CN110090636B - Cerium-containing aluminum hydroxide dry glue powder and preparation method thereof, and alumina carrier and application thereof - Google Patents
Cerium-containing aluminum hydroxide dry glue powder and preparation method thereof, and alumina carrier and application thereof Download PDFInfo
- Publication number
- CN110090636B CN110090636B CN201810091330.4A CN201810091330A CN110090636B CN 110090636 B CN110090636 B CN 110090636B CN 201810091330 A CN201810091330 A CN 201810091330A CN 110090636 B CN110090636 B CN 110090636B
- Authority
- CN
- China
- Prior art keywords
- aluminum hydroxide
- aging
- cerium
- containing aluminum
- glue powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims abstract description 91
- 239000000843 powder Substances 0.000 title claims abstract description 61
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 45
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003292 glue Substances 0.000 title claims abstract description 45
- 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 37
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 71
- 239000011268 mixed slurry Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 39
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000975 co-precipitation Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 40
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- -1 butyl aluminium Chemical compound 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 claims description 2
- 239000001164 aluminium sulphate Substances 0.000 claims description 2
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 2
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 2
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 22
- 239000011148 porous material Substances 0.000 description 19
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [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 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 229910052796 boron Inorganic materials 0.000 description 1
- OCFSGVNHPVWWKD-UHFFFAOYSA-N butylaluminum Chemical compound [Al].[CH2]CCC OCFSGVNHPVWWKD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion 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
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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Abstract
The invention relates to the field of aluminum hydroxide dry glue powder, and discloses cerium-containing aluminum hydroxide dry glue powder as well as a preparation method and application thereof, wherein the method comprises the following steps of 1) preparing mixed slurry containing nano cerium oxide and dihydric alcohol; 2) carrying out coprecipitation reaction on an aluminum salt and a precipitator to obtain a solution containing aluminum hydroxide sol, and carrying out first aging on the obtained solution containing the aluminum hydroxide sol; 3) mixing the product of the step 2) with the product of the step 1) and then carrying out secondary aging; 4) and (3) carrying out solid-liquid separation and drying on the aged product in the step 3), wherein the dihydric alcohol is 2-amino-1, 3-propylene glycol and/or triethylene glycol. The method is beneficial to enriching cerium on the surface of the alumina carrier, highly dispersing and improving the physical and chemical properties of the aluminum hydroxide dry glue powder.
Description
Technical Field
The invention relates to the field of aluminum hydroxide dry glue powder, in particular to cerium-containing aluminum hydroxide dry glue powder and a preparation method thereof, and an alumina carrier prepared from the cerium-containing aluminum hydroxide dry glue powder and application thereof.
Background
With the increasing deterioration of crude oil and the stricter requirements of environmental regulations, the requirement for oil quality is increasing. Hydrogenation is one of the main methods for reducing sulfide and nitride in fuel oil in order to meet the requirements of environmental regulations. In the hydrogenation process, the catalyst plays an important role. Currently, most of the catalysts used are alumina as a carrier and metals of group VIII and/or group VIB as active components. The surface property of single alumina can not meet the use requirement of the catalyst, for example, the interaction force between active metal on the surface of the alumina and a carrier is stronger, inactive spinel species are easily formed, so that the active component of the metal is not easy to be vulcanized, and the activity is reduced. The acting force between the active component and the carrier is reduced, and the method becomes a key technology for preparing the high-activity hydrotreating catalyst.
In order to prepare a highly active, highly stable hydroprocessing catalyst, many researchers have chemically modified the supported alumina to achieve the desired physical and chemical properties. If additives such as magnesium, titanium, boron, fluorine, silicon, zinc, zirconium, vanadium, phosphorus and the like are added, the interaction between alumina and active components and the acidity of the surface of the alumina are mainly changed, the stability of the alumina is improved, and the like.
EP0339640 discloses a method for producing alumina containing titanium by a coprecipitation method, which can produce titanium-containing alumina having good dispersibility, but the coprecipitation method has a problem of phase retention, and the main role of titanium dioxide cannot be sufficiently exerted. The coprecipitation condition cannot simultaneously satisfy the coprecipitation of a plurality of substances, and the physical and chemical properties of the carrier are influenced.
CN200410050777.5 discloses a preparation method of a macroporous alumina carrier. Adding an auxiliary agent solution containing boric acid into a mixed material of an alumina precursor and a pore-expanding agent, kneading, molding, drying and roasting to obtain a final carrier, wherein the auxiliary agent solution can also contain auxiliary agents such as silicon, phosphorus, magnesium, zinc, titanium and the like. In the method, titanium is introduced as an auxiliary agent in a kneading mode, and the titanium is unevenly distributed on the surface of the alumina carrier, so that the physicochemical property of the carrier is influenced.
CN200610013758.4 discloses a preparation method of a supported zirconia catalyst carrier. The carrier is zirconia, alumina, silica, oxidation state, magnesia, active carbon or molecular sieve, and the catalyst carrier loaded with zirconia is prepared through isovolumetric impregnation or excessive impregnation of the carrier with solution prepared with zirconia or zirconium nitrate, drying and roasting. The activity of the catalyst prepared by the method is not greatly changed.
CN1289636A discloses a method for preparing titanium-containing aluminum hydroxide by precipitating titanium salt in aluminum hydroxide slurry, which is easy to corrode equipment due to the chloride ion and sulfate ion contained in the titanium salt solution, and can generate gas polluting environment during the roasting process, thus limiting the industrial application.
CN103785446A discloses a preparation method of hydrocracking catalyst, the preparation steps of the catalyst prepared by the method are complicated, and the activity of the catalyst is not improved sufficiently.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides cerium-containing aluminum hydroxide dry glue powder and a preparation method thereof, and an alumina carrier prepared from the cerium-containing aluminum hydroxide dry glue powder and application thereof. The cerium is enriched on the surface of the alumina carrier prepared from the cerium-containing aluminum hydroxide dry glue powder and is highly dispersed, so that the reaction activity of the catalyst can be improved.
In order to achieve the above objects, in one aspect, the present invention provides a method for preparing cerium-containing aluminum hydroxide dry glue powder, wherein the method comprises the following steps,
1) preparing mixed slurry containing nano cerium oxide and dihydric alcohol;
2) carrying out coprecipitation reaction on an aluminum salt and a precipitator to obtain a solution containing aluminum hydroxide sol, and carrying out first aging on the obtained solution containing the aluminum hydroxide sol;
3) mixing the product of the step 2) with the product of the step 1) and then carrying out secondary aging;
4) carrying out solid-liquid separation and drying on the product aged in the step 3),
wherein the dihydric alcohol is 2-amino-1, 3-propanediol and/or triethylene glycol.
In a second aspect, the invention provides cerium-containing aluminum hydroxide dry glue powder prepared according to the method of the invention.
In a third aspect, the invention provides an alumina carrier prepared from the cerium-containing aluminum hydroxide dry glue powder of the invention.
In a third aspect, the invention provides the use of a hydroprocessing catalyst having as a carrier the alumina carrier of the invention in a hydroprocessing process.
According to the preparation method of the cerium-containing aluminum hydroxide dry glue powder, the mixed slurry containing the nano cerium oxide and the dihydric alcohol is added in the aging stage of the aluminum hydroxide sol to inhibit the aggregation of the nano cerium oxide on the aluminum hydroxide sol and improve the interaction force of the cerium oxide and the aluminum hydroxide sol, and in the obtained cerium-containing aluminum hydroxide dry glue powder, the cerium oxide is uniformly distributed, a stable Al-O-Ce bond can be formed in an aluminum oxide carrier prepared from the cerium-containing aluminum hydroxide dry glue powder, the cerium oxide and the aluminum oxide are uniformly distributed, the synergistic effect of the cerium oxide and the aluminum oxide in the aluminum oxide carrier is improved, and the aluminum oxide carrier can be used for preparing a hydrotreating catalyst with excellent properties and improving the reaction activity of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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 preparation method of the cerium-containing aluminum hydroxide dry glue powder provided by the invention comprises the following steps,
1) preparing mixed slurry containing nano cerium oxide and dihydric alcohol;
2) carrying out coprecipitation reaction on an aluminum salt and a precipitator to obtain a solution containing aluminum hydroxide sol, and carrying out first aging on the obtained solution containing the aluminum hydroxide sol;
3) mixing the product of the step 2) with the product of the step 1) and then carrying out secondary aging;
4) carrying out solid-liquid separation and drying on the product aged in the step 3),
wherein the dihydric alcohol is 2-amino-1, 3-propanediol and/or triethylene glycol.
According to the present invention, the content of the nano cerium oxide in the mixed slurry is preferably 2 to 30% by weight, more preferably 10 to 30% by weight, and still more preferably 10 to 25% by weight, from the viewpoint of production cost.
In addition, the particle size of the nano cerium oxide is preferably 10 to 100nm, more preferably 10 to 40nm, and even more preferably 30 to 40nm, from the aspect of the service performance of the modified cerium-containing aluminum hydroxide dry glue powder.
According to the present invention, the content of the diol in the mixed slurry is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, and still more preferably 0.8 to 3% by weight, from the viewpoint of more uniform dispersion of cerium oxide on the surface of alumina.
Preferably, the diol is triethylene glycol.
The method for preparing the mixed slurry containing nano-cerium oxide and glycol of the present invention is not particularly limited, and may be a method generally used in the art, for example, a cerium oxide slurry containing an appropriate amount of 2-amino-1, 3-propanediol may be added thereto and stirred uniformly. The temperature and time of stirring are not particularly limited, and for example, the stirring time may be 5 to 30min, preferably 10 to 25min, at room temperature (e.g., 10 to 40 ℃). The solvent in the cerium oxide slurry may be, for example, water.
According to the invention, in step 2), the aluminum salt is preferably one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum formate, aluminum oxalate, butyl aluminum and ethyl aluminum; more preferably aluminium sulphate.
According to the invention, in the step 2), the precipitant is one or more of sodium hydroxide, ammonium hydroxide, potassium aluminate, sodium aluminate and ammonia water; more preferably potassium aluminate and/or sodium aluminate.
According to the invention, in step 2), the amounts of the aluminum salt and the precipitant can vary within wide limits, and preferably the molar ratio of the amounts of the aluminum salt and the precipitant is 1: 1-10; more preferably 1: 3-6.
According to the present invention, in step 2), the conditions of the coprecipitation reaction are not particularly limited and may be conditions conventional in the art, and preferably, the conditions of the coprecipitation reaction include: the temperature of the coprecipitation reaction is 55-62 ℃, the pH value of the coprecipitation reaction is 7.5-8.8, and the coprecipitation reaction time is 10-100 min; more preferably, the conditions of the coprecipitation reaction include: the temperature of the coprecipitation reaction is 55-62 ℃, the pH value of the coprecipitation reaction is 8.0-8.2, and the coprecipitation reaction time is 35-65 min.
Further, it is preferable that the coprecipitation reaction is carried out such that the concentration of aluminum hydroxide in the resulting solution containing an aluminum hydroxide sol is 1 to 30g/100mL in terms of aluminum oxide; more preferably, the coprecipitation reaction is carried out such that the concentration of aluminum hydroxide in the resulting solution containing an aluminum hydroxide sol is 5 to 10g/100mL in terms of aluminum oxide.
The mode of the above-mentioned coprecipitation reaction is not particularly limited, and may be a reaction mode which is conventional in the art. Preferably, the above-mentioned coprecipitation reaction is co-current coprecipitation.
According to the invention, the conditions of the first ageing comprise: aging at 50-62 deg.C and pH of 8.0-8.7 for 5-50 min; preferably, the aging temperature is 55-62 ℃, the aging pH value is 8.0-8.5, and the aging time is 10-30 min.
According to the invention, in the step 3), the product obtained in the step 1) is used in an amount such that the content of the nano cerium oxide in the cerium-containing aluminum hydroxide dry glue powder is 1-10 wt%; preferably, the product of the step 1) is used in an amount such that the content of the nano cerium oxide in the cerium-containing aluminum hydroxide dry glue powder is 2-6 wt%. The use of the product of step 1) in the above range has the effect of increasing the interaction force of cerium oxide and aluminum oxide.
According to the present invention, preferably, the conditions of the second aging include: compared with the first aging, the aging temperature is increased by 2-6 ℃, the aging pH is increased by 0.2-1.0, and the aging time is 15-50 min. More preferably, the conditions of the second aging include: compared with the first aging, the aging temperature is increased by 2-5 ℃, the aging pH is increased by 0.2-0.5, and the aging time is 20-40 min.
According to the present invention, in step 4), the solid-liquid separation may be performed by a method conventional in the art, and for example, the solid-liquid separation may be performed by filtration, centrifugation, or the like. The conditions are well known in the art and will not be described herein in detail.
Further, the solid-liquid separation is preferably followed by washing, and for example, washing with water may be carried out.
According to the present invention, in the step 4), the drying is not particularly limited and may be a condition conventional in the art, for example, the drying temperature may be 80 to 150 ℃, preferably 100 to 130 ℃, and the drying time may be 1 to 10 hours, preferably 4 to 8 hours.
The invention also provides cerium-containing aluminum hydroxide dry glue powder prepared by the preparation method.
The cerium oxide content in the cerium-containing aluminum hydroxide dry glue powder obtained by the preparation method is 1-20 wt%, preferably 2-6 wt%; specific surface area of 400-520m2Per g, preferably 400-450m2(ii)/g; the pore volume is 0.9-1.5mL/g, preferably 0.95-1.2 mL/g; average holeThe diameter is 0.9nm-1.5nm, preferably 0.9-1.1 nm; the dispersion of cerium is between 0.3 and 0.5, preferably between 0.35 and 0.45.
The invention also provides an alumina carrier prepared from the cerium-containing aluminum hydroxide dry glue powder.
According to the present invention, the alumina support may be prepared by a method generally used in the art, and preferably, the alumina support is prepared by the following method.
The alumina carrier is prepared by mixing aluminum hydroxide dry glue powder, SB powder, sesbania powder and citric acid, then mixing with an acidic solution (which can be performed in a rolling machine for example) for 3-60 minutes, then forming, and then drying and roasting. Wherein, the forming can be carried out by adopting a forming method which is conventional in the field, for example, extrusion can be carried out; the drying conditions may include: drying at 15-180 deg.C for 0.2-30 hr, preferably at 40-180 deg.C for 3-8 hr; the conditions for the firing may include: the roasting temperature is 180-600 ℃, the roasting time is 0.2-30 hours, preferably, the roasting temperature is 400-600 ℃, and the roasting time is 3-8 hours.
In addition, relative to 100 parts by weight of the aluminum hydroxide dry glue powder, the amount of the SB powder is 5-15 parts by weight, the amount of the sesbania powder is 1-4 parts by weight, and the amount of the citric acid is 2-6 parts by weight.
The weight ratio of the mixed material of the aluminum hydroxide dry glue powder, the SB powder, the sesbania powder and the citric acid to the acid solution is preferably 1: 1.2-1.5.
The acid in the acidic solution may be, for example, one or more of nitric acid, acetic acid, and tartaric acid. The concentration of the acid in the acidic solution may be, for example, 1.5 to 3.5 wt%.
The invention also provides the application of the hydrotreating catalyst using the alumina carrier as a carrier in the hydrotreating process.
The hydrotreating catalyst uses metals of the VIII group and the VIB group as active metal components, the metal of the VIII group is preferably Co and/or Ni, the metal of the VIB group is preferably W and/or Mo, the content of the metal of the VIII group is 1-15 wt%, preferably 4-10 wt% calculated by oxide, and the content of the metal of the VIB group is 10-30 wt%, preferably 15-25 wt% calculated by oxide based on the weight of the catalyst. The hydrotreating catalyst is prepared by a conventional catalyst preparation technology such as a kneading method or an impregnation method, and the like, which is not described herein in detail.
In the hydrotreating process of the hydrotreating catalyst using the alumina carrier as the carrier, the specific reaction conditions are as follows: the reaction pressure is 4-12MPa, preferably 8-10 MPa; the reaction temperature is 350-380 ℃, and preferably 365-375 ℃; the hydrogen-oil ratio is 400: 1-1200: 1, preferably 600: 1-1000: 1.
the action and effect of the present invention will be further illustrated by the following examples, which are not intended to limit the process of the present invention.
The preparation process of the mixed slurry of the nano cerium oxide and the triethylene glycol is as follows: adding a proper amount of triethylene glycol into the stirred nano cerium oxide aqueous solution, and stirring for 25 min.
The preparation process of the aluminum hydroxide sol comprises the following steps: adding proper amount of deionized water into colloid forming device, and neutralizing acidic aluminum salt solution such as aluminum sulfate, aluminum chloride, aluminum nitrate and the like with alkaline precipitant such as sodium hydroxide or ammonium hydroxide or alkali metal aluminum salt aqueous solution such as potassium aluminate or sodium aluminate and the like to form aluminum hydroxide slurry.
The dispersion was measured by XPS in the following examples and comparative examples, in the following way:
1) carrying out XPS (X-ray photoelectron spectroscopy, produced by ThermoFisher company in America, and the model is Multilab 2000) analysis on the prepared cerium-containing aluminum hydroxide dry glue powder sample, specifically, compacting and fixing cerium-containing aluminum hydroxide dry glue powder sample powder on an indium foil of a sample holder in a glove box filled with argon, transferring the sample holder into a preparation cabin of the spectrometer, carrying out air extraction treatment, transferring into an analysis cabin, and testing by taking Al K0 as a photoelectron source and combining energy Eb of 1486.6 eV;
2) performing sorting calculation on the analyzed data;
3) the degree of dispersion was calculated according to the following formula.
Dispersion (surface atomic molar concentration ratio) ═ Ce At.%/Al At.%.
Specific surface area, pore size and average pore size were determined on a large multi-station fully automated specific surface and porosity analyzer, ASAP2420, manufactured by micromeritics and gon, usa.
CeO in cerium-containing aluminum hydroxide dry glue powder2The content is determined by X-ray fluorescence spectrum analysis.
In the following examples and comparative examples, unless otherwise specified, the atmosphere for low-temperature drying and high-temperature baking was air atmosphere.
Example 1
(1) Preparing mixed slurry of nano cerium oxide and triethylene glycol, wherein the content of the nano cerium oxide in the mixed slurry is 10 wt%, the content of the triethylene glycol is 0.8 wt%, and the balance is water, and the particle size of the nano cerium oxide is 40 nm;
(2) preparing a sodium aluminate aqueous solution with the concentration of 30g/L and an aluminum sulfate aqueous solution with the concentration of 40g/L, adding the sodium aluminate aqueous solution and the aluminum sulfate aqueous solution into a neutralization reaction device in a concurrent flow manner under the stirring condition, controlling the pH value to be 8.2, the temperature to be 55 ℃ and the neutralization time to be 55min to obtain a solution containing aluminum hydroxide sol (wherein the concentration of aluminum hydroxide in the solution containing aluminum hydroxide sol is 5g/100mL calculated by alumina), adding the mixed slurry prepared in the step (1) after aging for 10min, and continuing aging, wherein the adding weight of the mixed slurry prepared in the step (1) is 8 wt% of the weight of the solution containing aluminum hydroxide sol; controlling the aging temperature to be 58 ℃ and the aging pH to be 8.2 before adding the mixed slurry, and continuing aging for 20min after adding the mixed slurry, wherein the aging temperature is increased by 2.5 ℃ and the aging pH is increased by 0.5 compared with the aging temperature before adding the mixed solution;
(3) and filtering, washing and drying the aged material to obtain the cerium-containing aluminum hydroxide dry glue powder A, wherein the drying temperature is 110 ℃, and the drying time is 6 hours.
The obtained cerium-containing aluminum hydroxide dry glue powder A has the pore volume, the specific surface area, the dispersity, the average pore diameter and CeO2The contents are shown in Table 1.
Example 2
(1) Preparing mixed slurry of nano cerium oxide and triethylene glycol, wherein the content of the nano cerium oxide in the mixed slurry is 15 wt%, the content of the triethylene glycol in the mixed slurry is 1 wt%, and the balance is water, and the particle size of the nano cerium oxide is 30 nm;
(2) preparing a sodium aluminate aqueous solution with the concentration of 30g/L and an aluminum sulfate aqueous solution with the concentration of 40g/L, adding the sodium aluminate aqueous solution and the aluminum sulfate aqueous solution into a neutralization reaction device in a concurrent flow manner under the stirring condition, controlling the pH value to be 8.0, the temperature to be 60 ℃, and the neutralization time to be 35min to obtain a solution containing aluminum hydroxide sol (wherein, the concentration of aluminum hydroxide in the solution containing aluminum hydroxide sol is 10g/100mL calculated by alumina), adding the mixed slurry prepared in the step (1) after aging for 30min, and continuing aging, wherein the adding weight of the mixed slurry prepared in the step (1) is 9 wt% of the weight of the solution containing aluminum hydroxide sol; controlling the aging temperature to be 60 ℃ and the aging pH to be 8.0 before adding the mixed slurry, and continuing aging for 30min after adding the mixed slurry, wherein the aging temperature is increased by 3.5 ℃ and the aging pH is increased by 0.5 compared with the aging temperature before adding the mixed solution;
(3) and filtering, washing, drying and roasting the aged material to obtain cerium-containing aluminum hydroxide dry glue powder B, wherein the drying temperature is 120 ℃, and the drying time is 6 hours.
The obtained cerium-containing aluminum hydroxide dry glue powder B has the pore volume, the specific surface area, the dispersity, the average pore diameter and CeO2The contents are shown in Table 1.
Example 3
(1) Preparing mixed slurry of nano cerium oxide and triethylene glycol, wherein the content of the nano cerium oxide in the mixed slurry is 20 wt%, the content of the triethylene glycol in the mixed slurry is 2 wt%, the balance is water, and the particle size of the nano cerium oxide is 40 nm;
(2) preparing a sodium aluminate aqueous solution with the concentration of 30g/L and an aluminum sulfate aqueous solution with the concentration of 40g/L, adding the sodium aluminate aqueous solution and the aluminum sulfate aqueous solution into a neutralization reaction device in a concurrent flow manner under the stirring condition, controlling the pH value to be 8.0, the temperature to be 60 ℃ and the neutralization time to be 55min to obtain a solution containing aluminum hydroxide sol (wherein, the concentration of aluminum hydroxide in the solution containing aluminum hydroxide sol is 10g/100mL calculated by alumina), adding the mixed slurry prepared in the step (1) after aging for 30min, and continuing aging, wherein the adding weight of the mixed slurry prepared in the step (1) is 10 wt% of the weight of the solution containing aluminum hydroxide sol; controlling the aging temperature to be 62 ℃ and the aging pH to be 8.5 before adding the mixed slurry, and continuing aging for 25min after adding the mixed slurry, wherein the aging temperature is increased by 4 ℃ and the aging pH is increased by 0.3 compared with the aging temperature before adding the mixed solution;
(3) and filtering, washing, drying and roasting the aged material to obtain cerium-containing aluminum hydroxide dry glue powder C, wherein the drying temperature is 120 ℃, and the drying time is 8 hours.
The obtained cerium-containing aluminum hydroxide dry glue powder C has the pore volume, the specific surface area, the dispersity, the average pore diameter and CeO2The contents are shown in Table 1.
Example 4
(1) Preparing mixed slurry of nano cerium oxide and triethylene glycol, wherein the content of the nano cerium oxide in the mixed slurry is 25 wt%, the content of propylene glycol phenyl ether in the mixed slurry is 3 wt%, and the particle size of the nano cerium oxide is 40 nm;
(2) preparing a sodium aluminate aqueous solution with the concentration of 30g/L and an aluminum sulfate aqueous solution with the concentration of 40g/L, adding the sodium aluminate aqueous solution and the aluminum sulfate aqueous solution into a neutralization reaction device in a concurrent flow manner under the stirring condition, controlling the pH value to be 8.2, the temperature to be 60 ℃ and the neutralization time to be 55min to obtain a solution containing aluminum hydroxide sol (wherein, the concentration of aluminum hydroxide in the solution containing aluminum hydroxide sol is 10g/100mL calculated by alumina), adding the mixed slurry prepared in the step (1) after aging for 30min, and continuing aging, wherein the adding weight of the mixed slurry prepared in the step (1) is 11 wt% of the weight of the solution containing aluminum hydroxide sol; controlling the aging temperature to be 60 ℃ and the aging pH to be 8.2 before adding the mixed slurry, and continuing aging for 40min after adding the mixed slurry, wherein the aging temperature is increased by 5 ℃ and the aging pH is increased by 0.2 compared with the aging temperature before adding the mixed solution;
(3) and filtering, washing, drying and roasting the aged material to obtain the cerium-containing aluminum hydroxide dry glue powder D, wherein the drying temperature is 110 ℃, and the drying time is 6 hours.
The obtained cerium-containing aluminum hydroxide dry glue powder D has the pore volume, the specific surface area, the dispersity, the average pore diameter and CeO2The contents are shown in Table 1.
Example 5
(1) Preparing mixed slurry of nano cerium oxide and triethylene glycol, wherein the content of the nano cerium oxide in the mixed slurry is 30 wt%, the content of the triethylene glycol in the mixed slurry is 3.0 wt%, and the particle size of the nano cerium oxide is 30 nm;
(2) preparing a sodium aluminate aqueous solution with the concentration of 30g/L and an aluminum sulfate aqueous solution with the concentration of 40g/L, adding the sodium aluminate aqueous solution and the aluminum sulfate aqueous solution into a neutralization reaction device in a concurrent flow manner under the stirring condition, controlling the pH value to be 8.0, the temperature to be 62 ℃, and the neutralization time to be 55min to obtain a solution containing aluminum hydroxide sol (wherein, the concentration of aluminum hydroxide in the solution containing aluminum hydroxide sol is 10g/100mL calculated by alumina), adding the mixed slurry prepared in the step (1) after aging for 30min, and continuing aging, wherein the adding weight of the mixed slurry prepared in the step (1) is 12 wt% of the weight of the solution containing aluminum hydroxide sol; controlling the aging temperature to be 60 ℃ and the aging pH to be 8.0 before adding the mixed slurry, and continuing aging for 30min after adding the mixed slurry, wherein the aging temperature is increased by 2 ℃ and the aging pH is increased by 0.5 compared with the aging temperature before adding the mixed solution.
(3) And filtering, washing, drying and roasting the aged material to obtain cerium-containing aluminum hydroxide dry glue powder E, wherein the drying temperature is 130 ℃, and the drying time is 8 hours.
The obtained cerium-containing aluminum hydroxide dry glue powder E has the pore volume, the specific surface area, the dispersity, the average pore diameter and CeO2The contents are shown in Table 1.
Comparative example 1
The procedure was carried out in the same manner as in example 1 except that the slurry was free of diethylene glycol to obtain cerium-containing aluminum hydroxide dry-gel powder F, which had been obtained in the same manner as in example 1, in terms of pore volume, specific surface area, dispersion degree, average pore diameter and CeO2The contents are shown in Table 1.
Comparative example 2
The same procedure as in example 1 was conducted except that the mixed slurry prepared in step (1) was added during the coprecipitation to obtain cerium-containing aluminum hydroxide dry gel powder G, and the obtained cerium-containing aluminum hydroxide dry gel powder F had a pore volume, a specific surface area, a dispersion degree, an average pore diameter, and CeO2The contents are shown in Table 1.
TABLE 1
| Physicochemical Properties | Pore volume, ml/g | Specific surface area, m2/g | Degree of dispersion, ICeIAl | Average pore diameter, nm | CeO2,wt％ |
| A | 1.18 | 444 | 0.42 | 0.93 | 2 |
| B | 1.16 | 426 | 0.39 | 0.98 | 3 |
| C | 1.14 | 416 | 0.40 | 0.86 | 4 |
| D | 1.10 | 401 | 0.36 | 1.00 | 5 |
| E | 0.96 | 400 | 0.33 | 1.03 | 6 |
| F | 0.82 | 385 | 0.23 | 0.85 | 2 |
| G | 0.85 | 396 | 0.26 | 0.87 | 2 |
Test example 1
Respectively weighing 220 g of dry aluminum hydroxide powder purchased from Nicotiana constant brightness chemical company Limited under the trade name YH-28 and 220 g of dry rubber powder of examples and comparative examples, respectively adding 110 g of SB powder, 4 g of sesbania powder and citric acid, uniformly mixing, adding 450 g of acid solution, wherein the concentration of nitric acid in the acid solution is 2 wt%, and the balance of distilled water. Grinding for 25min, extruding with 1.7mm diameter sheet, heating at 120 deg.CDrying for 12 hours, and roasting for 3 hours at 550 ℃ to obtain the catalyst carrier. The carrier is impregnated by impregnation liquid containing Mo and Ni to obtain the catalysts C-1 to C-8, wherein the content of molybdenum oxide in the catalysts is 24 weight percent, and the content of nickel oxide is 4 weight percent. And (3) performing activity evaluation on the catalyst, wherein the raw oil is catalytic diesel oil, the nitrogen content is 1800ng/ul, the sulfur content is 1.8%, and the evaluation conditions are as follows: the reaction pressure is 8.5MPa, the reaction temperature is 368 ℃, and the space velocity is 2.0h-1Hydrogen-oil ratio 650: 1, the evaluation results are shown in Table 2. Wherein, the catalyst C-0 is a catalyst prepared from aluminum hydroxide dry glue powder which is purchased from Nicoti Henghui chemical company Limited and has the trade name of YH-28, and the dry glue powder used by the catalysts C-1 to C-7 is cerium-containing aluminum hydroxide dry glue powder A to G prepared in the examples and the comparative examples respectively. The relative activity takes the hydrodesulfurization activity and the hydrodenitrogenation activity of the catalyst C-0 as reference, and the calculation formula is as follows:
the relative desulfurization activity of the catalyst ═ the hydrodesulfurization activity of the catalyst ÷ the hydrodesulfurization activity of the catalyst C-0 × 100%;
the relative denitrification activity of the catalyst is the hydrodenitrogenation activity of the catalyst ÷ the hydrodenitrogenation activity of the catalyst C-0 multiplied by 100%;
the relative desulfurization and denitrification activities of catalyst C-0 were recorded as 100.
TABLE 2
| Catalyst numbering | C-0 | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Relative denitrification activity,% | 100 | 152 | 154 | 149 | 147 | 137 | 127 | 130 |
| Relative desulfurization activity of% | 100 | 134 | 150 | 130 | 128 | 121 | 110 | 113 |
As is clear from the description in Table 2, the activity of the catalyst using the alumina carrier as the carrier prepared from the cerium-containing aluminum hydroxide dry-gel powder prepared by the method of the present invention is significantly higher than that of the catalyst prepared in the comparative example.
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 (16)
1. A method for preparing cerium-containing aluminum hydroxide dry glue powder is characterized by comprising the following steps,
1) preparing mixed slurry containing nano cerium oxide and dihydric alcohol;
2) carrying out coprecipitation reaction on an aluminum salt and a precipitator to obtain a solution containing aluminum hydroxide sol, and carrying out first aging on the obtained solution containing the aluminum hydroxide sol;
3) mixing the product of the step 2) with the product of the step 1) and then carrying out secondary aging;
4) carrying out solid-liquid separation and drying on the product aged in the step 3),
wherein the dihydric alcohol is 2-amino-1, 3-propanediol and/or triethylene glycol.
2. The method according to claim 1, wherein the content of the nano cerium oxide in the mixed slurry is 2 to 30% by weight.
3. The method of claim 1, wherein the nano-ceria has a particle size of 10-100 nm.
4. The method according to claim 1, wherein the content of the glycol in the mixed slurry is 0.1-10 wt%.
5. The method of claim 4, wherein the glycol is triethylene glycol.
6. The method according to any one of claims 1 to 5, wherein the aluminium salt is one or more of aluminium sulphate, aluminium chloride, aluminium nitrate, aluminium formate, aluminium oxalate, butyl aluminium and ethyl aluminium.
7. The process of any one of claims 1 to 5, wherein the precipitating agent is one or more of sodium hydroxide, ammonium hydroxide, potassium aluminate, sodium aluminate and aqueous ammonia.
8. The process according to any one of claims 1 to 5, wherein the aluminium salt and the precipitating agent are used in a molar ratio of 1: 1-10.
9. The method of any one of claims 1-5, wherein the conditions of the co-precipitation reaction comprise: the temperature of the coprecipitation reaction is 55-62 ℃, the pH value of the coprecipitation reaction is 7.5-8.8, and the coprecipitation reaction time is 10-100 min.
10. The method according to claim 9, wherein the coprecipitation reaction is such that the concentration of aluminum hydroxide in the resulting solution containing an aluminum hydroxide sol is 1 to 30g/100mL in terms of alumina.
11. The method of any of claims 1-5, wherein the first aging condition comprises: aging at 55-62 deg.C and pH of 8.0-8.5 for 10-30 min.
12. The method of claim 11, wherein the second aging condition comprises: compared with the first aging, the aging temperature is increased by 2-6 ℃, the aging pH is increased by 0.2-1.0, and the aging time is 15-50 min.
13. The method as claimed in any one of claims 1 to 5, wherein in the step 3), the product of the step 1) is used in an amount such that the content of the nano cerium oxide in the cerium-containing aluminum hydroxide dried gel powder is 1 to 10% by weight.
14. The cerium-containing aluminum hydroxide dry-glue powder prepared by the method of any one of claims 1 to 13.
15. An alumina support prepared from the cerium-containing aluminum hydroxide dry-gel powder of claim 14.
16. Use of a hydrotreating catalyst on the alumina support of claim 15 as a support in a hydrotreating process.
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