumina grains are adhered together to form an alumina carrier with certain strength,
preferably, the drying temperature is 60-150 ℃ and the drying time is 3-48 hours; the roasting temperature is 800-1200 ℃ and the roasting time is 3-48 hours;
in the roasting process, different heating rates are selected according to different powder raw materials and forming aids, preferably, the heating rate is 30-150 ℃/h at the temperature below 500 ℃, and the heating rate is 100-280 ℃/h at the temperature above 500 ℃.
The invention also aims to provide the alumina carrier or the alumina carrier prepared by the preparation method, which is used for preparing catalysts in the petrochemical industry field.
alpha-Al added in the invention 2 O 3 The powder is Al which has been subjected to high temperature roasting treatment 2 O 3 The particle size and the volume of the powder cannot be reduced in the subsequent roasting process; the pseudo-boehmite powder crystal grains for forming are gradually dehydrated along with the high-temperature roasting process to form crystal grains with higher crystallization degree, and the crystal grains are adhered; the two crystal particles do not synchronously change the particle size and the volume in the high-temperature roasting process, and the alpha-Al 2 O 3 The grains of the powder play a role in supporting and dispersing the pseudo-boehmite grains, so that the pore diameter of the obtained alumina carrier is increased, the pore volume is increased, and the water absorption rate is increased.
The invention adds alpha-Al in the preparation process 2 O 3 The powder is prepared from alumina powder with a certain composition, sesbania powder, starch, cellulose and other forming aids, la, ce, mg and other aids, the types and the amounts of acid solutions are limited, and the drying conditions and the high-temperature roasting conditions are controlled, so that the alumina carrier with larger pore volume, pore diameter and water absorption rate, smaller bulk density and better comprehensive performance can be prepared. The preparation method of the alumina carrier provided by the invention is simple.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
the specific surface area is measured by adopting a nitrogen physical adsorption BET method;
bulk density is calculated by measuring the mass of 100mL of alumina carrier, and average value is obtained after each sample is measured for 3 times;
pore volume and the most probable pore diameter are measured by mercury intrusion method, and are carried out by referring to the pore volume measuring method of the common alumina carrier;
the strength is measured by a universal particle strength measuring instrument, and the average value of 20 particle carrier measurement results is taken;
the water absorption is obtained by taking 20g of alumina carrier, immersing in water for 10 minutes, taking out, draining off surface water, and measuring weight increment.
Example 1
180g of pseudo-boehmite powder and 20g of alpha-Al are weighed 2 O 3 The powder, 8g sesbania powder and 10g starch are mixed uniformly in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 252.4m 2 Per g, pore volume 0.944ml/g, bulk density 0.33g/ml; alpha-Al 2 O 3 The powder is obtained by roasting pseudo-boehmite at 1400℃, and the alpha-Al thereof 2 O 3 The content is 98.0%, the average grain diameter is 5 μm, and the mass content of Na, fe and Si is less than 0.01%. 2.00g of concentrated nitric acid, 2.00g of acetic acid and 1.517g of lanthanum nitrate are weighed and added into 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. Baking at 120deg.C for 12hr, and baking at 1175deg.C for 6hr, wherein the heating rate is controlled at 100deg.C/hr below 500deg.C and 200deg.C/hr above 500deg.C, to obtain alumina carrier S1 with La load of 0.35%.
Example 2
150g of pseudo-boehmite powder and 50g of alpha-Al are weighed 2 O 3 Powder, 6g of sesbania powder, 5g of starch and 3g of crosslinked polyethylene microspheres with the particle size of about 40 microns are uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 252.4m 2 Per g, pore volume 0.944ml/g, bulk density 0.33g/ml; alpha-Al 2 O 3 The powder is obtained by roasting pseudo-boehmite at 1500℃, and the alpha-Al thereof 2 O 3 The content is 99.5%, the average grain diameter is 12 μm, and the mass content of Na, fe and Si is less than 0.01%. 3.00g of concentrated nitric acid, 1.745g of cerium nitrate are weighed and added withInto 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, the calcination temperature raising process was the same as in example 1, and the calcination temperature was 1165℃to obtain alumina carrier S2 having a Ce loading of 0.40%.
Example 3
188g of pseudo-boehmite powder and 12g of alpha-Al are weighed 2 O 3 The powder, 8g sesbania powder, 2g cellulose and 3g ammonium carbonate are mixed uniformly in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 245.7m 2 Per g, pore volume 0.869ml/g, bulk density 0.22g/ml; alpha-Al 2 O 3 The powder was the same as in example 1. 1.00g of concentrated nitric acid, 3g of acetic acid and 0.365g of potassium nitrate were weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The baking conditions were the same as in example 1 to obtain alumina carrier S3 having a K loading of 0.10%.
Example 4
170g of pseudo-boehmite powder and 20g of alpha-Al are weighed 2 O 3 Powder, 10g of alumina trihydrate powder, 6g of sesbania powder and 5g of urea are uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 257.9m 2 Per gram, pore volume of 1.16ml/g, bulk density of 0.23g/ml; alpha-Al 2 O 3 The powder is obtained by roasting high-purity aluminum hydroxide at 1500 ℃, the average grain diameter of the powder is 75 mu m, and the alpha-Al 2 O 3 99.5% of Na, fe and Si, and about 0.05% of Si. The same as in example 1. 2.00g of concentrated nitric acid, 1g of acetic acid and 1.517g of lanthanum nitrate are weighed and added into 190g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, and the calcination procedure was the same as in example 1, at 1180℃to give alumina support S4 having a La loading of 0.35%.
Example 5
Weigh 170g of pseudo-thinDiaspore powder, 20g alpha-Al 2 O 3 Powder, 10g of quick deoxidized aluminum powder, 6g of sesbania powder and 6g of starch are uniformly mixed in a mixer and transferred into a kneader. Wherein the physical properties of the pseudo-boehmite powder are the same as those of example 1; alpha-Al 2 O 3 The powder is obtained by roasting high-purity aluminum hydroxide at 1500 ℃, ammonium fluoride is added in the roasting process, and the formed alpha-Al 2 O 3 The powder crystal grain is in the shape of flake, the average grain diameter is 51 mu m, and the alpha-Al 2 O 3 99.5% of Na, fe and Si, and about 0.05% of Si. 2.00g of concentrated nitric acid, 1g of acetic acid and 8.936g of magnesium nitrate were weighed and added to 190g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The baking conditions were the same as in example 4 to obtain alumina carrier S5 having Mg loading of 0.60%.
Comparative example 1
200g of pseudo-boehmite powder, 8g of sesbania powder and 4g of starch are weighed, uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 189.9m 2 Per g, pore volume 0.804ml/g, bulk density 0.25g/ml. 2.80g of concentrated nitric acid was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, and the calcination procedure was the same as in example 1, at 1195℃to obtain alumina carrier D1.
Comparative example 2
Weighing 196g of pseudo-boehmite powder and 4g of alpha-Al 2 O 3 The powder, 8g sesbania powder and 4g starch are mixed uniformly in a mixer and transferred into a kneader. Wherein pseudo-boehmite powder and alpha-Al 2 O 3 The physical properties of the powder were the same as in example 1. 2.80g of concentrated nitric acid, 0.174g of lanthanum nitrate was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The baking conditions were the same as in comparative example 1 to obtain alumina carrier D2 having a La loading of 0.04%.
Comparative example 3
190g of pseudo-boehmite powder and 10g of alpha-Al are weighed 2 O 3 The powder, 8g sesbania powder and 4g starch are mixed uniformly in a mixer and transferred into a kneader. Wherein the physical properties of the pseudo-boehmite powder are the same as those of comparative example 1, alpha-Al 2 O 3 The powder is obtained by roasting common aluminum hydroxide at 1300 ℃, and the average grain diameter of the powder is 4 mu m, alpha-Al 2 O 3 93.9%, si 0.2%, na and Fe 0.1%. 2.80g of concentrated nitric acid was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The baking conditions were the same as in comparative example 1 to obtain alumina carrier D3.
The alumina supports prepared in the above examples and comparative examples were measured for bulk density, strength, water absorption, pore volume and the most probable pore size. Wherein the specific surface area is measured by adopting a nitrogen physical adsorption BET method, and the specific surface area of the alumina carrier obtained by the examples 1-5 is 20-50 m 2 /g; bulk density is calculated by measuring the mass of 50ml of alumina carrier, and taking average value after each sample is measured for 3 times; pore volume and the most probable pore diameter are measured by mercury intrusion method; the water absorption rate is measured by immersing the carrier in deionized water, standing for 30 minutes after immersing, pouring out excess deionized water and sucking free water on the surface of the carrier. The measurement results are shown in Table 1 below.
TABLE 1 physical Property measurements of alumina Carriers obtained in examples and comparative examples
| Numbering device | Bulk Density (g/ml) | Intensity (Nm) | Water absorption (%) | Pore volume (ml/g) | Most probable aperture (mum) |
| S1 | 0.569 | 48.9 | 65.2 | 0.70 | 0.165 |
| S2 | 0.576 | 41.9 | 63.1 | 0.75 | 0.168 |
| S3 | 0.589 | 53.1 | 61.2 | 0.68 | 0.155 |
| S4 | 0.610 | 65.8 | 57.8 | 0.63 | 0.138 |
| S5 | 0.632 | 67.1 | 54.5 | 0.67 | 0.143 |
| D1 | 0.731 | 83.3 | 54.5 | 0.53 | 0.102 |
| D2 | 0.749 | 88.0 | 49.8 | 0.62 | 0.116 |
| D3 | 0.726 | 78.0 | 52.3 | 0.58 | 0.121 |
According to the data in Table 1, the S1-S5 alumina carriers prepared by the method have high water absorption rate, large pore volume and large most probable pore diameter, and are beneficial to preparing supported metal catalysts; at the same time, the bulk density is reduced, and the catalyst dosage prepared by using the alumina carrier can be reduced under the condition of the same filling volume. Although the strength of the alumina carrier is somewhat reduced, the average strength is greater than 40Nm, which meets most catalyst preparation requirements.
The preparation method of the alumina carrier is simple, and alpha-Al can be adjusted 2 O 3 The addition amount of the powder is selected from pseudo-boehmite powder and alpha-Al with different physical parameters 2 O 3 The powder, the content of other auxiliary agents during molding is adjusted to obtain the alumina carrier with low bulk ratio, high water absorption and large pore volume, and the catalyst is suitable for preparing catalysts in the petrochemical industry field.
Claims (12)
1. The alumina carrier is characterized in that the water absorption rate of the alumina carrier is 40-70%, the pore volume is 0.6-0.9 ml/g, and the most probable pore diameter is 0.100-0.300 mu m.
2. The alumina carrier of claim 1, wherein the alumina carrier comprises a silica,
the water absorption rate of the alumina carrier is 50-65%, the pore volume is 0.63-0.8 ml/g, and the most probable pore diameter is 0.120-0.250 mu m; and/or the number of the groups of groups,
the specific surface area of the alumina carrier is 5-120 m 2 Per gram, bulk density of 0.3-0.9 g/ml, strength of 20-200 Nm; preferably, the specific surface area of the alumina carrier is 20-100 m 2 Per gram, bulk density of 0.5-0.8 g/ml and strength of 30-100 Nm.
3. The alumina carrier of claim 1, wherein the alumina carrier comprises a silica,
the alumina carrier also contains 0.01 to 1 weight percent of alkali metal element, alkaline earth metal element and/or rare earth metal element.
4. The alumina carrier of claim 3, wherein the alumina carrier comprises a silica,
the alkali metal element is at least one of Na, K and Li; and/or the number of the groups of groups,
the alkaline earth metal element is at least one selected from Mg and Ca; and/or the number of the groups of groups,
the rare earth metal element is selected from at least one of La, ce, pr, Y, preferably selected from at least one of La and Ce.
5. A process for producing an alumina carrier according to any one of claims 1 to 4, comprising the steps of powder mixing, kneading and molding, and drying and calcining, preferably comprising the steps of:
step 1, uniformly mixing components including alumina powder and auxiliary agents to obtain powder to be kneaded;
step 2, adding an acidic aqueous solution into the powder to be kneaded for kneading and molding;
and step 3, drying and roasting the kneaded product to obtain the alumina carrier.
6. The method according to claim 5, wherein in step 1:
the alumina powder comprises pseudo-boehmite powder and alpha-Al 2 O 3 Powder, and optionally alumina trihydrate powder and/or fast deoxidized aluminum powder; and/or the number of the groups of groups,
the auxiliary agent is at least one selected from silicon-containing compounds and forming pore-forming auxiliary agents.
7. The method according to claim 6, wherein,
the specific surface area of the pseudo-boehmite powder is 200-300 m 2 Per gram, pore volume of 0.5-1.2 ml/g and bulk density of 0.2-0.4 g/ml; and/or the number of the groups of groups,
the alpha-Al 2 O 3 alpha-Al in the powder 2 O 3 The content is more than 95%, the particle diameter of the powder is 2-100 mu m, and the mass content of Na, fe and Si is less than 0.1%; and/or the number of the groups of groups,
the alpha-Al 2 O 3 The powder is 5-30wt%, preferably 5-20wt% of the total weight of the alumina powder; and/or the number of the groups of groups,
the weight of the alumina powder body of the trihydrate accounts for 0-10% of the total weight of the alumina powder body; and/or the number of the groups of groups,
the mass of the rapid deoxidized aluminum powder accounts for 0-10% of the total mass of the aluminum oxide powder.
8. The method according to claim 6, wherein,
the silicon-containing compound is selected from water-insoluble silicon-containing compounds, preferably at least one of dry silica gel, nano silica and silicon carbide; and/or the number of the groups of groups,
the Si element in the silicon-containing compound is 0 to 1.35 percent of the total weight of the alumina powder, preferably 0 to 0.9 percent; and/or the number of the groups of groups,
the shaping pore-forming auxiliary agent is at least one of natural organic matters, high molecular polymers and decomposable alkaline compounds, preferably at least one of sesbania powder, starch, methyl cellulose, hydroxypropyl methyl cellulose, sodium hydroxymethyl cellulose, polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol, polyacrylate acrylic acid, urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate; and/or the number of the groups of groups,
the dosage of the forming pore-forming auxiliary agent is 0-20% of the total mass of the alumina carrier, and is preferably 0-10%.
9. The method according to claim 5, wherein in the step 2:
the acid in the acidic aqueous solution is at least one selected from organic acid, inorganic acid and acidic salt compounds, preferably at least one selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and ammonium dihydrogen phosphate; and/or the number of the groups of groups,
the mass percentage concentration of the acid in the acidic aqueous solution is 0.1-10%, preferably 0.1-5%; and/or the number of the groups of groups,
the weight ratio of the acidic aqueous solution to the powder to be kneaded is 0.5-5: 1, preferably 0.6 to 2:1, a step of; and/or the number of the groups of groups,
the acidic aqueous solution is further added with a soluble auxiliary agent, preferably, the soluble auxiliary agent is at least one selected from alkali metal compounds, alkaline earth metal compounds and rare earth metal compounds.
10. The method according to claim 9, wherein,
the acid in the acidic aqueous solution is at least one selected from nitric acid, acetic acid, oxalic acid and citric acid; and/or the number of the groups of groups,
the alkali metal compound is selected from inorganic salt compounds of metals Na, K and Li, preferably at least one selected from nitrate and chloride of metals Na, K and Li; and/or the number of the groups of groups,
the alkaline earth metal compound is selected from inorganic salt compounds of metal Mg and Ca, preferably at least one of nitrate and chloride of metal Mg and Ca; and/or the number of the groups of groups,
the rare earth metal compound is selected from soluble rare earth metal salt compounds, preferably at least one selected from nitrate and chloride of La, ce, pr, Y; and/or the number of the groups of groups,
the metal in the soluble auxiliary agent accounts for 0 to 1.35 percent, preferably 0 to 0.9 percent of the total usage of the alumina powder in terms of the mass percent of metal elements.
11. The method according to claim 5, wherein in the step 3:
the drying temperature is 60-150 ℃ and the drying time is 3-48 hours; and/or the number of the groups of groups,
the roasting temperature is 800-1200 ℃ and the roasting time is 3-48 hours; and/or the number of the groups of groups,
in the roasting process, the temperature rising rate is 30-150 ℃/h at the temperature below 500 ℃, and the temperature rising rate is 100-280 ℃/h at the temperature above 500 ℃.
12. An alumina carrier according to any one of claims 1 to 4 or an alumina carrier prepared by the preparation method according to any one of claims 5 to 11, for use in the preparation of catalysts in the petrochemical industry.
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| CN116618002A (en) * | 2023-05-04 | 2023-08-22 | 鲁西催化剂有限公司 | Alumina-based adsorbent and preparation method thereof |
| CN116688970A (en) * | 2023-08-08 | 2023-09-05 | 山东锐海环境科技有限公司 | High-strength catalyst composite carrier and preparation method thereof |
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| CN116618002A (en) * | 2023-05-04 | 2023-08-22 | 鲁西催化剂有限公司 | Alumina-based adsorbent and preparation method thereof |
| CN116688970A (en) * | 2023-08-08 | 2023-09-05 | 山东锐海环境科技有限公司 | High-strength catalyst composite carrier and preparation method thereof |
| CN116688970B (en) * | 2023-08-08 | 2023-10-27 | 山东锐海环境科技有限公司 | High-strength catalyst composite carrier and preparation method thereof |
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