CN107999047B - Boron-containing hydrated alumina composition, molded body, preparation method and application of boron-containing hydrated alumina composition, catalyst and preparation method of catalyst - Google Patents
Boron-containing hydrated alumina composition, molded body, preparation method and application of boron-containing hydrated alumina composition, catalyst and preparation method of catalyst Download PDFInfo
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- CN107999047B CN107999047B CN201610966585.1A CN201610966585A CN107999047B CN 107999047 B CN107999047 B CN 107999047B CN 201610966585 A CN201610966585 A CN 201610966585A CN 107999047 B CN107999047 B CN 107999047B
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- Prior art keywords
- hydrated alumina
- composition
- boron
- alumina
- compound
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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 718
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 311
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 310
- 239000000203 mixture Substances 0.000 title claims abstract description 273
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 177
- 239000011240 wet gel Substances 0.000 claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000001035 drying Methods 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 50
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 159
- 239000007788 liquid Substances 0.000 claims description 96
- 239000000499 gel Substances 0.000 claims description 88
- 238000000926 separation method Methods 0.000 claims description 76
- 239000012298 atmosphere Substances 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 54
- 238000004519 manufacturing process Methods 0.000 claims description 50
- 238000000465 moulding Methods 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 43
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 28
- 229920000926 Galactomannan Polymers 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- 150000004684 trihydrates Chemical class 0.000 claims description 19
- 229920003086 cellulose ether Polymers 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- -1 galactan Polymers 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 208000005156 Dehydration Diseases 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 229920000609 methyl cellulose Polymers 0.000 claims description 9
- 239000001923 methylcellulose Substances 0.000 claims description 9
- 235000010981 methylcellulose Nutrition 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 238000011085 pressure filtration Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 6
- 229920000057 Mannan Polymers 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229920002683 Glycosaminoglycan Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 42
- 239000000463 material Substances 0.000 abstract description 30
- 239000000428 dust Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003292 glue Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 75
- 238000005470 impregnation Methods 0.000 description 50
- 238000009740 moulding (composite fabrication) Methods 0.000 description 50
- 238000001125 extrusion Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000001914 filtration Methods 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 21
- 238000004846 x-ray emission Methods 0.000 description 21
- 239000003921 oil Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000007790 solid phase Substances 0.000 description 19
- 241000219782 Sesbania Species 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 18
- 238000001354 calcination Methods 0.000 description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 16
- 239000012265 solid product Substances 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 12
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000004676 glycans Chemical class 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 6
- 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 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 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 4
- 229940024545 aluminum hydroxide Drugs 0.000 description 4
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- 238000007865 diluting Methods 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
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- 238000007493 shaping process Methods 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
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- 229920000570 polyether Polymers 0.000 description 3
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- 238000010298 pulverizing process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- GCQUOBKUEHYBMC-UHFFFAOYSA-N 3-(diethylamino)-7,8-dihydro-6h-cyclopenta[2,3]thieno[2,4-b][1,3]oxazin-1-one Chemical compound O=C1OC(N(CC)CC)=NC2=C1C(CCC1)=C1S2 GCQUOBKUEHYBMC-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000002411 adverse Effects 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
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- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 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 1
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000245214 Mentha canadensis Species 0.000 description 1
- 235000016278 Mentha canadensis Nutrition 0.000 description 1
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- 101100063942 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dot-1 gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 229920000159 gelatin Polymers 0.000 description 1
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- 229910001679 gibbsite Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
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- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
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Images
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
- B01J23/70—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
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/883—Molybdenum and nickel
-
- B01J35/647—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G45/08—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 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a boron-containing hydrated alumina composition, a forming body, a preparation method, application, a catalyst and a preparation method thereof
The value is 5 or less. The invention also discloses a catalyst with hydrogenation catalysis function and a preparation method thereof, and a hydrotreating method, wherein the catalyst takes a formed body formed by the boron-containing hydrated alumina composition as a carrier. The invention prepares the formed body with higher strength by taking the hydrated alumina wet gel as the initial raw material, omits the step of drying the hydrated alumina wet gel, and does not need to additionally introduce water to prepare the pseudoboehmite dry glue powder into the formed material when preparing the formed raw material, thereby simplifying the overall process flow, reducing the overall operation energy consumption, avoiding the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material, and greatly improving the operation environment.
Description
Technical Field
The invention relates to the technical field of alumina forming, in particular to a boron-containing hydrated alumina composition and a preparation method thereof, and also relates to a boron-containing hydrated alumina formed body and an alumina formed body which are formed by the boron-containing hydrated alumina.
Background
In the conventional method, an alumina molded body, particularly a γ -alumina molded body, is often used as an adsorbent or a carrier of a supported catalyst because of its good pore structure, suitable specific surface area and high heat resistance stability. The alumina is usually prepared from dried hydrated alumina, such as pseudoboehmite, by molding, drying and high-temperature roasting.
Based on the above knowledge, as shown in fig. 1, the prepared wet alumina gel needs to be dried to obtain the pseudoboehmite dry gel powder, then the pseudoboehmite dry gel powder is taken as a starting point, the extrusion aid and the optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and after kneading and forming, the formed product is dried and optionally calcined to be used as the adsorbent or the carrier. The main problems of this preparation method are the high dust pollution and the high energy consumption.
In order to reduce dust pollution and improve working environment, researchers have realized that raw materials used for forming should be changed, and have begun to try to prepare alumina formed products using hydrated alumina wet gel or semi-dried pseudo-boehmite as raw materials.
US4613585 discloses a process for preparing an alumina catalyst support, which comprises the steps of:
(a) pouring an aluminum sulfate solution and a sodium aluminate solution simultaneously into a vessel containing deionized water to react the aluminum sulfate solution and the sodium aluminate solution under reaction conditions of pH6.0 to 8.5 and a temperature of 50 to 65 ℃, thereby preparing a first aqueous slurry containing amorphous aluminum hydroxide;
(b) adding an aqueous sodium aluminate solution to the first aqueous slurry in an amount sufficient to neutralize the first aqueous slurry, the total amount of sodium aluminate solution used in steps (a) and (b) corresponding to 0.95-1.05 of the stoichiometric amount of aluminum sulfate used in step (a), thereby preparing a second aqueous slurry having Al in the second aqueous slurry2O3A concentration of 7 wt% or more;
(c) filtering amorphous aluminum hydroxide in the second water slurry to obtain a filter cake, washing the obtained filter cake with dilute ammonia water, washing with dilute nitric acid solution, washing with dilute ammonia water to remove sulfate radical anions and sodium cation impurities, and adjusting the pH value of the filter cake to be within the range of 7.5-10.5;
(d) then, without aging the filter cake, the filter cake is dewatered on a filter press and Al is added thereto2O3Is increased to 28 to 35% by weight and the filter cake is kneaded in a self-cleaning type mixer at a pH in the range of 7.5 to 10.5 for a residence time of 10s or more to grow the pseudoboehmite particles in a short time, thereby obtaining agglomerates containing these particles;
(e) extruding the dough obtained in step (d) to form an extrudate, and then drying and roasting to obtain the extrudate.
From the method disclosed in US4613585, although the hydrated alumina wet gel can be shaped, there are limitations from the conditions for preparing amorphous aluminum hydroxide to kneading equipment and kneading conditions, resulting in complicated process operations. Also, the support prepared by the method should not have high strength and hardly meet the requirements for industrial applications because of high content of free water in the extrudate prepared by the method and the porosity of the extrudate obtained by drying and firing. Meanwhile, the carrier prepared by the method is difficult to regulate and control the pore structure of the carrier, so that the requirements of various use occasions are difficult to meet.
CN103769118A discloses a heavy oil hydrogenation catalyst, which comprises a carrier and an active component, wherein the carrier is alumina, the active component is metal of VIII group and/or VIB group, the VIII group metal is Co or Ni, the VIB group metal is Mo or W, and the alumina is prepared by molding pseudo-boehmite with a dry basis content of below 50%. The preparation process of the pseudo-boehmite with the dry basis content of less than 50 percent comprises the following steps: (1) carrying out neutralization gelling reaction on the aluminum salt solution and a precipitator; (2) filtering and recovering a solid product of the gelling reaction; (3) the solid product is dried to obtain the product with the dry content of below 50 percent.
CN103769118A adopts pseudoboehmite with a dry content of less than 50% to prepare an alumina carrier, and the pseudoboehmite with a dry content of less than 50% is obtained by drying a solid product separated from a mixture obtained by gelling reaction, which is a method difficult to implement in the actual operation process, mainly because:
(1) the incompletely dried pseudo-boehmite has strong viscosity and difficult transfer, and is easy to cause secondary dust pollution;
(2) drying is started from the surface, and the drying of a wet solid product separated from a mixture obtained by the gelling reaction belongs to incomplete drying, so that a sandwich biscuit phenomenon exists, namely, the surface of part of the pseudo-boehmite is dried (namely, the dried surface is basically free of free water), the inner part is still kept in a wet state (namely, the content of the free water in the non-dried inner part is basically kept at the level before drying), hard particles are formed because the surface is dried, and when the pseudo-boehmite which is not completely dried through is added with a peptizer and/or a binder and the like and is kneaded and formed, the hard particles formed in the drying process are easy to cause blockage in the extrusion process, so that the production efficiency is influenced;
(3) the dry basis of the pseudo-boehmite is difficult to be stably controlled, the instability of the dry basis can cause great interference to the forming, so that the forming process is also very unstable, the unqualified product quantity is increased, and the production efficiency is low;
(4) CN103769118A adopts a conventional forming process during forming, however, because the dry basis (35-50%) of the pseudo-boehmite adopted by the method is far lower than the conventional dry basis content (about 70%), namely the water content is high, extrusion pressure is not generated basically in the extrusion forming process, the carrier obtained after drying and roasting an extrudate has basically no mechanical strength, and the carrier can be pulverized only by applying a little external force, so that the possibility of industrial application is not provided, and the problem is the biggest problem faced by the technology.
In summary, how to simplify the preparation process of the alumina carrier and reduce the operation energy consumption, and at the same time, reduce the dust pollution in the preparation process of the alumina carrier is still an urgent technical problem to be solved on the premise of ensuring that the alumina carrier meeting the use industrial use requirements can be obtained.
Disclosure of Invention
The invention aims to simplify the preparation process flow of the alumina carrier, reduce the dust pollution in the preparation process of the alumina carrier and simultaneously ensure that the prepared carrier can meet the industrial use requirement.
Aiming at the problems of the preparation of alumina carriers of US4613585 and CN103769118A, the inventor of the present invention has a new approach to mix a compound containing at least two proton acceptor sites in the molecular structure with hydrated alumina wet gel directly from the synthesis reaction, and the formed mixture can be shaped, and the shaped body obtained by drying and optional roasting can have the strength meeting the industrial requirements. The present invention has been completed based on this finding.
According to a first aspect of the present invention there is provided a boron-containing hydrated alumina composition comprising hydrated alumina, a compound having at least two proton acceptor sites and a boron-containing compound,
of said composition
A value of 5 or less, said
The values are obtained by the following methodAnd (3) determination: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
according to a second aspect of the present invention, there is provided a process for preparing a boron-containing hydrated alumina composition, which comprises mixing the components of a feedstock composition comprising a hydrated alumina wet gel, a compound having at least two proton acceptor sites and a boron-containing compound, the i-value of the hydrated alumina wet gel being not less than 60%, the compound having at least two proton acceptor sites being used in such an amount that the composition finally prepared is a boron-containing hydrated alumina composition
The value of the amount of the organic acid is 5 or less,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the above-mentioned
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w1Is calculated by formula I
The value of the one or more of,
according to a third aspect of the present invention there is provided a boron-containing hydrated alumina composition produced by the process of the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a boron-containing hydrated alumina compact formed from the boron-containing hydrated alumina composition of the first aspect of the present invention or the boron-containing hydrated alumina composition of the third aspect of the present invention.
According to a fifth aspect of the present invention, there is provided a method for producing a boron-containing hydrated alumina compact, which comprises forming the boron-containing hydrated alumina composition according to the first aspect of the present invention or the boron-containing hydrated alumina composition according to the third aspect of the present invention, and drying the obtained form.
According to a sixth aspect of the present invention, there is provided a boron-containing hydrated alumina compact produced by the method of the fifth aspect of the present invention.
According to a seventh aspect of the present invention, there is provided an alumina compact formed from the boron-containing hydrated alumina composition of the first aspect of the present invention or the boron-containing hydrated alumina composition of the third aspect of the present invention.
According to an eighth aspect of the present invention, there is provided a method for producing an alumina formed body, which comprises forming the boron-containing hydrated alumina composition according to the first aspect of the present invention or the boron-containing hydrated alumina composition according to the third aspect of the present invention, and drying and firing the obtained formed body.
According to a ninth aspect of the present invention, there is provided an alumina compact produced by the method according to the eighth aspect of the present invention.
According to a tenth aspect of the present invention, there is provided a method for producing a hydrous alumina, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%, more preferably not more than 82%, further preferably not more than 80%, and further preferably not more than 78.5%;
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(2) mixing the first hydrated alumina wet gel, a compound having at least two proton acceptor sites and a boron-containing compound using the method of the second aspect of the invention to obtain a boron-containing hydrated alumina composition;
(3) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(4) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(5) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
According to an eleventh aspect of the present invention, there is provided a method for producing a hydrous alumina, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel,
in (2-1) and (2-2), the solid-liquid separation is carried out under such conditions that the second hydrated alumina wet gel has an i value of not less than 60%, preferably not less than 62%, more preferably not more than 82%, further preferably not more than 80%, further preferably not more than 78.5%,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(3) mixing a second hydrated alumina wet gel, a compound having at least two proton acceptor sites and a boron-containing compound using the method of the second aspect of the invention to obtain a boron-containing hydrated alumina composition;
(4) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(5) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(6) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
According to a twelfth aspect of the present invention, there is provided a molded body produced by the method according to the tenth or eleventh aspect of the present invention.
According to a thirteenth aspect of the present invention, there is provided a boron-containing hydrated alumina compact according to the present invention and use of the alumina compact as a carrier or adsorbent.
According to a fourteenth aspect of the present invention, there is provided a catalyst having a hydrogenation catalytic action, comprising a carrier and a hydrogenation active component supported on the carrier, wherein the carrier is a boron-containing hydrated alumina compact according to the present invention or an alumina compact according to the present invention.
According to a fifteenth aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation active component on a carrier, wherein the carrier is a boron-containing hydrated alumina compact according to the present invention or an alumina compact according to the present invention.
According to a sixteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having hydrocatalytic action, wherein the catalyst having hydrocatalytic action is the catalyst according to the fourteenth aspect of the present invention or the catalyst prepared by the method according to the fifteenth aspect of the present invention.
Compared with the prior process method (as shown in figure 1) for preparing the alumina carrier by taking the pseudo-boehmite dry glue powder as the starting material, the invention directly takes the hydrated alumina wet gel prepared by the synthesis reaction as the starting material for forming, and has the following advantages:
(1) the step of drying the hydrated alumina wet gel in the prior art is omitted, and when the forming raw material is prepared, the pseudo-boehmite dry glue powder is prepared into a formable material without additionally introducing water, so that the overall process flow is simplified, and the overall operation energy consumption is reduced;
(2) avoids dust pollution caused by adopting the pseudo-boehmite dry glue powder as a raw material, and greatly improves the operation environment.
Compared with the prior art, such as US4613585 and CN103769118A, which directly takes the hydrated alumina wet gel as the starting material to prepare the carrier, the process of the invention is simpler and has stronger operability, and can effectively improve the strength of the finally prepared formed body, and simultaneously can adjust the pore size distribution of the finally prepared formed body, thereby meeting the requirements of various use occasions. The reason why the present invention can produce a molded body having a higher strength from a hydrated alumina wet gel as a starting material may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel interact to form hydrogen bonds to adsorb the free water in the hydrated alumina wet gel, and simultaneously, the compound with at least two proton acceptor sites and the hydroxyl in the molecular structure of the hydrated alumina can also perform hydrogen bond interaction to play a role of physical peptization, so that the hydrated alumina wet gel can be molded, and the finally prepared molded body has higher strength.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of a molding process commonly used in current industrial applications.
FIG. 2 is a preferred embodiment of a method of making a boron-containing hydrated alumina composition according to the present invention.
Fig. 3 is a preferred embodiment of a molding process flow according to the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
According to a first aspect of the present invention there is provided a boron-containing hydrated alumina composition comprising hydrated alumina, a compound having at least two proton acceptor sites and a boron-containing compound.
The hydrated alumina may be one or more selected from alumina trihydrate and alumina monohydrate. The hydrated alumina preferably comprises alumina monohydrate, more preferably alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudo-boehmite. In a preferred embodiment of the invention, the hydrated alumina contains pseudoboehmite, more preferably pseudoboehmite. The hydrated alumina composition according to this preferred embodiment is particularly suitable for the preparation of shaped bodies for use as catalyst supports.
According to the boron-containing hydrated alumina composition, the hydrated alumina is directly sourced from the wet hydrated alumina gel and is not sourced from the dry hydrated alumina gel powder. In the present invention, the term "hydrated alumina wet gel" means an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for lowering its i value to 60% or less (preferably 62% or less). In the present invention, the value of i is determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the synthesis reaction refers to a reaction for preparing an aluminum hydroxide gel, and may be a synthesis reaction of a hydrated alumina gel commonly used in the art, and specifically, a precipitation method (including an acid method and an alkaline method), a hydrolysis method, an seeded precipitation method, and a rapid dehydration method may be mentioned. The synthesized hydrated alumina gel may be either a hydrated alumina gel that has not undergone aging or a hydrated alumina gel that has undergone aging. The specific operating methods and conditions for the precipitation, hydrolysis, seeding and flash dehydration processes may be routinely selected and will be described hereinafter. The hydrated alumina wet gel can be obtained by optionally aging the hydrated alumina gel obtained by the synthesis reaction, washing and performing solid-liquid separation, and collecting the solid phase.
Unlike hydrated alumina derived from dry gelatine powder, the hydrated alumina directly derived from hydrated alumina gel undergoes a phase change during storage. For example, the phase of the hydrated alumina in the composition after exposure to ambient temperature and under closed conditions may change for 72 hours. The ambient temperature depends on the environment in which it is placed and may typically be in the range of 5-50 deg.C, such as 20-40 deg.C. The closed condition means that the composition is placed in a closed container, which may be a closed container (such as a can, pail or box) or a closed flexible wrap (such as a lidded bag), which may be paper and/or a polymeric material, preferably a polymeric material such as plastic.
In one example, where the hydrated alumina directly derived from the hydrated alumina gel comprises pseudo-boehmite (e.g., the hydrated alumina directly derived from the hydrated alumina gel is pseudo-boehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after being left to stand being higher than the alumina trihydrate content in the composition before being left to stand. In this example, the alumina trihydrate content in the composition after placement is generally increased by at least 0.5%, preferably by at least 1%, preferably by from 1.1% to 2%, based on the total amount of alumina trihydrate content in the composition before placement.
The boron-containing hydrated alumina composition according to the present invention further contains a compound having at least two proton acceptor sites. The boron-containing hydrated alumina composition according to the present invention can be used for molding (particularly extrusion molding) without using dry rubber powder as a starting material, and the reason why the resulting molded article has a higher strength may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel generate hydrogen bond interaction, so that the free water is adsorbed, and simultaneously, the compound and the hydroxyl in the molecular structure of the hydrated alumina generate interaction to play a role in peptization.
In the compound having at least two proton acceptor sites, the proton acceptor site refers to a site capable of forming a hydrogen bond with water and a hydroxyl group in the molecular structure of the compound. Specific examples of the proton acceptor site include, but are not limited to, one or two or more of fluorine (F), oxygen (O), and nitrogen (N). Specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, compounds having one or more groups selected from hydroxyl groups, carboxyl groups, amino groups, ether linkages, aldehyde groups, carbonyl groups, amide groups, and fluorine atoms in the molecular structure, preferably hydroxyl groups and/or ether linkages.
The compound having at least two proton acceptor sites may be an organic compound, an inorganic compound, or a combination of an organic compound and an inorganic compound. An organic compound having at least two proton acceptor sites is employed, which can be removed by a calcination process. By using an inorganic compound having at least two proton acceptor sites, part of the elements in the inorganic compound can remain in the finally produced shaped body, whereby auxiliary elements can be introduced into the shaped body by means of the inorganic compound.
In a preferred embodiment of the present invention, the compound having at least two proton acceptor sites is a polymer having a plurality of (e.g., three or more) proton acceptor sites in a molecular structure. According to this preferred embodiment, a better physical peptization effect is obtained, which further increases the strength of the finally produced shaped body, in particular when shaping is carried out by an extrusion process. Preferably, the polymer is an organic polymer. According to the preferred embodiment, specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, one or more of polyhydroxy compounds, polyethers, and acrylic-type polymers.
The polyol compound may be exemplified by, but not limited to, polysaccharides, etherified polysaccharides and polyols.
The polysaccharide may be isopolyThe sugar may be a heteropolysaccharide or a combination of a homopolysaccharide and a heteropolysaccharide. Specific examples of the polysaccharide and its etherified product include, but are not limited to, dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide. The cellulose ether is an ether derivative in which hydrogen atoms of partial hydroxyl groups in a cellulose molecule are substituted with hydrocarbon groups, and the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl and unsubstituted hydrocarbyl. The unsubstituted hydrocarbon group is preferably an alkyl group (e.g., C)1-C5Alkyl groups of (ii). In the present invention, C1-C5Specific examples of the alkyl group of (1) include C1-C5Straight chain alkyl of (2) and C3-C5The branched alkyl group of (a), may be, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl. The substituted hydrocarbon group may be, for example, an alkyl group substituted with a hydroxyl group, a carboxyl group, a cyano group or an aryl group (e.g., C)1-C5Alkyl substituted by hydroxy, C1-C5Alkyl substituted by carboxyl, C substituted by aryl1-C5Alkyl) which may be phenyl or naphthyl. Specific examples of the substituted hydrocarbon group may include, but are not limited to: cyano, benzyl, phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose.
Specific examples of the polyol include, but are not limited to, one or more of polyvinyl alcohol, partially acetalized polyvinyl alcohol (the acetalization degree may be 95% or less, preferably 80% or less, more preferably 70% or less, and further preferably 50% or less), polyether polyol, and polyester polyol.
Specific examples of the polyether include, but are not limited to, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, and polytetrahydrofuran.
The acrylic acid-type polymer refers to a polymer containing acrylic acid-type monomer units, which may be specifically, but not limited to, acrylic acid monomer units and alkyl acrylic acid monomer units (preferably, C)1-C5More preferably a methacrylic acid monomer unit). Specific examples of the acrylic polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-methyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, methacrylic acid-methyl acrylate copolymer, and methacrylic acid-methyl methacrylate copolymer.
In this preferred embodiment, the compound having at least two proton acceptor sites more preferably contains a polysaccharide and/or an etherified polysaccharide, and still more preferably a polysaccharide and/or an etherified polysaccharide.
In a more preferred embodiment of the invention, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. According to this more preferred embodiment, the moulded body formed from the composition according to the invention has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.
In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.
In the boron-containing hydrated alumina composition of the present invention, the boron-containing compound may be a boron-containing compound that is conventional in the art, and may be, for example, at least one of boric acid, sodium borate, boron oxide and ammonium borate.
Compositions according to the inventionIs/are as follows
The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, and further preferably 3.2 or less.
The value may be 1.2 or more, preferably 1.3 or more, and more preferably 1.4 or more. In one embodiment, the hydrated alumina composition is
The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.85, for example, may be 1.85 to 3.5, more preferably not less than 1.9, for example, may be 1.9 to 3.2. The hydrated alumina composition according to this embodiment can produce shaped bodies having a bimodal distribution of pore sizes. In another embodiment, of the hydrated alumina composition
The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. The hydrated alumina composition according to this embodiment can produce a shaped body having a monomodal distribution of pore diameters.
In the present invention,
the values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
the composition according to the invention, the compound having at least two proton acceptor sites being present in an amount such that the composition
The value meets the above requirements. Preferably, the compound having at least two proton acceptor sites may be contained in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, and still more preferably 3.5 to 17 parts by weight, relative to 100 parts by weight of the hydrated alumina.
According to the composition of the invention, the boron-containing compound is represented by B, relative to 100 parts by weight of the hydrated alumina2O3The content may be 1.5 to 40 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 to 25 parts by weight.
The composition according to the invention may or may not contain a peptizing agent. The peptizing agent may be an agent having a gelling effect, which is generally used in the technical field of preparation of alumina moldings, and specific examples thereof may include, but are not limited to, alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid, and trichloroacetic acid.
According to the composition of the present invention, the compound having at least two proton acceptor sites can perform a physical peptization effect, particularly when the compound having at least two proton acceptor sites is a polymer containing at least two proton acceptor sites, so that the amount of a peptizing agent can be reduced, and even the peptizing agent can be omitted.
In a preferred embodiment of the present invention, the content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, with respect to 100 parts by weight of the hydrated alumina.
In a particularly preferred embodiment of the invention, the composition according to the invention does not contain a peptizing agent. According to the composition of this particularly preferred embodiment, when used for the production of a shaped body, the produced hydrated alumina shaped body can be used as an adsorbent or a carrier even if it is converted into an alumina shaped body without calcination, because when the unfired hydrated alumina shaped body contains a peptizing agent, the peptizing agent is dissolved during adsorption and impregnation, and is lost in a large amount, so that the shaped body is dissolved, pulverized, and collapsed in the channels, and finally loses its shape, and thus cannot be used as an adsorbent or a carrier.
According to a second aspect of the present invention, there is provided a method for producing a boron-containing hydrated alumina composition, which comprises mixing the components of a raw material composition to obtain the boron-containing hydrated alumina composition, i.e., the mixture obtained by mixing is the boron-containing hydrated alumina composition.
According to the method for preparing a boron-containing hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a compound having at least two proton acceptor sites, and a boron-containing compound. The types of said compound having at least two proton acceptor sites and said boron-containing compound have been described in detail above and will not be described in detail herein.
The hydrated alumina wet gel can be synthesized by a conventional method, for example, by one or more of precipitation (including acid and alkaline methods), hydrolysis, seed separation, and flash dehydration. Generally, the hydrated alumina gel solution is obtained by optionally aging, washing and solid-liquid separation.
The precipitation method comprises an acid method and an alkali method. The acid method is to precipitate aluminum salt with alkaline compound. The alkaline method is to carry out precipitation reaction on aluminate by using an acidic compound. In the precipitation method, after the mixture obtained by the precipitation reaction is optionally aged (preferably, aged), solid-liquid separation is performed, and the separated solid phase is washed to obtain the hydrated alumina wet gel.
The kind of the aluminum salt and the aluminate may be conventionally selected. Specific examples of the aluminum salt may include, but are not limited to, one or two or more of aluminum sulfate, aluminum chloride, and aluminum nitrate. Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate, potassium metaaluminate, and magnesium metaaluminate.
The basic compound and the acidic compound may be conventionally selected. The alkaline compound can be various common compounds capable of making water alkaline, and can be selected from ammonia, hydroxide and alkaline salt. The hydroxide may be a common water-soluble hydroxide such as an alkali metal hydroxide. The basic salt may be a common salt that decomposes in water to make the water basic, such as meta-aluminates, carbonates and bicarbonates. Specific examples of the basic compound may include, but are not limited to, one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate. The acidic compound can be various common compounds capable of making water acidic, and can be inorganic acid and/or organic acid. Specific examples of the acidic compound may include, but are not limited to, one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, and oxalic acid. The carbonic acid may be generated in situ by the introduction of carbon dioxide.
The precipitation reaction may be carried out under conventional conditions, and the present invention is not particularly limited thereto. Generally, the alkaline compound or the acidic compound is used in such an amount that the pH of the aluminium salt solution or the aluminate solution is 6-10, preferably 7-9. The precipitation reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.
The method for preparing the hydrated alumina wet gel by the hydrolysis method may include: subjecting an aluminum-containing compound to hydrolysis reaction, optionally aging (preferably aging) the mixture obtained by the hydrolysis reaction, then performing solid-liquid separation, and washing the separated solid phase to obtain the hydrated alumina wet gel.
The aluminum-containing compound may be an aluminum-containing compound generally used in a process for preparing a hydrated alumina gel by a hydrolysis method. The aluminum-containing compound is preferably an organoaluminum compound which can undergo hydrolysis reaction, and more preferably an aluminum alkoxide. Specific examples of the aluminum-containing compound may include, but are not limited to, one or more of aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate.
The hydrolysis reaction of the present invention is not particularly limited, and may be carried out under conventional conditions. Generally, the hydrolysis reaction may be carried out at a pH of 3 to 11, preferably 6 to 10. The hydrolysis reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.
In the precipitation method and the hydrolysis method, the aging conditions are not particularly limited and may be carried out under conventional conditions. In general, the ageing can be carried out at temperatures of from 35 to 98 deg.C, preferably from 40 to 80 deg.C. The duration of the aging may be 0.2 to 6 hours.
The method for preparing the hydrated alumina wet gel by the seed precipitation method can comprise the following steps: adding seed crystals into the supersaturated aluminate solution, decomposing to generate aluminum hydroxide, carrying out solid-liquid separation on a mixture obtained by decomposition, and washing a separated solid phase to obtain the hydrated alumina wet gel. Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate, potassium metaaluminate, and magnesium metaaluminate.
The method for preparing the hydrated alumina wet gel by the rapid dehydration method may include: calcining hydrated alumina at 600-950 deg.C, preferably 650-800 deg.C, performing hydrothermal treatment on the calcined product, and performing solid-liquid separation on the mixture obtained by the hydrothermal treatment to obtain hydrated alumina wet gel. The duration of the calcination may be 1 to 6 hours, preferably 2 to 4 hours. The hydrothermal treatment may be carried out at a temperature of 120 to 200 c, preferably 140 to 160 c. The hydrothermal treatment is usually carried out under autogenous pressure in a closed vessel.
In the precipitation method, the hydrolysis method, the seed precipitation method and the rapid dehydration method, the solid-liquid separation can be performed by a conventional method, and specifically, the solid-liquid separation can be performed by filtration, centrifugation or a combination of the two.
According to the method for preparing the boron-containing hydrated alumina composition of the present invention, the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%. The i value of the hydrated alumina wet gel is preferably not higher than 82%, more preferably not higher than 80%, and further preferably not higher than 78.5%.
The hydrated alumina wet gel with the value i meeting the requirement can be obtained by controlling the solid-liquid separation conditions when the prepared hydrated alumina gel-containing solution is subjected to solid-liquid separation. In one embodiment of the present invention, the solid-liquid separation is performed once or twice or more, and at least the last solid-liquid separation is performed by a pressure filtration apparatus and/or a vacuum filtration apparatus. In this embodiment, the value of the hydrated alumina wet gel i obtained is controlled by adjusting the magnitude of the applied pressure and/or vacuum. Specific examples of the pressure filtration device include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. In order to control the i value of the obtained hydrated alumina wet gel, natural wind or pressurized wind can be adopted to blow the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.
According to the method for producing a boron-containing hydrated alumina composition of the present invention, the hydrated alumina wet gel obtained by the solid-liquid separation is generally not subjected to a dehydration treatment for reducing the i value thereof to 60% or less (preferably 62% or less).
According to the method for preparing a boron-containing hydrated alumina composition of the present invention, the compound having at least two proton acceptor sites is used in an amount enabling the final preparation of the hydrated alumina composition
The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, and further preferably 3.2 or less. The compound having at least two proton acceptor sites is preferably used in an amount such that the final prepared hydrated alumina composition is
The value is 1.2 or more, preferably 1.3 or more, and more preferably 1.4 or more. In one embodiment, the compound having at least two proton acceptor sites is preferably used in an amount such that the final prepared hydrated alumina composition is
The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.85, for example, may be 1.85 to 3.5, more preferably not less than 1.9, for example, may be 1.9 to 3.2. The hydrated alumina composition according to this embodiment can produce shaped bodies having a bimodal distribution of pore sizes. In another embodiment, the compound having at least two proton acceptor sites is preferably used in an amount such that the final prepared hydrated alumina composition is
The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. The hydrated alumina composition according to this embodiment can produce a shaped body having a monomodal distribution of pore diameters.
Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, and still more preferably 3.5 to 17 parts by weight, relative to 100 parts by weight of the hydrated alumina wet gel.
In a more preferred embodiment, the compound having at least two proton acceptor sites comprises galactomannan and cellulose ether. The molded body formed from the composition according to this more preferred embodiment has higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.
In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.
The content of the boron-containing compound in the raw material mixture may be carried out according to the content of boron element expected to be introduced in the finally prepared boron-containing hydrated alumina compositionAnd (4) selecting. Generally, the boron-containing compound is represented by B relative to 100 parts by weight of the hydrated alumina wet gel2O3The amount may be 1.5 to 40 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 to 25 parts by weight.
According to the method of preparing the boron-containing hydrated alumina composition of the present invention, the boron-containing compound, the compound having at least two proton acceptor sites, and the hydrated alumina wet gel may be mixed in various mixing sequences.
In one embodiment, the boron-containing compound may be mixed during the preparation of the hydrated alumina wet gel, the boron-containing compound may be added to the prepared hydrated alumina wet gel, a part of the boron-containing compound may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the boron-containing compound may be added to the prepared hydrated alumina wet gel, and the mixing of the boron-containing compound may be performed at one, two, or three of the above-mentioned addition timings. When the boron-containing compound is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the boron-containing compound may be performed in one, two, three or four of the precipitation reaction process, the aging process, the solid-liquid separation process and the washing process. Preferably, the operation of mixing the boron-containing compound is carried out in a solid-liquid separation process.
In another embodiment, the boron-containing compound is mixed after the hydrated alumina wet gel is prepared. In this embodiment, the boron-containing compound may be mixed with the hydrated alumina wet gel first, followed by mixing of the compound having at least two proton acceptor sites; alternatively, the compound having at least two proton acceptor sites may be mixed with the hydrated alumina wet gel prior to mixing the boron-containing compound; it is also possible to first mix a portion of the boron-containing compound with the wet gel of hydrated alumina and then mix the remaining portion of the boron-containing compound with a compound having at least two proton acceptor sites.
According to the method for preparing the boron-containing hydrated alumina composition of the present invention, the raw material mixture may or may not contain a peptizing agent. Preferably, the content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, with respect to 100 parts by weight of hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, the method for producing a boron-containing hydrated alumina composition according to the present invention more preferably does not include the step of adding a peptizing agent to the raw material mixture.
According to the method for preparing the boron-containing hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with the compound having at least two proton acceptor sites and the boron-containing compound by a conventional method. The hydrated alumina wet gel may be mixed under shear with a compound having at least two proton acceptor sites and a boron-containing compound. In one embodiment, the mixing is by stirring. The hydrated alumina wet gel may be mixed with the compound having at least two proton acceptor sites and the boron-containing compound in a vessel having a stirring device by stirring to mix them uniformly to obtain the boron-containing hydrated alumina composition according to the present invention. The stirring can be carried out in a vessel with a stirring device or in a beater. In another embodiment, the mixing is by kneading. The hydrated alumina wet gel may be kneaded with a compound having at least two proton acceptor sites and a boron-containing compound in a kneader to obtain the boron-containing hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the method for preparing the boron-containing hydrated alumina composition of the present invention, stirring and mixing may be used in combination to mix the hydrated alumina wet gel with the compound having at least two proton acceptor sites and the boron-containing compound. In this case, it is preferable to perform stirring and kneading.
According to the method for producing a hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the boron-containing hydrated alumina composition can be produced
The value satisfies the above requirements. In general, from the viewpoint of improving the homogeneity of mixingFrom the viewpoint of the quality, water may be additionally added during the mixing process. Generally, the weight ratio of the supplemental added water to the compound having at least two proton acceptor sites may be from 5 to 15: 1, preferably 8 to 12: 1, more preferably 9 to 10: 1.
according to a third aspect of the present invention there is provided a boron hydrated alumina containing composition produced by the process of the second aspect of the present invention.
The boron-containing hydrated alumina composition according to the present invention can be shaped by a conventional method to obtain a hydrated alumina carrier or an alumina carrier.
According to a fourth aspect of the present invention, there is provided a boron-containing hydrated alumina compact formed from the boron-containing hydrated alumina composition of the first aspect of the present invention or the boron-containing hydrated alumina composition of the third aspect of the present invention.
The boron-containing hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain the boron-containing hydrated alumina molded article according to the present invention.
The molding method is not particularly limited, and various molding methods commonly used in the art may be employed, for example: extrusion, spraying, spheronization, tableting or a combination thereof. In a preferred embodiment of the invention, the shaping is carried out by means of extrusion.
The temperature at which the shaped article is dried may be a conventional choice in the art. Generally, the temperature of the drying may be 60 ℃ or more and not higher than 350 ℃, preferably 80 to 300 ℃, more preferably 110 to 260 ℃. The drying time can be properly selected according to the drying temperature, so that the volatile content in the finally obtained boron-containing hydrated alumina forming body meets the use requirement. Generally, the duration of the drying may be 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours, and further preferably 2 to 4 hours. The drying may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed by nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.
The boron-containing hydrated alumina forming body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, or butterfly.
The boron-containing hydrated alumina forming body has abundant pore structures and adjustable pore size distribution.
In one embodiment, the boron-containing hydrated alumina compact has a bimodal pore size distribution as measured by mercury intrusion. Wherein the most probable pore size is 4-20nm (preferably 5-15nm) and more than 20nm (such as 20.5-35nm, preferably 21-30 nm).
In another embodiment, the boron-containing hydrated alumina formed bodies have a unimodal pore size distribution as measured by mercury intrusion. Wherein the pore diameter of the most probable pore is 4-25nm, preferably 15-22 nm.
According to the boron-containing hydrated alumina formed body of the present invention, the boron-containing hydrated alumina formed body has high strength. In general, the boron-containing hydrated alumina compact according to the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm is acceptable), preferably 12N/mm or more, and more preferably 15N/mm or more. In one example, the boron-containing hydrated alumina compact has a radial crush strength of 12 to 35N/mm, preferably 15 to 35N/mm. In a more preferred embodiment, the boron-containing hydrated alumina compact has a radial crush strength of 15 to 32N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.
According to a fifth aspect of the present invention, there is provided a method for producing a boron-containing hydrated alumina compact, which comprises forming the boron-containing hydrated alumina composition according to the first aspect of the present invention or the boron-containing hydrated alumina composition according to the third aspect of the present invention, and drying the obtained formed product to obtain the boron-containing hydrated alumina compact.
The methods and conditions for the shaping and drying are the same as those described for the fourth aspect of the present invention and will not be described in detail here.
According to the invention containing boronProcess for the preparation of hydrated alumina moldings by modification of boron-containing hydrated alumina compositions
Values to obtain hydrated alumina shaped bodies with different pore size distributions.
In one embodiment of the invention, the boron-containing hydrated alumina composition
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of said boron-containing hydrated alumina composition
The value is not less than 1.85, and may be, for example, 1.85 to 3.5. More preferably, of said boron-containing hydrated alumina composition
The value is not less than 1.9, and may be, for example, 1.9 to 3.2. The pore size of the boron-containing hydrated alumina moldings prepared according to this embodiment is bimodal as determined by mercury intrusion. The most probable pore diameters are 4-20nm (preferably 5-15nm) and more than 20nm (e.g. 20.5-35nm, preferably 21-30nm), respectively.
In another embodiment of the present invention, the boron-containing hydrated alumina composition
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of said boron-containing hydrated alumina composition
The value is not higher than 1.7, and may be, for example, 1.3 to 1.7. The pore size of the boron-containing hydrated alumina moldings produced according to this embodiment has a monomodal distribution, determined by mercury intrusion. The mode pore size is 4-25nm, preferably 15-22 nm.
According to a sixth aspect of the present invention, there is provided a boron-containing hydrated alumina compact produced by the method of the fifth aspect of the present invention.
The boron-containing hydrated alumina forming body prepared by the method has higher strength. Generally, the boron-containing hydrated alumina compact produced by the method of the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm), preferably 12N/mm or more, and more preferably 15N/mm or more. In one example, the boron-containing hydrated alumina compact produced by the process of the present invention has a radial crush strength of from 12 to 35N/mm, preferably from 15 to 35N/mm. In a more preferred embodiment, the boron-containing hydrated alumina compact produced by the process of the present invention has a radial crush strength of from 15 to 32N/mm.
According to a seventh aspect of the present invention, there is provided an alumina compact formed from the boron-containing hydrated alumina composition of the first aspect of the present invention or the boron-containing hydrated alumina composition of the third aspect of the present invention.
The boron-containing hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and fired in sequence to obtain the alumina molded body.
The methods and conditions for the shaping and drying are the same as those described for the fourth aspect of the present invention and will not be described in detail here.
The conditions for calcination in the present invention are not particularly limited, and may be selected conventionally in the art. Specifically, the temperature of the calcination may be 450 to 1500 ℃. In addition, the calcination temperature can be optimized according to the type of the hydrated alumina. In one embodiment, the hydrated alumina is pseudoboehmite and the calcination temperature is preferably 450 to 1100 ℃, more preferably 460 to 1000 ℃, and even more preferably 500 to 950 ℃. In another embodiment, the hydrated alumina is gibbsite and the calcination temperature is preferably from 800 to 1500 ℃, more preferably from 900 to 1400 ℃. The duration of the calcination may be 1 to 8 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed of nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.
The alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, or butterfly.
The alumina formed body has abundant pore structure and adjustable pore size distribution.
In one embodiment, the pore size distribution of the alumina compact is bimodal as determined by mercury intrusion. The most probable pore diameters are 4-20nm (preferably 7-18nm) and more than 20nm (e.g., 20-40nm, preferably 20-30nm), respectively.
In another embodiment, the pore size of the aluminum oxide shaped body is unimodal as determined by mercury intrusion. The pore size of the most probable pore is 4 to 20nm, preferably 10 to 20 nm.
According to the alumina formed body of the present invention, the alumina formed body has high strength. In general, the alumina molded body according to the present invention has a radial crush strength of 10N/mm or more (for example, may be 10 to 55N/mm), preferably 12N/mm or more, and more preferably 15N/mm or more. In one example, the alumina compact has a radial crush strength of 12 to 35N/mm, preferably 15 to 35N/mm. In a more preferred embodiment, the alumina compact has a radial crush strength of 15 to 32N/mm.
According to an eighth aspect of the present invention, there is provided a method for producing an alumina formed body, which comprises forming the boron-containing hydrated alumina composition according to the first aspect of the present invention or the boron-containing hydrated alumina composition according to the third aspect of the present invention, and drying and firing the obtained formed body.
The methods and conditions for forming, drying and firing are the same as those described in the seventh aspect of the present invention and will not be described in detail herein.
According to the method for producing an alumina molded body of the present invention, it is possible to modify the boron-containing hydrated alumina composition
To obtain alumina shaped bodies with different pore size distributions.
In one embodiment of the invention, the boron-containing hydrated alumina composition
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of said boron-containing hydrated alumina composition
The value is not less than 1.85, and may be, for example, 1.85 to 3.5. More preferably, of said boron-containing hydrated alumina composition
The value is not less than 1.9, and may be, for example, 1.9 to 3.2. The pore diameters of the alumina moldings produced according to this embodiment are bimodal, as determined by mercury intrusion. The most probable pore diameters are 4-20nm (preferably 7-18nm) and more than 20nm (e.g., 20.1-40nm, preferably 20.2-30nm), respectively.
In another embodiment of the present invention, the boron-containing hydrated alumina composition
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of said boron-containing hydrated alumina composition
The value is not higher than 1.7, and may be, for example, 1.3 to 1.7. The pore diameter of the aluminum oxide shaped bodies produced according to this embodiment is unimodal as determined by mercury intrusion. The pore size of the most probable pore is 4 to 20nm, preferably 10 to 20 nm.
According to a ninth aspect of the present invention, there is provided an alumina compact produced by the method of the eighth aspect of the present invention.
The alumina formed body prepared by the method has higher strength. Generally, the alumina compact produced by the method of the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm is acceptable), preferably 12N/mm or more, and more preferably 15N/mm or more. In one example, the alumina compact produced by the process of the invention has a radial crush strength of from 12 to 35N/mm, preferably from 15 to 35N/mm. In a more preferred embodiment, the alumina shaped bodies produced by the process according to the invention have a radial crush strength of from 15 to 32N/mm.
According to a tenth aspect of the present invention, there is provided a method for producing and molding hydrated alumina, as shown in fig. 2, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
(2) mixing the first hydrated alumina wet gel, a compound having at least two proton acceptor sites and a boron-containing compound using the method of the second aspect of the invention to obtain a boron-containing hydrated alumina composition;
(3) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(4) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(5) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
In the method according to the tenth aspect of the present invention, the operation of mixing the boron-containing compound may be performed during any of the operations of step (1) and/or step (2), and specifically, the operation of mixing the boron-containing compound may be performed during at least one of the preparation process of the hydrated alumina gel solution of step (1), the washing process, the solid-liquid separation process, and the mixing process of step (2).
In the step (1), the hydrated alumina gel solution is a hydrated alumina gel-containing solution which is obtained by a hydrated alumina gel synthesis reaction and is aged or not aged. The hydrated alumina gel solution can be prepared on site or transported from other production sites. Preferably, the hydrated alumina gel solution is a hydrated alumina wet gel solution prepared in situ. The synthesis method and conditions of the hydrated alumina gel have been described in detail above and will not be described herein.
Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in the step (1) to remove acidic substances and alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the presence of the acidic substances and the alkaline substances on the hydrated alumina gel is avoided, and meanwhile, the solid content of the hydrated alumina gel solution is increased. The washing in step (1) may be carried out under conventional conditions as long as the amounts of acidic substances and basic substances in the hydrated alumina gel solution can be reduced to meet the usual requirements.
In step (1), the solid-liquid separation conditions are such that the i-value content of the first hydrated alumina wet gel satisfies the i-value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention, that is, the i-value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 82%, more preferably not higher than 80%, and still more preferably not higher than 78.5%.
In step (2), the first hydrated alumina wet gel is mixed with a compound having at least two proton acceptor sites and a boron-containing compound using the method of the second aspect of the invention to obtain a boron-containing hydrated alumina composition. The i value of the first hydrated alumina wet gel fed to step (2) satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention.
In the step (2), the hydrated alumina composition can be determined according to the intended pore size distribution of the hydrated alumina molded body or the alumina molded body
Value of the method according to the fifth aspect of the invention and rootThe method according to the eighth aspect of the present invention is described in detail, and will not be described in detail.
In the step (3), the boron-containing hydrated alumina composition obtained in the step (2) is molded to obtain a boron-containing hydrated alumina molding. The forming method and the shape of the formed object can refer to the related description of the forming in the foregoing, and are not repeated herein.
In the step (4), the boron-containing hydrated alumina forming product obtained in the step (3) is dried to obtain a boron-containing hydrated alumina forming product. The drying conditions for drying the boron-containing hydrated alumina molding to obtain the boron-containing hydrated alumina molding are described in detail in the method of the fifth aspect of the present invention, and will not be described herein again.
Depending on the type of shaped body to be expected, step (5) may or may not be carried out. When step (5) is carried out, the whole of the boron-containing hydrated alumina compact obtained in step (4) may be fed to step (5) and calcined; part of the boron-containing hydrated alumina compact obtained in the step (4) may be fed to the step (5), so that the boron-containing hydrated alumina compact and the alumina compact can be simultaneously produced. The conditions for the calcination have been described in detail in the method of the eighth aspect of the present invention, and are not described herein again.
According to an eleventh aspect of the present invention, there is provided a method for producing and molding hydrated alumina, as shown in fig. 2, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
optionally (2), treating the first hydrated alumina wet gel with (2-1) or (2-2),
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel;
(3) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites and a boron-containing compound by using the method of the second aspect of the present invention to obtain a boron-containing hydrated alumina composition, wherein the hydrated alumina wet gel is the first hydrated alumina wet gel or the second hydrated alumina wet gel;
(4) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(5) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(6) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
In the method according to the eleventh aspect of the present invention, the operation of mixing the boron-containing compound may be performed during any of the operations of step (1), step (2) and step (3), and specifically, the operation of mixing the boron-containing compound may be performed during at least one of the preparation process and washing process of the hydrated alumina gel solution of step (1), the pulping process and solid-liquid separation process of step (2) and the mixing process of step (3).
In the step (1), the hydrated alumina gel solution is a hydrated alumina gel-containing solution which is obtained by a hydrated alumina gel synthesis reaction and is aged or not aged. The hydrated alumina gel solution can be prepared on site or transported from other production sites. Preferably, the hydrated alumina gel solution is a hydrated alumina wet gel solution prepared in situ. The synthesis method and conditions of the hydrated alumina gel have been described in detail above and will not be described herein.
Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in the step (1) to remove acidic substances and alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the presence of the acidic substances and the alkaline substances on the hydrated alumina gel is avoided, and meanwhile, the solid content of the hydrated alumina gel solution is increased. The washing in step (1) may be carried out under conventional conditions as long as the amounts of acidic substances and basic substances in the hydrated alumina gel solution can be reduced to meet the usual requirements.
In step (1), solid-liquid separation is also involved in the washing process to squeeze out the wash water to give a first hydrated alumina wet gel. The i value of the first hydrated alumina wet gel may be a value satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention, or may be a value higher than the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention.
In one embodiment, the first hydrated alumina wet gel has an i value content which satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention, i.e., the i value of the first hydrated alumina wet gel is not less than 60%, preferably not less than 62%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 82%, more preferably not higher than 80%, and still more preferably not higher than 78.5%.
According to this embodiment, the first hydrated alumina wet gel may be fed directly to step (3) to be mixed with a compound having at least two proton acceptor sites and a boron-containing compound. This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device can be compactly arranged, so that the discharge of the washing device can directly enter the mixing device.
According to this embodiment, the first hydrated alumina wet gel may also be sent to step (2) for treatment with (2-1). This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device cannot be compactly arranged, so that the discharge of the washing device cannot directly enter the mixing device.
In another embodiment, the first hydrated alumina wet gel has an i value of greater than 82% and fails to meet the requirements of the second aspect of the invention for mixing with a compound having at least two proton acceptor sites and a boron-containing compound. According to this embodiment, the first hydrated alumina wet gel is sent to step (2) and treated with either (2-1) or (2-2).
This embodiment is particularly suitable for the case where the separation capacity or the operating conditions of the solid-liquid separation device in the washing apparatus are insufficient to control the i value of the first hydrated alumina wet gel to satisfy the requirements described in the second aspect of the present invention, and the case where the washing apparatus and the mixing apparatus cannot be compactly arranged.
In the step (2), the first hydrated alumina wet gel is treated by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water to form a slurry, which can improve the transport properties of the hydrated alumina wet gel.
In the step (2-1), the amount of water added is selected according to the specific transportation equipment, so that the formed slurry can meet the transportation requirement.
The second hydrated alumina wet gel obtained in the step (2) has an i value satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention, that is, the i value of the hydrated alumina wet gel is not less than 60%, preferably not less than 62%. The second hydrated alumina wet gel preferably has an i value of not higher than 82%, more preferably not higher than 80%, and further preferably not higher than 78.5%.
The second hydrated alumina wet gel having an i value satisfying the above requirements can be obtained by controlling the conditions of the solid-liquid separation in the step (2). The method for adjusting the i value of the hydrated alumina wet gel by selecting the solid-liquid separation method and the conditions thereof has been described in detail above and will not be described in detail herein.
In step (3), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with a compound having at least two proton acceptor sites and a boron-containing compound using the method according to the second aspect of the present invention to obtain a boron-containing hydrated alumina composition. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to step (3) satisfy the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the present invention.
In the step (3), the hydrated alumina composition can be determined according to the desired pore size distribution of the boron-containing hydrated alumina compact or alumina compact
This is illustrated in the method according to the fifth aspect of the invention and in the method according to the eighth aspect of the invention and will not be described in detail here.
In the step (4), the boron-containing hydrated alumina composition obtained in the step (3) is molded to obtain a boron-containing hydrated alumina molding. The forming method and the shape of the formed object can refer to the related description of the forming in the foregoing, and are not repeated herein.
And (5) drying the boron-containing hydrated alumina forming product obtained in the step (4) to obtain a boron-containing hydrated alumina forming product. The drying conditions for drying the boron-containing hydrated alumina molding to obtain the boron-containing hydrated alumina molding are described in detail in the method of the fifth aspect of the present invention, and will not be described herein again.
Depending on the type of shaped body to be expected, step (6) may or may not be carried out. When step (6) is carried out, the whole of the boron-containing hydrated alumina compact obtained in step (5) may be fed to step (6) and calcined; part of the boron-containing hydrated alumina compact obtained in the step (5) may be fed to the step (6), so that the boron-containing hydrated alumina compact and the alumina compact can be simultaneously produced. The conditions for the calcination have been described in detail in the method of the eighth aspect of the present invention, and are not described herein again.
According to a twelfth aspect of the present invention, there is provided a boron-containing hydrated alumina compact or alumina compact produced by the method according to the tenth or eleventh aspect of the present invention.
The boron-containing hydrated alumina formed bodies and alumina formed bodies produced by the method according to the tenth aspect of the present invention have high strength. In general, the radial crush strength of the boron-containing hydrated alumina compact and the alumina compact may be 10N/mm or more (for example, 10 to 55N/mm), preferably 12N/mm or more, and more preferably 15N/mm or more, respectively. In one example, the hydrated alumina compact and the alumina compact each have a radial crush strength of 12 to 35N/mm, preferably 15 to 35N/mm. In a more preferred example, the hydrated alumina compact and the alumina compact each have a radial crush strength of 15 to 32N/mm.
The boron-containing hydrated alumina forming body and the alumina forming body according to the present invention can be produced by using a hydrated alumina production forming system which can include a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a forming unit, a drying unit and optionally a calcining unit,
the hydrated alumina gel production unit is characterized in that an output port of a hydrated alumina gel solution of the hydrated alumina gel production unit is communicated with an input port of a washing material to be separated of the solid-liquid separation and washing unit, an output port of a solid-phase material of the solid-liquid separation and washing unit is communicated with an input port of a solid-phase material of the mixing unit, an output port of a mixed material of the mixing unit is communicated with an input port of a raw material of the forming unit, an input port of a material to be dried of the drying unit is communicated with an output port of a formed product of the forming unit, and an input port of a material to be calcined of the.
The hydrated alumina gel production unit is used for generating a hydrated alumina gel solution through a synthesis reaction. The method for synthesizing the hydrated alumina gel may be a conventional method such as the precipitation method, the hydrolysis method, the seed precipitation method, and the rapid dehydration method described above, and will not be described in detail herein.
The hydrated alumina gel production unit may perform a synthesis reaction using a conventional reactor to obtain a hydrated alumina gel solution, which is not particularly limited in the present invention.
The solid-liquid separation and washing unit is used for carrying out solid-liquid separation and washing on the hydrated alumina gel aqueous solution output by the hydrated alumina gel production unit to obtain hydrated alumina wet gel
The value satisfies the requirement of being able to be mixed with a compound having at least two proton acceptor sites and a boron-containing compound according to the second aspect of the present invention.
The solid-liquid separation and washing unit can perform solid-liquid separation and washing by various methods commonly used, thereby obtaining
A hydrated alumina gel having a value that satisfies the mixing requirements with a compound having at least two proton acceptor sites and a boron-containing compound. The solid-liquid separation and washing unit may employ conventional solid-liquid separation devices, such as: a filtration device, a centrifugation device, or a combination of both. When the solid-liquid separation unit includes a filtration device, the filtration device may be one or a combination of two or more of a gravity filtration device, a pressure filtration device, and a vacuum filtration device. Preferably, the filtration means comprises at least a pressure filtration means. Specific examples of the pressure filtration device include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. For controlling the hydrated alumina wet gel obtained
Value of, the solid-liquid separationAnd the washing unit can also comprise a purging device, and natural wind or pressurized wind is adopted to purge the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.
The solid-liquid separation and washing unit may comprise one or more solid-liquid separation subunits, preferably at least one solid-liquid separation subunit and the last solid-liquid separation subunit being a pressure filtration device and/or a vacuum filtration device, so that the solid-phase material (i.e. hydrated alumina wet gel) obtained by the solid-liquid separation unit is
The value is such that the requirements for mixing with the compound having at least two proton acceptor sites and the boron-containing compound according to the second aspect of the invention are met. By adjusting the magnitude of the applied pressure or vacuum, the final hydrated alumina wet gel can be treated
The value is adjusted. When the solid-liquid separation unit comprises more than two solid-liquid separation subunits, except that the last solid-liquid separation subunit preferably adopts a solid-liquid separation mode taking pressure as a driving force, the other solid-liquid separation subunits can adopt a pressurizing filter device and/or a vacuum filter device, or do not adopt the pressurizing filter device and the vacuum filter device, and preferably adopt the pressurizing filter device and/or the vacuum filter device.
The solid-liquid separation and washing unit can wash the separated solid phase by adopting a conventional washing device. For example, a spray device may be used to spray wash water onto the surface of the separated solid phase. In order to improve the washing effect and the washing efficiency, shearing and/or oscillation may be applied to the solid phase during or after the spraying, and the spray water and the solid phase may be mixed uniformly with the shearing, such as stirring.
The solid-liquid separation unit is arranged in the hydrated alumina gel production unit by taking the material flow direction of the hydrated alumina gel as the referenceAnd the mixing unit is used for separating the gel solution output by the hydrated alumina gel production unit to obtain
The hydrated alumina wet gel, which has a value that meets the mixing requirements, provides the raw materials for the mixing unit.
In a preferred embodiment, the solid-liquid separation unit may comprise a washing subunit, a diluting subunit, a conveying subunit and a second solid-liquid separation subunit, from the viewpoint of facilitating the transportation of the material, on the premise that the mixing unit is provided with the hydrated alumina gel satisfying the requirements,
the washing subunit is used for collecting and washing a solid phase in the hydrated alumina gel solution output by the hydrated alumina gel production unit;
the diluting subunit is used for diluting the solid phase output by the washing subunit with water to obtain slurry;
the conveying subunit is used for conveying the slurry output by the diluting subunit into a second solid-liquid separation subunit;
and the second solid-liquid separation subunit is used for carrying out solid-liquid separation on the slurry to obtain hydrated alumina wet gel.
The conveying subunit may employ any of a variety of conventional conveying devices, such as a conveyor belt. The delivery sub-unit and the washing sub-unit may be integrated together, for example in one device, so that washing is performed during delivery, improving production efficiency. For example: a conveying belt with a solid-liquid separation function is adopted, and a spraying device is arranged above solid-phase materials of the conveying belt, so that washing and solid-liquid separation are carried out in the conveying process.
The mixing unit comprises an auxiliary agent adding device for adding an auxiliary agent to the hydrated alumina wet gel, wherein the auxiliary agent adding device at least adds a compound with at least two proton acceptor sites and a boron-containing compound to the hydrated alumina wet gel when the production system is in operation.
The mixing unit may employ conventional mixing devices such as various conventional mixers, kneaders, or a combination of both. The forming unit may employ conventional forming devices, such as: an extrusion device, a spraying device, a rounding device, a tabletting device or a combination of more than two. The drying unit may employ a conventional drying device, and the present invention is not particularly limited thereto. The baking unit may employ a conventional baking apparatus, and the present invention is not particularly limited thereto.
According to the production molding system of the present invention, the production molding system is not provided with a dehydration unit sufficient to reduce the i value of the hydrated alumina wet gel to 60% or less (preferably 62% or less) between the solid phase material discharge port of the solid-liquid separation and washing unit and the hydrated alumina wet gel input port of the mixing unit, based on the flow direction of the hydrated alumina gel.
In the actual production process, a mixing unit, a forming unit, a drying unit and a roasting unit can be additionally arranged on the basis of the existing hydrated alumina gel production device, so that the production and the forming of the hydrated alumina gel are integrated.
The method for producing the molded body by using the above hydrated alumina production molding system may comprise the steps of:
(1) feeding raw materials for producing the hydrated alumina gel solution into a hydrated alumina gel production unit for reaction to obtain the hydrated alumina gel solution;
(2) sending the hydrated alumina gel solution into a solid-liquid separation unit for solid-liquid separation to obtain hydrated alumina wet gel;
(3) mixing the hydrated alumina wet gel with a compound having at least two proton acceptor sites and a boron-containing compound in the mixing unit using the method of the second aspect of the invention to obtain a boron-containing hydrated alumina composition;
(4) molding the boron-containing hydrated alumina composition in a molding unit to obtain a boron-containing hydrated alumina molding;
(5) drying the boron-containing hydrated alumina forming product in a drying unit to obtain a boron-containing hydrated alumina forming product;
(6) and roasting at least part of the boron-containing hydrated alumina forming body in a roasting unit to obtain the alumina forming body.
According to a thirteenth aspect of the present invention, there is provided the use of the boron-containing hydrated alumina shaped body or the alumina shaped body according to the present invention as a carrier or adsorbent.
The boron-containing hydrated alumina moldings and alumina moldings according to the invention are particularly suitable as supports for supported catalysts. The supported catalyst may be any of various catalysts commonly used in the art that can have a boron-containing hydrated alumina compact and/or an alumina compact as a carrier. Preferably, the catalyst is a catalyst having a hydrogenation catalytic effect. That is, the boron-containing hydrated alumina formed body and the alumina formed body according to the present invention are particularly suitable as a carrier of a catalyst having a hydrogenation catalytic action.
The active component having a hydrogenation catalytic action may be supported on the boron-containing hydrated alumina compact or alumina compact according to the present invention by various methods commonly used in the art (e.g., impregnation), such as: the catalyst having a hydrogenation catalytic action can be obtained by impregnating the shaped body of the invention with an aqueous solution containing the active component and then drying and optionally calcining the shaped body loaded with the active component.
According to a fourteenth aspect of the present invention, there is provided a catalyst having a hydrogenation catalytic action, which comprises a carrier and a hydrogenation active component supported on the carrier, wherein the carrier is a boron-containing hydrated alumina compact according to the present invention and/or an alumina compact according to the present invention.
The hydrogenation active component may be of conventional choice. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating of hydrocarbon oil, the content of the support may be 30 to 93 wt%, preferably 50 to 91 wt%, more preferably 72 to 89 wt%, based on the total amount of the catalyst; the content of the group VIII metal element may be 2 to 15% by weight, preferably 3 to 10% by weight, more preferably 3 to 8% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 5 to 55 wt.%, preferably 6 to 40 wt.%, more preferably 8 to 20 wt.%, calculated as oxide.
According to a fifteenth aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation active component on a carrier, wherein the carrier is a boron-containing hydrated alumina compact and/or an alumina compact according to the present invention.
The method for producing a catalyst having a hydrogenation catalytic action according to the present invention preferably further comprises a step of producing a molded body, which is a hydrated alumina molded body and/or an alumina molded body. In this step, a molded body is produced by the method according to the fifth aspect, the eighth aspect, the tenth aspect or the eleventh aspect of the present invention.
According to the preparation method of the catalyst with hydrogenation catalysis, the hydrogenation active component can be selected conventionally. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The VIII group metal element is preferably cobalt and/or nickel, and the VIB group metal element is preferably molybdenum and/or tungsten. The loading amount of the hydrogenation active component on the carrier can be properly selected according to the specific application of the catalyst. For example, when the prepared catalyst is used for hydrotreating hydrocarbon oil, the loading amounts of the group VIII metal element and the group VIB metal element on the carrier based on the total amount of the prepared catalyst enable the contents of the group VIII metal element and the group VIB metal element in the finally prepared catalyst to meet the requirements of the fourteenth aspect of the present invention.
According to the preparation method of the catalyst having hydrogenation catalysis of the present invention, the hydrogenation active component can be supported on the carrier by various methods commonly used in the art, such as: and (4) dipping. The impregnation may be a saturated impregnation or an excess impregnation.
According to the preparation method of the catalyst with hydrogenation catalysis, the hydrogenation active components can be loaded on the carrier at the same time, and the hydrogenation active components can also be loaded on the carrier in a plurality of times.
According to the process for the preparation of the catalyst having a hydrocatalytic effect according to the present invention, the impregnated support may be dried and optionally calcined under conditions commonly used in the art. Generally, the drying conditions include: the temperature can be 100-200 ℃, preferably 120-150 ℃; the duration may be 1 to 15 hours, preferably 2 to 10 hours, more preferably 2 to 4 hours. The roasting conditions comprise: the temperature can be 350-550 ℃, preferably 400-500 ℃; the duration may be 1 to 8 hours, preferably 2 to 6 hours, more preferably 2 to 3 hours.
According to a sixteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having hydrocatalytic action, wherein the catalyst having hydrocatalytic action is the catalyst according to the fourteenth aspect of the present invention or the catalyst prepared by the method according to the fifteenth aspect of the present invention.
The hydrotreating method of the present invention is not particularly limited with respect to the kind of hydrocarbon oil and the hydrotreating conditions, and may be a routine choice in the art. Specifically, the hydrocarbon oil may be various heavy mineral oils, synthetic oils, or mixed distillates of heavy mineral oils and synthetic oils, such as: the hydrocarbon oil may be one or more selected from crude oil, distillate oil, solvent refined oil, cerate, under-wax oil, fischer-tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil. The hydrotreating conditions include: the temperature can be 300-380 ℃; in terms of gauge pressure, the pressure gauge is,the pressure can be 4-15 MPa; the liquid hourly space velocity of the hydrocarbon oil can be 1-3 hours-1(ii) a The hydrogen-oil volume ratio may be 200-1000.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the radial crush strength of the molded articles prepared was measured by the method specified in RIPP 25-90.
In the following examples and comparative examples, the following methods were used to measure
The value: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
in the following examples and comparative examples, the value of i was determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
in the following examples and comparative examples, the water absorption of the molded articles prepared were measured by the following method: drying the molded body to be tested at 120 ℃ for 4 hours, then sieving by using a 40-mesh standard sieve, and weighing 20g of oversize as a sample to be tested (marked as w)3) The sample to be tested is soaked in 50g of deionized water for 30 minutes, after filtration, the solid phase is drained for 5 minutes, and the weight of the drained solid phase is then weighed (denoted as w)4) The water absorption was calculated using the following formula:
in the following examples and comparative examples, the pore size distribution of the molded articles prepared was measured by mercury intrusion method.
In the following examples and comparative examples, the dry content was determined by baking a sample to be tested at 600 ℃ for 4 hours.
In the following examples and comparative examples, the composition of the catalyst was determined by x-ray fluorescence spectroscopy (i.e., XRF).
Examples 1 to 16 are intended to illustrate the boron-containing hydrated alumina composition, the molded body and the method of producing the same of the present invention.
Example 1
The hydrated alumina wet gel used in this example was a boron-containing pseudo-boehmite wet cake (the wet cake was numbered as SLB-1) obtained by adding boric acid to a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, available from Changling division, petrochemical, China) during aging and washing the hydrated alumina gel solution with a belt filter, and the i value of the wet cake was 78.0% and B was measured to be the same as that of the wet cake2O3The boron content was 5 wt%.
(1) 240g of the wet cake numbered SLB-1 was placed in a beaker, followed by addition of 6g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same below) and 3.6g of sesbania powder (having a galactomannan content of 80% by weight, purchased from Beijing chemical Co., Ltd., the same below), and stirring with a mechanical stirrer for 10 minutes to obtain a mixture which was the boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips by using a disc-shaped orifice plate with the diameter of 1.6mm on an F-26 type double-screw extruder (manufactured by general scientific and technical industries of southern China university, the same shall apply hereinafter). Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry alumina hydrate strips HT-1, the property parameters of which are listed in Table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain an alumina dry strip OT-1, wherein the property parameters of the alumina dry strip OT-1 are listed in Table 1.
Example 2
An alumina dry strip and a catalyst were prepared in the same manner as in example 1, except that, in the step (4), the alumina hydrate dry strip prepared in the step (3) was calcined at 980 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-2, the property parameters of which are shown in Table 1.
Example 3
(1) 4kg of the wet cake numbered SLB-1 was mixed with 400g of deionized water and beaten for 1 minute, and the resulting slurry was fed to a plate and frame filter press, and the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes to obtain a wet cake (numbered LB-1). The wet cake numbered LB-1 was determined to have an i value of 64.8%.
(2) 600g of wet cake LB-1 was placed in a beaker, 9.0g of hydroxyethyl methylcellulose (purchased from Shanghai Hui Guang Fine chemical Co., Ltd., the same applies hereinafter) and 3.0g of sesbania powder (having a galactomannan content of 85% by weight, purchased from Beijing chemical Co., Ltd.) were added and stirred with a mechanical stirrer for 10 minutes to obtain a boron-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.
(3) And (3) extruding the boron-containing hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the diameter of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-3 having the property parameters listed in table 1.
(5) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 480 ℃ for 7 hours in an air atmosphere to obtain an alumina dry strip OT-3, wherein the property parameters of the alumina dry strip OT-3 are listed in Table 1.
Example 4
Shaped bodies and catalysts were prepared in the same manner as in example 3, except that sesbania powder was not used in step (2) and the amount of hydroxyethyl methylcellulose was 11.6g, and properties of the boron-containing hydrated alumina composition, hydrated alumina dry strip HT-4 and alumina dry strip OT-4 were as shown in Table 1.
Example 5
Shaped bodies and catalysts were prepared in the same manner as in example 3, except that hydroxyethyl methylcellulose was not used in step (2) and sesbania powder was used in an amount of 13.6g, and properties of the boron-containing hydrated alumina composition, hydrated alumina dry strip HT-5 and alumina dry strip OT-5 were as shown in Table 1.
Example 6
A molded body and a catalyst were produced in the same manner as in example 3, except that 3g of nitric acid (HNO) was further added in the step (2) while adding hydroxyethyl methylcellulose and sesbania powder3In an amount of 65 wt.%), the properties of the prepared boron-containing hydrated alumina composition, hydrated alumina dry strip HT-6 and alumina dry strip OT-6 are listed in table 1.
Comparative example 1
(1) 600g of wet filter cake with the number of LB-1 is dried for 2 hours at the temperature of 80 ℃ in the air atmosphere to obtain the boron-containing pseudo boehmite powder, and the i value of the boron-containing pseudo boehmite powder is 50 percent. The boron-containing pseudo-boehmite powder was left at ambient temperature (25-30 ℃) for 72 hours under a closed condition (placed in a sealed plastic bag), and no formation of alumina trihydrate was detected after the left standing.
(2) Extruding the boron-containing pseudo-boehmite powder prepared in the step (1) on an F-26 type double-screw extruder by using a circular orifice plate with the diameter of 2.0 mm. The extruder has large heat productivity during extrusion (the extruder body is hot and a large amount of hot air is emitted), and the extruder frequently trips during extrusion, so that burrs are formed on the surface of an extruded material.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give DHT-1, a dry alumina hydrate strip, the property parameters of which are listed in Table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 7 hours in an air atmosphere to obtain alumina dry strip DOT-1, wherein the property parameters are listed in Table 1.
Comparative example 2
(1) And (3) drying 600g of wet filter cake with the LB-1 serial number for 3 hours at the temperature of 90 ℃ in the air atmosphere to obtain the boron-containing pseudo-boehmite powder, wherein the i value of the boron-containing pseudo-boehmite powder is 40%. The boron-containing pseudo-boehmite powder was left at ambient temperature (25-30 ℃) for 72 hours under a closed condition (placed in a sealed plastic bag), and no formation of alumina trihydrate was detected after the left standing.
(2) Placing 360g of the boron-containing pseudo-boehmite powder prepared in the step (1) in a beaker, adding 9.0g of hydroxyethyl methyl cellulose and 3.0g of sesbania powder (the content of galactomannan is 85 wt%), and stirring for 10 minutes by using a mechanical stirrer to obtain the boron-containing pseudo-boehmite composition.
(3) And (3) extruding the boron-containing pseudo-boehmite composition prepared in the step (2) into strips on an F-26 type double-screw extruder by using a circular orifice plate with the diameter of 2.0 mm. Wherein, the extruder frequently trips in the extrusion process, and the surface of the extruded material is smooth.
(4) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give dry alumina hydrate strips DHT-2 having the property parameters listed in Table 1.
(5) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 480 ℃ for 7 hours in an air atmosphere to obtain alumina dry strip DOT-3, wherein the property parameters of the alumina dry strip are listed in Table 1.
Comparative example 3
(1) 360g of boron-containing pseudo boehmite powder prepared in the same manner as in step (1) of comparative example 2 was placed in a beaker, and 9.0g of hydroxyethyl methyl cellulose, 3.0g of sesbania powder (galactomannan content 85% by weight) and 6g of nitric acid (HNO)365 wt.%) was stirred with a mechanical stirrer for 10 minutes to obtain a boron-containing pseudo-boehmite composition.
(2) And (2) extruding the boron-containing pseudo-boehmite composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a circular orifice plate with the diameter of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give dry alumina hydrate strips DHT-3 having the property parameters listed in Table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 7 hours in an air atmosphere to obtain alumina dry strip DOT-3, wherein the property parameters of the alumina dry strip are listed in Table 1.
Comparative example 4
A boron-containing hydrated alumina composition was prepared in the same manner as in example 3, except that hydroxyethylmethylcellulose and sesbania powder were not used, but 6.0g of paraffin was used. Of the resultant boron-containing hydrated alumina composition
The value was 1.63, and the boron-containing hydrated alumina composition could not be extrusion molded.
Comparative example 5
A boron-containing hydrated alumina composition was prepared in the same manner as in example 3, except that hydroxyethyl methylcellulose and sesbania powder were not used, but 6.0g of wood flour was used. Of the resultant boron-containing hydrated alumina composition
The value was 1.50, and the boron-containing hydrated alumina composition could not be extrusion molded.
Comparative example 6
The wet cake with the LB-1 designation was fed directly into an F-26 type twin-screw extruder and extruded into a rod using a circular orifice plate with a 2.0mm Φ diameter, with the result that extrusion molding could not be carried out.
Example 7
(1) 600g of wet cake LB-1, reference numerals 600g, was placed in a beaker and 5.2g of hydroxypropylmethylcellulose (available from Hakka chemical Co., Zhejiang, the same applies hereinafter) and 7.0g of sesbania powder (galactomannan content 85% by weight) were added and stirred with a mechanical stirrer for 10 minutes to obtain a boron-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.
(2) The boron-containing hydrated alumina composition prepared in the step (1) was extruded on a single screw extruder of the SK132S/4 type (BONNT corporation, usa) using a orifice plate composed of a circular shape having an outer diameter of Φ 4.0mm and having a cylinder of 1.2mm in the middle. Wherein, the extrusion process is smooth, and the surface of the extrusion material (Raschig ring) is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm, and the wet strips were dried at 70 ℃ for 2 hours in an air atmosphere, followed by drying at 120 ℃ for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-7, the property parameters of which are listed in Table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 940 ℃ for 3.5 hours in an air atmosphere to obtain an alumina dry strip OT-7, wherein the property parameters are listed in Table 1.
Example 8
(1) 600g of the wet cake numbered LB-1 were placed in a beaker and after adding 4g of methylcellulose, 2.2g of hydroxypropylmethylcellulose and 8g of sesbania powder (galactomannan content 85% by weight) and stirring for 10 minutes with a mechanical stirrer, a boron-containing hydrated alumina composition according to the invention was obtained, the parameters of which are listed in Table 1.
(2) Extruding the boron-containing hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a clover-shaped orifice plate with the phi of 2.5 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips of about 8cm in length, and the wet strips were dried at 110 ℃ for 4.5 hours in an air atmosphere to give dry alumina hydrate strips HT-8, the property parameters of which are listed in Table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 1000 ℃ for 1.5 hours in an air atmosphere to obtain an alumina dry strip OT-8, wherein the property parameters are listed in Table 1.
Example 9
(1) 600g of the wet cake numbered LB-1 were placed in a beaker, 4.4g of hydroxyethyl methylcellulose and 4.2g of hydroxypropyl methylcellulose were added and, after stirring for 10 minutes with a mechanical stirrer, the boron-containing hydrated alumina composition of the present invention was obtained, the property parameters of which are listed in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.8 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 200 c for 4 hours in an air atmosphere to give dry alumina hydrate strips HT-9 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 900 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-9, wherein the property parameters of the alumina dry strip OT-9 are listed in Table 1.
Example 10
(1) 5kg of the wet cake numbered SLB-1 was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.5MPa and maintained for 20 minutes, then the cake in the plate and frame was swept with pressurized air at 0.5MPa for 10 minutes, and the plate and frame was depressurized to obtain a wet cake (numbered LB-2). The i value of the wet cake was 64.3%.
(2) 500g of wet cake LB-2, reference numeral LB-2, was placed in a beaker, to which 8g of hydroxypropylmethylcellulose and 10g of sesbania powder (galactomannan content 85% by weight, available from Beijing Chemicals) were added and stirred for 10 minutes using a mechanical stirrer to obtain a boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(3) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.4 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-10, the property parameters of which are listed in table 1.
(5) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 650 ℃ for 2.5 hours in an air atmosphere to obtain an alumina dry strip OT-10, wherein the property parameters are listed in Table 1.
Example 11
(1) 5kg of the wet cake numbered SLB-1 was mixed with 400g of deionized water, 26.4g of methylcellulose and 16g of sesbania powder (galactomannan content 80% by weight) and beaten for 1 minute, and then the resulting slurry was fed to a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes, and the wet cake obtained by pressure-releasing the plate and frame was the boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-11 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-11, wherein the property parameters of the alumina dry strip OT-11 are listed in Table 1.
Example 12
The hydrated alumina wet gel used in this example was prepared by mixing CO2Method (sodium aluminate-CO)2The method is that hydrated alumina gel solution prepared from the new material of the catalyst of Haohao of Shaanxi county, Henan) is taken, sodium borate is added into the sodium aluminate solution, and the boron-containing pseudo-boehmite wet filter cake (the number of the wet filter cake is LB-3) is prepared after washing by a plate-and-frame filter press, and the i value of the wet filter cake is measured to be 63.6 percent, and B is used2O3The boron content was calculated as 12 wt%.
(1) 500g of wet cake LB-3, then 8g of methylcellulose and 10g of sesbania powder (galactomannan content 80% by weight) were added to the beaker and, after stirring for 10 minutes with a mechanical stirrer, the mixture obtained was a boron-containing hydrated alumina composition according to the invention, the parameters of which are given in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the diameter of 2.0mm, wherein the strip extruding process is smooth, and the surface of an extruded product is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 5cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-12 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-12, wherein the property parameters of the alumina dry strip OT-12 are listed in Table 1.
Example 13
The hydrated alumina wet gel used in the present example is a hydrated alumina gel solution prepared by sodium aluminate seeded precipitation (from Shandong division of aluminum, China), and sodium borate is added to the sodium aluminate solution, and 5kg of boron-containing alumina trihydrate wet filter cake is obtained by washing with a leaf filter, and B is added2O3The measured boron content was 20% by weight, 1000g of water was added to mix and pulp, the resulting slurry was pressed into a plate and frame filter press, the plate and frame pressure of the plate and frame filter was adjusted to 0.9MPa and held for 3 minutes, and then the filter cake in the plate and frame was swept with pressurized air of 0.6MPa for 5 minutes to give 2.5kg of a boron-containing alumina trihydrate wet cake (this wet cake was designated as LB-4) having an i value of 61.4% by weight.
(1) 500g of the wet cake LB-4 obtained in step (1) was placed in a beaker, then 5g of methylcellulose and 10g of sesbania powder (galactomannan content 80% by weight) were added and, after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-13 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 1400 ℃ for 2 hours in an air atmosphere to obtain an alumina dry strip OT-13, wherein the property parameters of the alumina dry strip OT-13 are listed in Table 1.
Example 14
The hydrated alumina wet gel used in this example was taken from Zibozimao ShandongCatalyst GmbH is prepared by calcining 1000g of pseudo-boehmite dry powder prepared by acid method (sodium aluminate-aluminum sulfate method) at 700 deg.C for 3 hr in air atmosphere to obtain 696g of alumina, placing 696g of alumina in 10L high-pressure reaction kettle, stirring with 5L of deionized water, sealing the high-pressure reaction kettle, reacting at 150 deg.C under self-pressure for 6 hr, cooling the high-pressure reaction kettle to room temperature (25 deg.C) after reaction, adding boron oxide, adding B2O3The calculated boron content is 10 weight percent, slurry obtained by the reaction is sent into a plate-and-frame filter press, the plate-and-frame pressure of the plate-and-frame filter press is adjusted to 0.5MPa and kept for 10 minutes, then filter cakes in the plate-and-frame filter press are blown and swept by 10MPa pressurized air for 3 minutes, and the plate-and-frame filter press is decompressed to obtain the wet filter cake LB-5 containing boron hydrated alumina. The phase of the wet cake was determined to be boron containing pseudo-boehmite and the i value of the wet cake was 60.1%.
(1) 500g of the wet cake numbered LB-5 were placed in a beaker, then 6.3g of methylcellulose and 10g of sesbania powder (galactomannan content 85% by weight) were added and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-14 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 4 hours in an air atmosphere to obtain an alumina dry strip OT-14, wherein the property parameters of the alumina dry strip OT-14 are listed in Table 1.
Example 15
The hydrated alumina wet gel used in this example was prepared by the method described in "New Process for preparing alumina by hydrolysis of Low-carbon Alkoxylaluminum", test method ", in" Petroleum institute (Petroleum processing) ", 10 th, 4 thThe preparation method comprises aging for 12 hr, distilling off isopropanol and water, adding 500g water, adding boron oxide, and adding B2O3The calculated boron content was 15% by weight, and the slurry was stirred with a mechanical stirrer for 1 minute, pressed into a plate and frame filter, and the pressure of the plate and frame was adjusted to 0.7MPa for 8 minutes, and then the cake in the plate and frame was blown with 7MPa of pressurized air for 4 minutes to obtain 200g of a wet cake (No. LB-6). The phase of the wet cake was determined to be boron containing pseudo-boehmite and the i value of the wet cake was 65.7%.
(1) 200g of the wet cake numbered LB-6 were placed in a beaker, then 2.8g of methylcellulose and 4.5g of sesbania powder (galactomannan content 80% by weight) were added and, after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a boron-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the boron-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-15 having the property parameters listed in table 1.
(4) And (3) roasting the hydrated alumina dry strip prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain an alumina dry strip OT-15, wherein the property parameters of the alumina dry strip OT-15 are listed in Table 1.
Example 16
(1) 5kg of the wet filter cake numbered SLB-1 was mixed with 700g of deionized water and beaten for 1 minute, the resulting slurry was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.5MPa and held for 3 minutes, and after the filter cake in the plate and frame was swept with pressurized air of 0.5MPa for 3 minutes, the plate and frame was depressurized to obtain a wet filter cake (numbered LB-7). The wet cake numbered LB-5 was determined to have an i value of 75 wt%.
(2) 500g of wet cake LB-7, numbered 500g, were placed in a beaker and 8g of hydroxypropylmethylcellulose and 10g of sesbania powder (galactomannan content 85% by weight) were added and stirred for 10 minutes using a mechanical stirrer to obtain boron-containing hydrated alumina compositions of the present invention, the property parameters of which are listed in Table 1.
(3) And (3) extruding the boron-containing hydrated alumina composition prepared in the step (2) into strips on an F-26 type double-screw extruder by using a round orifice plate with the diameter of 3.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strips having a length of about 6cm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry alumina hydrate strips HT-16 having the property parameters listed in table 1.
(5) And (3) roasting the hydrated alumina dry strip prepared in the step (4) at 950 ℃ for 2.5 hours in an air atmosphere to obtain an alumina dry strip OT-16, wherein the property parameters are listed in Table 1.
TABLE 1
1: the composition after standing was allowed to stand at ambient temperature (25-30 ℃) in a closed condition (in a sealed plastic bag) for 72 hours, and the content of alumina trihydrate in the composition after standing was increased more than before standing.
The results of examples 1-16 demonstrate that the hydrated alumina wet gel is not dried into dry gel powder or semi-dry gel powder, but is directly mixed with a compound having at least two proton acceptor sites and a boron-containing compound, the obtained mixture can be directly used for molding, and the obtained molded body has higher strength, thereby avoiding the problems of severe working environment, high energy consumption and low strength of the prepared molded body when the conventional molded body is prepared by taking the dry gel powder or the semi-dry gel powder as a starting material.
Experimental examples 1 to 9 are provided to illustrate a catalyst having a hydrogenation catalytic action according to the present invention, a preparation method thereof, and a hydrotreating method thereof.
Experimental example 1
(1) Dissolving 19.4g of nickel nitrate and 18.4g of ammonium heptamolybdate in water to prepare 122.3mL of impregnation liquid; the obtained impregnation solution was impregnated into 114.3g of the alumina hydrate dry strip prepared in example 1 for 4 hours. After filtration, the obtained solid product was dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 3 hours to obtain the catalyst CH-1 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 19.4g of nickel nitrate and 18.4g of ammonium heptamolybdate in water to prepare 95.2mL of impregnation liquid; the obtained impregnation solution was impregnated into 80g of the alumina dry strip prepared in example 1 for 4 hours. After filtration, the obtained solid product is dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 3 hours to obtain the catalyst CO-1 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 2
(1) Dissolving 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate in water to prepare 100.5mL of impregnation liquid; the obtained impregnation solution was impregnated into 114.3g of the alumina hydrate dry strip prepared in example 3 for 4 hours. After filtration, the obtained solid product is dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 3 hours to obtain the catalyst CH-2 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate in water to prepare 72.8mL of impregnation liquid; the obtained impregnation solution was impregnated into 80g of the alumina dry strip prepared in example 3 for 4 hours. After filtration, the obtained solid product is dried at 120 ℃ for 4 hours and then roasted at 400 ℃ for 3 hours to obtain the catalyst CO-2 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 3
The catalyst was prepared in the same manner as in experimental example 2, wherein (1) 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate were dissolved in water to prepare 121.1mL of an impregnation solution; the obtained impregnation liquid was impregnated with 114.3g of the alumina hydrate dry strip prepared in example 4 to obtain the catalyst CH-3 of the present invention. The composition of the catalyst was determined using XRF, with the results shown in table 2;
(2) dissolving 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate in water to prepare 88mL of impregnation liquid; the obtained impregnation solution was impregnated with 80g of the alumina dry strands prepared in example 4 to obtain the catalyst CO-3 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 4
The catalyst was prepared in the same manner as in experimental example 2, wherein (1) 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate were dissolved in water to prepare 117.7mL of an impregnation solution; the obtained impregnation liquid was impregnated with 114.3g of the alumina hydrate dry strip prepared in example 5 to obtain CH-4 catalyst of the present invention. The composition of the catalyst was determined using XRF, with the results shown in table 2;
(2) in the preparation method, 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate are dissolved in water to prepare 87.2mL of impregnation liquid; the obtained impregnation solution was impregnated with 80g of the alumina dry strands prepared in example 5 to obtain the catalyst CO-4 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 5
The catalyst was prepared in the same manner as in experimental example 2, wherein (1) 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate were dissolved in water to prepare 107.4mL of an impregnation solution; 114.3g of the alumina hydrate dry strip prepared in example 6 was impregnated with the obtained impregnation solution, with the result that the phenomena of structural collapse and pulverization occurred during the impregnation;
(2) in the preparation method, 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate are dissolved in water to prepare 84mL of impregnation liquid; the obtained impregnation solution was impregnated with 80g of the alumina dry strands prepared in example 6 to obtain CO-5 catalyst of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental comparative example 1
The catalyst was prepared in the same manner as in experimental example 2, wherein (1) 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate were dissolved in water to prepare 123.4mL of an impregnation solution; 114.3g of the alumina hydrate dry strip prepared in comparative example 1 was impregnated with the obtained impregnation solution, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) in the method, 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate are dissolved in water to prepare 91.2mL of impregnation liquid; the obtained impregnation liquid was impregnated with 80g of the alumina dry strip prepared in comparative example 1 to obtain catalyst DCO-1. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental comparative example 2
The catalyst was prepared in the same manner as in experimental example 2, wherein (1) 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate were dissolved in water to prepare 118.9mL of an impregnation solution; 114.3g of the alumina hydrate dry strip prepared in comparative example 3 was impregnated with the obtained impregnation solution, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) in the preparation method, 11.7g of nickel nitrate and 20.9g of ammonium heptamolybdate are dissolved in water to prepare 86.4mL of impregnation liquid; the obtained impregnation liquid was impregnated with 80g of the alumina dry strip prepared in comparative example 3 to obtain a catalyst DCO-2. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 6
(1) Dissolving 19.4g of cobalt nitrate and 18.4g of ammonium heptamolybdate in water to prepare 100.6mL of impregnation liquid; the resulting impregnation solution was impregnated with 114.3g of the alumina hydrate dry strip prepared in example 10 for 4 hours. After filtration, the obtained solid product was dried at 120 ℃ for 4 hours and calcined at 400 ℃ for 3 hours to obtain the catalyst CH-6 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 19.4g of cobalt nitrate and 18.4g of ammonium heptamolybdate in water to prepare 67.2mL of impregnation liquid; the obtained impregnation solution was impregnated into 80g of the alumina dry strip prepared in example 10 for 4 hours. After filtration, the obtained solid product is dried at 120 ℃ for 4 hours and calcined at 400 ℃ for 3 hours to obtain the catalyst CO-6 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 7
(1) Dissolving 19.4g of cobalt nitrate and 20.9g of ammonium heptamolybdate in water to prepare 114.3mL of impregnation liquid; the obtained impregnation liquid was impregnated into 111g of the alumina hydrate dry strip prepared in example 11 for 4 hours. After filtration, the obtained solid product was dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 3 hours to obtain the catalyst CH-7 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 19.4g of cobalt nitrate and 20.9g of ammonium heptamolybdate in water to prepare 75.7mL of impregnation liquid; the obtained impregnation solution was impregnated into 78g of the alumina dry strip prepared in example 11 for 4 hours. After filtration, the obtained solid product is dried at 120 ℃ for 4 hours and then calcined at 400 ℃ for 3 hours to obtain the catalyst CO-7 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 8
(1) Dissolving 23.3g of cobalt nitrate and 17.2g of ammonium heptamolybdate in water to prepare 49.1mL of impregnation liquid; the obtained impregnation solution was impregnated into 114.3g of the alumina hydrate dry strip prepared in example 12 for 4 hours. After filtration, the obtained solid product was dried at 140 ℃ for 3 hours and then calcined at 450 ℃ for 2 hours to obtain the catalyst CH-8 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 23.3g of cobalt nitrate and 17.2g of ammonium heptamolybdate in water to prepare 33.6mL of impregnation liquid; the obtained impregnation solution was impregnated into 80g of the alumina dry strip prepared in example 12 for 4 hours. After filtration, the obtained solid product is dried at 140 ℃ for 3 hours and then calcined at 450 ℃ for 2 hours to obtain the catalyst CO-8 of the invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 9
(1) Dissolving 11.7g of nickel nitrate and 24.5g of ammonium heptamolybdate in water to prepare 75.9mL of impregnation liquid; the resulting impregnation solution was impregnated into 110g of the alumina hydrate dry strip prepared in example 15 for 4 hours. After filtration, the obtained solid product was dried at 150 ℃ for 2 hours and then calcined at 460 ℃ for 2 hours to obtain the catalyst CH-9 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 2.
(2) Dissolving 11.7g of nickel nitrate and 24.5g of ammonium heptamolybdate in water to prepare 51.6mL of solution; the resulting solution was impregnated with 77g of the dried alumina strip prepared in example 15 for 4 hours. After filtration, the obtained solid product was dried at 150 ℃ for 2 hours and then calcined at 460 ℃ for 2 hours to obtain the catalyst CO-9 of the present invention. The composition of the catalyst was determined by XRF and the results are shown in table 3.
TABLE 2
| Numbering | Catalyst numbering | NiO (wt%) | CoO (% by weight) | MoO3(wt%) |
| Experimental example 1 | CH-1 | 5 | / | 15 |
| Experimental example 2 | CH-2 | 3 | / | 17 |
| Experimental example 3 | CH-3 | 3 | / | 17 |
| Experimental example 4 | CH-4 | 3 | / | 17 |
| Experimental example 6 | CH-6 | / | 5 | 15 |
| Experimental example 7 | CH-7 | / | 5 | 17 |
| Experimental example 8 | CH-8 | / | 6 | 14 |
| Experimental example 9 | CH-9 | 3 | / | 20 |
TABLE 3
| Numbering | Catalyst numbering | NiO (wt%) | CoO (% by weight) | MoO3(wt%) |
| Experimental example 1 | CO-1 | 5 | 15 | |
| Experimental example 2 | CO-2 | 3 | / | 17 |
| Experimental comparative example 1 | DCO-1 | 3 | / | 17 |
| Experimental comparative example 2 | DCO-2 | 3 | / | 17 |
| Experimental example 3 | CO-3 | 3 | / | 17 |
| Experimental example 4 | CO-4 | 3 | / | 17 |
| Experimental example 5 | CO-5 | 3 | / | 17 |
| Experimental example 6 | CO-6 | / | 5 | 15 |
| Experimental example 7 | CO-7 | / | 5 | 17 |
| Experimental example 8 | CO-8 | / | 6 | 14 |
| Experimental example 9 | CO-9 | 3 | / | 20 |
Test examples 1-9 are intended to illustrate the hydrotreating process according to the invention.
The catalysts prepared in experimental examples 1 to 9 were evaluated for their catalytic performance by the following methods, and the results are shown in Table 4.
The catalysts prepared in the above examples were each crushed into particles of 2-3mm in diameter and charged into a mini-fixed bed reactor. The raw oil was a column and river atmospheric residue having a Ni element content of 71.7ppm, a V element content of 399ppm, an N content of 0.62 wt%, and an S content of 3.2 wt%. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the liquid hourly volume space velocity of the raw oil is 450h-1. The desulfurization rate was calculated according to the following formula:
testing of comparative examples 1-2
The catalysts prepared in experimental comparative examples 1-2 were evaluated for their catalytic performance in the same manner as in test examples 1-9, respectively, and the results of the experiments are shown in Table 4.
TABLE 4
The results of test examples 1 to 9 confirmed that the catalysts prepared using the boron-containing hydrated alumina compact and the alumina compact according to the present invention as a carrier have high catalytic activity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (55)
1. A boron-containing hydrated alumina composition comprising hydrated alumina, a compound having at least two proton acceptor sites, and a boron-containing compound, wherein the compound having at least two proton acceptor sites is one or more of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,
of said composition
A value of 1.2 to 5, said
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
the preparation method of the boron-containing hydrated alumina composition comprises the steps of mixing the components in a raw material composition to obtain the boron-containing hydrated alumina composition, wherein the raw material composition comprises a hydrated alumina wet gel, a compound with at least two proton acceptor sites and a boron-containing compound, the i value of the hydrated alumina wet gel is not less than 60% and not more than 78.5%, and the compound with at least two proton acceptor sites is used in an amount that the components in the finally prepared composition are mixed
The value is 1.2 to 5,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
2. the composition of claim 1, wherein the composition is
The value is 4 or less.
3. The composition of claim 2, wherein the composition is
The value is 3.5 or less.
4. The composition of claim 3, wherein the composition is
The value is 3.2 or less.
5. The composition of claim 1, wherein the composition is
The value is 1.3 or more.
6. The composition of claim 5, wherein the composition is a mixture of
The value is 1.4 or more.
7. The composition according to claim 1 or 2, wherein the compound having at least two proton acceptor sites is contained in an amount of 1 to 25 parts by weight, and the boron-containing compound is represented by B, relative to 100 parts by weight of the hydrated alumina2O3The content is 1.5-40 weight portions.
8. The composition of claim 7, wherein the compound having at least two proton acceptor sites is present in an amount of 2 to 20 parts by weight.
9. The composition of claim 8, wherein the compound having at least two proton acceptor sites is present in an amount of 3 to 18 parts by weight.
10. The composition of claim 9, wherein the compound having at least two proton acceptor sites is present in an amount of 3.5 to 17 parts by weight.
11. The composition of claim 7 wherein the boron-containing compound is represented by B2O3The content is 2-30 weight portions.
12. The composition of claim 11 wherein the boron-containing compound is represented by B2O3The content is 3-25 weight portions.
13. The composition of claim 1, wherein the compound having at least two proton acceptor sites is one or more of a galactan, a mannan, a galactomannan, and a cellulose ether.
14. The composition of claim 13, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
15. The composition of claim 13, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
16. The composition of claim 15, wherein the galactomannan is present in an amount of 10 to 70 wt% and the cellulose ether is present in an amount of 30 to 90 wt%, based on the total amount of the compound having at least two proton acceptor sites.
17. The composition of claim 16, wherein the galactomannan is present in an amount of 15 to 68 wt% and the cellulose ether is present in an amount of 32 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.
18. The composition of claim 17, wherein the galactomannan is present in an amount of 20 to 65 wt% and the cellulose ether is present in an amount of 35 to 80 wt%, based on the total amount of the compound having at least two proton acceptor sites.
19. The composition of any one of claims 1-6, wherein the hydrated alumina comprises pseudoboehmite.
20. The composition of claim 19, wherein the hydrated alumina is pseudoboehmite.
21. The composition of claim 19, wherein the composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, the amount of alumina trihydrate in the composition after standing being higher than the amount of alumina trihydrate in the composition before standing.
22. The composition of claim 21, wherein the alumina trihydrate content in the composition after placement is increased by at least 0.5% based on the total amount of alumina trihydrate content in the composition before placement.
23. The composition of claim 22, wherein the alumina trihydrate content of the composition after placement is increased by at least 1%, based on the total alumina trihydrate content of the composition before placement.
24. The composition of claim 23, wherein the alumina trihydrate content in the composition after placement is increased by 1.1% to 2% based on the total alumina trihydrate content in the composition before placement.
25. The composition of any one of claims 1-6, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel.
26. The composition of any one of claims 1-6, wherein the boron-containing compound is selected from at least one of boric acid, sodium borate, boron oxide, and ammonium borate.
27. The composition of any one of claims 1-6, wherein the composition is free of a peptizing agent.
28. The composition of claim 1, wherein the hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 60% or less.
29. The composition of claim 1, wherein the hydrated alumina wet gel is obtained by washing and solid-liquid separation of at least one hydrated alumina gel solution after optional aging.
30. The composition of claim 29 wherein the hydrated alumina gel solution is prepared by precipitation, hydrolysis, seeded precipitation, and flash dehydration.
31. The composition of claim 1, wherein the feedstock composition is free of a peptizing agent.
32. The composition according to claim 1, wherein the mixing is by stirring and/or kneading.
33. A boron-containing hydrated alumina compact formed from the boron-containing hydrated alumina composition of any one of claims 1 to 32.
34. The boron-containing hydrated alumina forming body of claim 33, wherein the boron-containing hydrated alumina forming body has a bimodal distribution of pore sizes, with a maximum probable pore size of 4 to 20nm and greater than 20nm, respectively, as measured by mercury intrusion; or
The boron-containing hydrated alumina formed body has a monomodal distribution of pore diameters, measured by mercury intrusion, and the most probable pore diameter is 4 to 25 nm.
35. A method for producing a boron-containing hydrated alumina molding, which comprises molding the boron-containing hydrated alumina composition according to any one of claims 1 to 32, and drying the resulting molded article.
36. A boron-containing hydrated alumina compact prepared by the method of claim 35.
37. An alumina compact formed from the boron-containing hydrated alumina composition of any one of claims 1 to 32.
38. Alumina shaped body according to claim 37 having a bimodal pore size distribution with a maximum probable pore size of 4-20nm and greater than 20nm, respectively, as determined by mercury intrusion; or
The pore diameter of the alumina formed body is unimodal distribution measured by mercury intrusion method, and the most probable pore diameter is 4-25 nm.
39. A method for producing an alumina molded body, which comprises molding the boron-containing hydrated alumina composition according to any one of claims 1 to 32, and drying and firing the resulting molded body.
40. An alumina shaped body made by the method of claim 39.
41. The boron-containing hydrated alumina compact of claim 33, 34 or 36, the alumina compact of claim 37, 38 or 40, wherein the radial crush strength of the boron-containing hydrated alumina compact and the alumina compact are each 10N/mm or greater.
42. The boron-containing hydrated alumina compact of claim 33, 34 or 36, the alumina compact of claim 37, 38 or 40, wherein the radial crush strength of the boron-containing hydrated alumina compact and the alumina compact are each 15-32N/mm.
43. A production and forming method of hydrated alumina comprises the following steps:
(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 60% and not more than 78.5%;
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(2) mixing the first hydrated alumina wet gel, a compound with at least two proton acceptor sites and a boron-containing compound to obtain a boron-containing hydrated alumina composition, wherein the compound with at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound with at least two proton acceptor sites is used in an amount of the finally prepared composition
A value of 1.2 to 5, said
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
(3) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(4) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(5) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
44. A production and forming method of hydrated alumina comprises the following steps:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) subjecting the first hydrated alumina wet gel to solid-liquid separation to obtain a second hydrated alumina wet gel, wherein in (2-1) and (2-2), the solid-liquid separation is performed under such conditions that the i value of the second hydrated alumina wet gel is not less than 60% and not more than 78.5%,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(3) mixing a second hydrated alumina wet gel, a compound with at least two proton acceptor sites and a boron-containing compound to obtain a boron-containing hydrated alumina composition, wherein the compound with at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound with at least two proton acceptor sites is used in an amount of the finally prepared composition
A value of 1.2 to 5, said
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
(4) molding the boron-containing hydrated alumina composition to obtain a boron-containing hydrated alumina molding;
(5) drying the boron-containing hydrated alumina forming product to obtain a boron-containing hydrated alumina forming product;
(6) optionally, at least a portion of the boron-containing hydrated alumina compact is calcined to produce an alumina compact.
45. The process according to claim 43 or 44, wherein the solid-liquid separation is carried out one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.
46. The method of claim 43 or 44, wherein the hydrated alumina gel solution is aged or unaged and the reaction mixture is prepared by one or more of precipitation, hydrolysis, seeding and flash dehydration.
47. A shaped body prepared by the method of any one of claims 43 to 46.
48. The molded body according to claim 47, wherein the molded body has a radial crush strength of 10N/mm or more.
49. The shaped body according to claim 48, wherein the shaped body has a radial crush strength of from 15 to 32N/mm.
50. Use of the boron-containing hydrated alumina shaped body of claim 33, 34 or 36, the alumina shaped body of claim 37, 38 or 40 or the shaped body of any one of claims 47 to 49 as a carrier or adsorbent.
51. The use according to claim 50, wherein the support is a support for a supported catalyst.
52. The use according to claim 51, wherein the support is a support for a supported hydrogenation catalyst.
53. A catalyst having a hydrogenation catalytic action, which comprises a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is the boron-containing hydrated alumina compact of claim 33, 34 or 36, the alumina compact of claim 37, 38 or 40 or the compact of any one of claims 47 to 49.
54. A process for producing a catalyst having a hydrogenation catalytic action, which comprises supporting a hydrogenation-active component on a carrier, wherein the carrier is the boron-containing hydrated alumina compact of claim 33, 34 or 36, the alumina compact of claim 37, 38 or 40 or the compact of any one of claims 47 to 49.
55. A hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a catalyst having hydroprocessing catalysis, wherein the catalyst having hydroprocessing catalysis is the catalyst of claim 53 or the catalyst prepared by the method of claim 54.
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