CN108014829B - Phosphorus-containing hydrated alumina composition, molded body and preparation method thereof, and catalyst and preparation method thereof - Google Patents
Phosphorus-containing hydrated alumina composition, molded body and preparation method thereof, and catalyst and preparation method thereof Download PDFInfo
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- CN108014829B CN108014829B CN201610958277.4A CN201610958277A CN108014829B CN 108014829 B CN108014829 B CN 108014829B CN 201610958277 A CN201610958277 A CN 201610958277A CN 108014829 B CN108014829 B CN 108014829B
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- Prior art keywords
- hydrated alumina
- composition
- phosphorus
- wet gel
- value
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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 578
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 288
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 287
- 239000011574 phosphorus Substances 0.000 title claims abstract description 287
- 239000000203 mixture Substances 0.000 title claims abstract description 241
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 187
- 239000011240 wet gel Substances 0.000 claims abstract description 168
- 230000008569 process Effects 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 41
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 146
- 238000000926 separation method Methods 0.000 claims description 82
- 239000007788 liquid Substances 0.000 claims description 80
- 239000000499 gel Substances 0.000 claims description 72
- 238000005406 washing Methods 0.000 claims description 57
- 238000002156 mixing Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 22
- 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 21
- 229920000926 Galactomannan Polymers 0.000 claims description 21
- 229920003086 cellulose ether Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- 150000004684 trihydrates Chemical class 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- -1 galactan Polymers 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 229920000609 methyl cellulose Polymers 0.000 claims description 13
- 239000001923 methylcellulose Substances 0.000 claims description 13
- 235000010981 methylcellulose Nutrition 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
- 230000000694 effects Effects 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000002902 bimodal effect Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 229920000057 Mannan Polymers 0.000 claims description 5
- 238000004898 kneading 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims 1
- 238000002459 porosimetry Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 31
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003292 glue Substances 0.000 abstract description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 49
- 239000000243 solution Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001125 extrusion Methods 0.000 description 20
- 238000001914 filtration Methods 0.000 description 19
- 239000007790 solid phase Substances 0.000 description 19
- 238000004846 x-ray emission Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 241000219782 Sesbania Species 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 8
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000007796 conventional method Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000642 polymer Polymers 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 5
- 239000002253 acid Substances 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
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007865 diluting Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 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
- 230000002378 acidificating effect Effects 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
- 239000003463 adsorbent Substances 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
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000000626 Daucus carota Species 0.000 description 2
- 229920000869 Homopolysaccharide Polymers 0.000 description 2
- 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
- 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
- 235000011054 acetic acid Nutrition 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
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 235000005770 birds nest Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012071 phase 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 235000005765 wild carrot Nutrition 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
- 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 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002307 Dextran 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
- 239000001828 Gelatine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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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- 238000006359 acetalization reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 235000013312 flour Nutrition 0.000 description 1
- 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
- 239000000295 fuel oil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 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
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000011736 potassium bicarbonate Substances 0.000 description 1
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 229910052717 sulfur Inorganic materials 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
- 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/67—Pore distribution monomodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a phosphorus-containing hydrated alumina composition, a preparation method thereof, a formed body, a preparation method and application thereof, and a production forming system
The value is 1.8-5. 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 phosphorus-containing hydrated alumina composition as a carrier. The invention prepares the forming body with higher strength by taking the hydrated alumina wet gel as the starting material, omits the step of drying the hydrated alumina wet gel, simplifies the overall process flow, reduces the operation energy consumption, avoids the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material, and greatly improves the operation environment. The catalyst prepared by using the molded body formed by the hydrated oxide composition as a carrier shows higher catalytic activity in the hydrotreatment of hydrocarbon oil.
Description
Technical Field
The invention relates to the technical field of alumina forming, in particular to a phosphorus-containing hydrated alumina composition and a preparation method thereof, a hydrated alumina forming body and an alumina forming body which are formed by the phosphorus-containing hydrated alumina, and further relates to a catalyst with hydrogenation catalysis effect and a preparation method thereof, wherein the catalyst takes the forming body formed by the phosphorus-containing hydrated alumina composition as a carrier, and a hydrogenation treatment method adopting the catalyst.
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 can be modified by introducing an auxiliary phosphorus element into the formed body so as to meet the requirements of specific application occasions, such as: the hydrofining catalyst is prepared by adopting the phosphorus-containing alumina forming body as a carrier, and the hydrofining performance of the catalyst can be modulated. 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 hydrated alumina gel needs to be dried to obtain pseudo-boehmite dry gel powder, then the pseudo-boehmite dry gel powder is taken as a starting point, an extrusion aid, an auxiliary agent (such as a phosphorus-containing compound shown in fig. 1) and an optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and the mixture is kneaded and formed, and the formed product is dried and optionally calcined to be used as an adsorbent or a 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 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 phosphorus-containing hydrated alumina composition comprising hydrated alumina, a phosphorus-containing compound and a compound having at least two proton acceptor sites,
of said composition
A value of 1.8 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,
according to a second aspect of the present invention, there is provided a process for the preparation of a phosphorus-containing hydrated alumina composition, which comprises mixing the components of a feedstock composition comprising a hydrated alumina wet gel having an i value of not less than 60%, a phosphorus-containing compound, and a compound having at least two proton acceptor sites in an amount such that the composition finally prepared is a hydrated alumina composition, to give the hydrated alumina composition
The value is 1.8 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,
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 phosphorus-containing hydrated alumina composition prepared by the process of the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a phosphorus-containing hydrated alumina molded body formed from the phosphorus-containing hydrated alumina composition of the first aspect of the present invention or the phosphorus-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 phosphorus-containing alumina compact formed from the phosphorus-containing hydrated alumina composition of the first aspect of the present invention or the phosphorus-containing hydrated alumina composition of the third aspect of the present invention.
According to a sixth aspect of the present invention, there is provided a process for the preparation of a shaped body, which comprises shaping a phosphorus-containing hydrated alumina composition according to the first aspect of the present invention or a phosphorus-containing hydrated alumina composition according to the third aspect of the present invention, drying and optionally firing the obtained shaped body.
According to a seventh aspect of the present invention, there is provided a shaped article produced by the method of the sixth aspect of the present invention.
According to an eighth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing phosphorus, 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 with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a phosphorus-containing hydrated alumina composition;
(3) forming the phosphorus-containing hydrated alumina composition to obtain a phosphorus-containing hydrated alumina forming product;
(4) drying the phosphorus-containing hydrated alumina forming product to obtain a phosphorus-containing hydrated alumina forming product;
(5) optionally, roasting at least part of the phosphorus-containing hydrated alumina forming body to obtain a phosphorus-containing alumina forming body,
wherein the method further comprises an operation of mixing a phosphorus-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a phosphorus-containing compound.
According to a ninth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing phosphorus, 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 with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a phosphorus-containing hydrated alumina composition;
(4) forming the hydrated alumina composition to obtain a phosphorus-containing hydrated alumina forming product;
(5) drying the phosphorus-containing hydrated alumina forming product to obtain a phosphorus-containing hydrated alumina forming product;
(6) optionally, roasting at least part of the phosphorus-containing hydrated alumina forming body to obtain a phosphorus-containing alumina forming body;
wherein the method further comprises an operation of mixing a phosphorus-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a phosphorus-containing compound.
According to a tenth aspect of the present invention, there is provided a molded body produced by the method according to the eighth aspect or the ninth aspect of the present invention.
According to an eleventh 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 phosphorus-containing hydrated alumina compact according to the present invention or a phosphorus-containing alumina compact according to the present invention.
According to a twelfth aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, the method comprising supporting a hydrogenation-active component on a carrier, wherein the carrier is a phosphorus-containing hydrated alumina compact according to the present invention or a phosphorus-containing alumina compact according to the present invention.
According to a thirteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having a hydrocatalytic action, wherein the catalyst having a hydrocatalytic action is the catalyst according to the eleventh aspect of the present invention or the catalyst prepared by the method according to the twelfth aspect of the present invention.
Compared with the prior process method (as shown in figure 1) for preparing the phosphorus-containing 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 uses the hydrated alumina wet gel as the starting material to prepare the carrier, the process of the invention is simpler, has stronger operability and can effectively improve the strength of the finally prepared molded body. 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.
The catalyst with hydrogenation catalysis prepared by using the formed body as a carrier shows higher catalyst activity in hydrocarbon oil hydrogenation treatment.
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 hydrated alumina composition in accordance with 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 phosphorus-containing hydrated alumina composition comprising hydrated alumina, a phosphorus-containing compound and a compound having at least two proton acceptor sites.
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 phosphorus-containing hydrated alumina composition according to this preferred embodiment is particularly suitable for preparing shaped bodies for use as catalyst supports.
According to the phosphorus-containing hydrated alumina composition of the present invention, the hydrated alumina is directly derived from the hydrated alumina wet gel and not from the hydrated alumina dry gel powder. In the present invention, the term "hydrated alumina wet gel" refers to an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for reducing its i value to 60% or less (preferably 62% or less, more preferably 64% 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%, more preferably by from 1.1% to 2%, based on the total amount of alumina trihydrate content in the composition before placement.
The phosphorus-containing hydrated alumina composition according to the present invention further contains a compound having at least two proton acceptor sites. The phosphorus-containing hydrated alumina composition according to the present invention can be used for molding (particularly extrusion molding) without using a 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 can be a homopolysaccharide, a heteropolysaccharide or a combination of the homopolysaccharide and the 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 preferablyIs alkyl (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 polypropyleneAcids, polymethacrylic acid, acrylic acid-methyl acrylate copolymers, acrylic acid-methyl methacrylate copolymers, methacrylic acid-methyl acrylate copolymers, and methacrylic acid-methyl methacrylate copolymers.
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.%, even more preferably from 25 to 60 wt.%, even more preferably from 30 to 55 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the content of the cellulose ether may be 30 to 90% by weight, preferably 32 to 85% by weight, more preferably 35 to 80% by weight, still more preferably 40 to 75% by weight, and still more preferably 45 to 70% by weight.
The phosphorus-containing hydrated alumina composition according to the present invention contains a phosphorus-containing compound. The phosphorus-containing compound may be a phosphorus-containing compound conventional in the art, and may be, for example, at least one of phosphoric acid, sodium phosphate, aluminum phosphate, ammonium hydrogen phosphate, and ammonium phosphate.
The composition according to this embodiment is particularly suitable for the preparation of a support for a catalyst having a hydrocatalytic effect. The content of phosphorus in the phosphorus-containing hydrated alumina composition can be determined by X-ray fluorescence spectroscopy (XRF). In addition, the phosphorus-containing hydrated alumina composition can also be obtained by calculating the feeding amount, and in the embodiment of the invention, the content of the phosphorus element in the phosphorus-containing hydrated alumina composition is calculated by adopting the feeding amount.
Of the compositions according to the invention
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 4, more preferably not less than 1.9, for example, may be 1.9 to 3.5, preferably 1.9 to 3.2. The phosphorus-containing hydrated alumina composition can prepare a formed body with bimodal 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 3 to 22 parts by weight, more preferably 4 to 20 parts by weight, relative to 100 parts by weight of the hydrated alumina; according to the composition of the invention, the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina2O5The 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 peptizing agent is contained in an amount of 5 parts by weight or less with respect to 100 parts by weight of 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 process for preparing a phosphorus-containing hydrated alumina composition, which comprises mixing the components of a feedstock composition to obtain the phosphorus-containing hydrated alumina composition, i.e. the mixture obtained by mixing is the phosphorus-containing hydrated alumina composition.
According to the method for producing a phosphorus-containing hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a phosphorus-containing compound and a compound having at least two proton acceptor sites. The types of compounds having at least two proton acceptor sites and phosphorous containing compounds have been described in detail above and will not be described in detail here.
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: roasting the hydrated alumina at the temperature of 600-950 ℃, preferably 650-800 ℃, carrying out hydrothermal treatment on the roasted product, and carrying out solid-liquid separation on the mixture obtained by the hydrothermal treatment, thereby obtaining the 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 120-200 deg.C, preferably 140-160 deg.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 phosphorus-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%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 62 to 78.5%.
The hydrated alumina wet gel having an i value satisfying the above requirements can be obtained by controlling the solid-liquid separation conditions in the solid-liquid separation of the prepared solution containing the hydrated alumina gel. 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 apparatus used for the pressure filtration 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 phosphorus-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 phosphorus-containing hydrated alumina composition of the present invention, the compound having at least two proton acceptor sites is used in an amount such that the finally prepared phosphorus-containing hydrated alumina composition is
The value is 1.8 to 5, preferably not less than 1.85, for example, 1.85 to 4, more preferably not less than 1.9, for example, 1.9 to 3.5, preferably 1.9 to 3.2. Shaped bodies having a bimodal pore size distribution can be produced from the composition.
Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 3 to 22 parts by weight, more preferably 4 to 20 parts by weight, relative to 100 parts by weight of the hydrated alumina wet gel. The hydrated alumina wet gel is calculated by hydrated alumina.
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.%, even more preferably from 25 to 60 wt.%, even more preferably from 30 to 55 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the content of the cellulose ether may be 30 to 90% by weight, preferably 32 to 85% by weight, more preferably 35 to 80% by weight, still more preferably 40 to 75% by weight, and still more preferably 45 to 70% by weight.
The amount of phosphorus-containing compound in the feed mixture can be selected based on the amount of elemental phosphorus that is expected to be incorporated in the phosphorus-containing hydrated alumina composition. Generally, the content of the phosphorus-containing compound in the raw material mixture is such that the phosphorus-containing compound is represented by P relative to 100 parts by weight of the hydrated alumina in the finally prepared phosphorus-containing hydrated alumina composition2O5The 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.
According to the method for preparing the phosphorus-containing hydrated alumina composition of the present invention, the raw material mixture may or may not contain a peptizing agent. Preferably, the peptizing agent is contained in an amount of 5 parts by weight or less with respect to 100 parts by weight of hydrated alumina, the hydrated alumina wet gel being based on the hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, the method for producing a phosphorus-containing hydrated alumina composition according to the present invention more preferably does not include a step of adding a peptizing agent to the raw material mixture.
According to the method for preparing the phosphorus-containing hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with a compound having at least two proton acceptor sites by a conventional method. The hydrated alumina wet gel may be mixed with a compound having at least two proton acceptor sites under shear. In one embodiment, the mixing is by stirring. The hydrated alumina wet gel and the compound having at least two proton acceptor sites may be mixed uniformly by stirring in a vessel having a stirring device to obtain the phosphorus-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 in a kneader to obtain the phosphorus-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 phosphorus-containing hydrated alumina composition of the present invention, stirring and mixing may be used in combination to mix the hydrated alumina wet gel with a compound having at least two proton acceptor sites. In this case, it is preferable to perform stirring and kneading.
According to the method of preparing the hydrated alumina composition of the present invention, the phosphorous-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 phosphorus-containing compound may be mixed during the preparation of the hydrated alumina wet gel, or the phosphorus-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, or a part of the phosphorus-containing compound may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the phosphorus-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, and the phosphorus-containing compound may be mixed at one, two, or three of the above-mentioned addition timings. When the phosphorus-containing compound is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the phosphorus-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. Whether the phosphorus-containing compound is mixed during the preparation of the hydrated alumina wet gel, and the timing of the mixing may be selected according to the type of precipitation reaction.
In another embodiment, the phosphorus-containing compound is mixed after the hydrated alumina wet gel is prepared. In this embodiment, this can be done in one of the following ways: (1) mixing a phosphorus-containing compound with a hydrated alumina wet gel, and then mixing a compound having at least two proton acceptor sites; (2) mixing a compound having at least two proton acceptor sites with a hydrated alumina wet gel, and then mixing a phosphorus-containing compound; (3) simultaneously mixing a phosphorus-containing compound and a compound having at least two proton acceptor sites with the hydrated alumina wet gel.
According to the method for preparing the hydrated alumina composition of the present invention, it is preferable to mix the phosphorus-containing compound after the preparation of the hydrated alumina wet gel is completed.
According to the method for producing a phosphorus-containing hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the phosphorus-containing hydrated alumina composition can be produced
The value satisfies the above requirements. In general, water may be additionally added during the mixing process from the viewpoint of improving the homogeneity of the mixing. 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.
according to a third aspect of the present invention there is provided a phosphorus-containing hydrated alumina composition prepared by the process of the second aspect of the present invention.
The phosphorus-containing hydrated alumina composition according to the present invention can be molded by a conventional method to obtain a phosphorus-containing hydrated alumina carrier or a phosphorus-containing alumina carrier.
According to a fourth aspect of the present invention, there is provided a phosphorus-containing hydrated alumina molded body formed from the phosphorus-containing hydrated alumina composition according to the first aspect of the present invention or the phosphorus-containing hydrated alumina composition according to the third aspect of the present invention.
The phosphorus-containing hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain the phosphorus-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 more than 350 ℃, preferably 80 to 300 ℃, more preferably 110 ℃ or 260 ℃. The drying time can be properly selected according to the drying temperature, so that the volatile content in the finally obtained hydrated alumina forming body can meet 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 phosphorus-containing hydrated alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, strip, sheet, bird's nest, or honeycomb, and specific examples of the strip may include, but are not limited to: clover, disk, cylinder and raschig ring.
The phosphorus-containing hydrated alumina molded body according to the present invention has a rich pore structure. The pore size distribution of the phosphorus-containing hydrated alumina formed body is bimodal as determined by mercury intrusion method. Wherein the most probable pore size is 4-20nm (preferably 6-18nm) and more than 20nm (such as 20.5-35 nm).
According to the phosphorus-containing hydrated alumina formed body of the present invention, the phosphorus-containing hydrated alumina formed body has high strength. In general, the phosphorus-containing hydrated 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 (for example, may be 12 to 50N/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 phosphorus-containing alumina compact formed from the phosphorus-containing hydrated alumina composition of the first aspect of the present invention or the phosphorus-containing hydrated alumina composition of the third aspect of the present invention.
The phosphorus-containing hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and calcined in sequence to obtain the phosphorus-containing 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 450-1500 ℃. In addition, the calcination temperature can be optimized according to the type of the hydrated alumina. In one embodiment, the hydrated alumina is a hydrated alumina, such as pseudo-boehmite and/or boehmite, and the calcination temperature is preferably 450-. In another embodiment, the hydrated alumina is gibbsite and the calcination temperature is preferably 800-1500 ℃, more preferably 900-1400 ℃. 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 phosphorus-containing alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, strip, sheet, bird's nest, or honeycomb, and specific examples of the strip may include, but are not limited to: clover, disk, cylinder and raschig ring.
The phosphorus-containing alumina moldings according to the invention have a rich pore structure. The pore size distribution of the phosphorus-containing hydrated alumina formed body is bimodal as determined by mercury intrusion method. Wherein the most probable pore size is 4-20nm (preferably 6-18nm) and more than 20nm (such as 20.5-35 nm).
According to the phosphorus-containing alumina molded body of the present invention, the phosphorus-containing alumina molded body has high strength. In general, the phosphorus-containing alumina molded body according to the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm is acceptable), and preferably 12N/mm or more (for example, 12 to 50N/mm is acceptable).
According to a sixth aspect of the present invention, there is provided a process for the preparation of a shaped body, which comprises shaping a phosphorus-containing hydrated alumina composition according to the first aspect of the present invention or a phosphorus-containing hydrated alumina composition according to the third aspect of the present invention, drying and optionally firing the obtained shaped body. The obtained molded product may be dried and then calcined to obtain a phosphorus-containing alumina molded product, or may be calcined to obtain a phosphorus-containing hydrated alumina molded product.
The methods and conditions for forming, drying and firing are the same as those described in the fourth and fifth aspects of the present invention and will not be described in detail herein.
The pore diameter of the shaped bodies produced by the process for the production of shaped bodies according to the invention is bimodal. Specifically, the pore size distribution of the phosphorus-containing hydrated alumina molded body is bimodal as measured by mercury intrusion method. 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).
According to a seventh aspect of the present invention, there is provided a shaped article produced by the method of the sixth aspect of the present invention. The shaped bodies have a high strength. In general, the radial crush strength of the molded article produced by the method according to the sixth aspect of the present invention is 10N/mm or more (for example, 10 to 55N/mm), and preferably 12N/mm or more (for example, 12 to 50N/mm).
According to an eighth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing phosphorus, 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 phosphorus-containing compound and a compound having at least two proton acceptor sites by using the method of the second aspect of the present invention to obtain a phosphorus-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) forming the phosphorus-containing hydrated alumina composition to obtain a phosphorus-containing hydrated alumina forming product;
(5) drying the phosphorus-containing hydrated alumina forming product to obtain a phosphorus-containing hydrated alumina forming product;
(6) optionally, roasting at least part of the phosphorus-containing hydrated alumina forming body to obtain a phosphorus-containing alumina forming body;
wherein the method further comprises an operation of mixing a phosphorus-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a phosphorus-containing compound.
The method for mixing the phosphorus-containing compound according to the production molding method of the present invention is the same as the method and the sequence described in the second aspect of the present invention, and will not be described in detail herein.
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 a compound having at least two proton acceptor sites according to the second aspect of the present invention, or may be higher than the i value of the hydrated alumina wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention.
In one embodiment, the first hydrated alumina wet gel has an i value which satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites 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%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 62 to 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. 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. 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 (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 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%. Specifically, the i value of the hydrated alumina wet gel may be 60 to 82%, preferably 62 to 80%, more preferably 62 to 78.5%.
As shown in fig. 2 and 3, at least a portion of the phosphorus-containing compound may be mixed in step (2). In the case of the method described in (2-1), the phosphorus-containing compound may be mixed in the dilution operation and/or the solid-liquid separation operation, as shown in FIGS. 2 and 3.
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 method of solid-liquid separation 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 phosphorus-containing compound and a compound having at least two proton acceptor sites by the method according to the second aspect of the present invention, thereby obtaining a phosphorus-containing hydrated alumina composition. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to the step (3) satisfy the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention.
In the step (4), the phosphorus-containing hydrated alumina composition obtained in the step (3) is molded to obtain a phosphorus-containing hydrated alumina molded product. 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 molded product of the phosphorus-containing hydrated alumina obtained in the step (3) to obtain a molded product of the phosphorus-containing hydrated alumina. The drying conditions for drying the shaped hydrated alumina product to obtain the molded hydrated alumina product containing phosphorus have been 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. In the case of performing step (6), the whole of the phosphorus-containing hydrated alumina molded body obtained in step (5) may be fed to step (6) and calcined; part of the phosphorus-containing hydrated alumina molded body obtained in the step (5) may also be fed to the step (6), so that the phosphorus-containing hydrated alumina molded body and the phosphorus-containing alumina molded body 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 ninth aspect of the present invention, there is provided a phosphorus-containing hydrated alumina molded body or a phosphorus-containing alumina molded body produced by the method according to the eighth aspect of the present invention.
The phosphorus-containing hydrated alumina formed body and the phosphorus-containing alumina formed body produced by the method according to the eighth aspect of the present invention have high strength. In general, the radial crush strength of the phosphorus-containing hydrated alumina molded body and the phosphorus-containing alumina molded body may be 10N/mm or more (for example, 10 to 55N/mm), and preferably 12N/mm or more (for example, 12 to 50N/mm).
The method according to the eighth aspect of the present invention may be carried out in a hydrated alumina production molding system comprising a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding 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 feeding the hydrated alumina gel aqueous solution output by the hydrated alumina gel production unit into the solid-liquid separation and washing unitCarrying out solid-liquid separation and washing 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 according to the second aspect of the present invention.
The solid-liquid separation and washing unit can adopt various common methods to carry out solid-liquid separation and washing, thereby obtaining
A hydrated alumina gel having a value that satisfies the mixing requirements with a compound having at least two proton acceptor sites. 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 and washing unit includes a filtering device, the filtering device may be one or a combination of two or more of a gravity filtering device, a pressure filtering device, and a vacuum filtering 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
The solid-liquid separation and washing unit can further comprise a blowing device, and natural wind or pressurized wind is 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.
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 and washing unit is
The value is such that the requirements for mixing with a compound having at least two proton acceptor sites 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 and washing 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 and filtering device and/or a vacuum filtering device, or do not adopt the pressurizing and filtering device and the vacuum filtering device, and preferably adopt the pressurizing and filtering device and/or the vacuum filtering 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 and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit based on the material flow direction of the hydrated alumina gel, and 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.
On the premise that the mixing unit can be provided with the hydrated alumina gel meeting the requirements, from the viewpoint of facilitating the transportation of materials, in a preferred embodiment, the solid-liquid separation and washing unit can comprise a washing subunit, a diluting subunit, a conveying subunit and a second solid-liquid separation subunit,
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.
As shown in fig. 2 and 3, a phosphorus-containing compound may be added to one, two, or three of the washing subunit, the diluting subunit, and the transporting subunit.
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 an optional phosphorus-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.
The production molding system is not provided with a dehydration unit which is enough to reduce the i value of the hydrated alumina wet gel to be less than 60 percent (preferably less than 62 percent) between the solid phase material outlet port of the solid-liquid separation and washing unit and the hydrated alumina wet gel inlet port of the mixing unit by taking the flow direction of the hydrated alumina gel as a reference.
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.
When the hydrated alumina production forming system is used for producing a formed body, the method can comprise the following steps:
(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 and washing unit for solid-liquid separation to obtain hydrated alumina wet gel;
(3) mixing said hydrated alumina wet gel with a compound having at least two proton acceptor sites in said mixing unit using the method of the second aspect of the invention to obtain a phosphorus-containing hydrated alumina composition;
(4) forming the phosphorus-containing hydrated alumina composition in a forming unit to obtain a phosphorus-containing hydrated alumina forming product;
(5) drying the molded product of the phosphorus-containing hydrated alumina in a drying unit to obtain a molded product of the phosphorus-containing hydrated alumina;
(6) roasting at least part of the phosphorus-containing hydrated alumina forming body in a roasting unit to obtain an alumina forming body;
wherein the operation of adding the phosphorus-containing compound is performed in one, two or three of the steps (1), (2) and (3) so that the hydrated alumina composition contains the phosphorus-containing compound.
The method for preparing the hydrated alumina gel solution in the step (1) has been described in detail above and will not be described in detail herein.
In the step (2), the solid-liquid separation condition is that the obtained hydrated alumina wet gel is
The value satisfies the requirements according to the second aspect of the present invention, and thus can be mixed with a compound having at least two proton acceptor sites to obtain a phosphorus-containing hydrated alumina composition.
In the step (3), the compound having at least two proton acceptor sites is added in an amount such that the phosphorus-containing hydrated alumina composition obtained is prepared
The values are such that they satisfy the requirements stated above. As mentioned above, the phosphorus-containing hydrated alumina composition may or may not contain a peptizing agent, i.e., in step (3), the peptizing agent may or may not be added to the hydrated alumina wet gel. In a preferred embodiment of the present invention, the peptizing agent is preferably added in an amount of 5 parts by weight or less relative to 100 parts by weight of a hydrated alumina wet gel in terms of hydrated alumina. In a particularly preferred embodiment of the invention, no peptizing agent is added to the hydrated alumina wet gel.
The forming in the step (4), the drying in the step (5) and the baking in the step (6) can refer to the related descriptions above, and are not described herein again.
The phosphorus-containing hydrated alumina molded bodies and the phosphorus-containing alumina molded bodies 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 phosphorus-containing hydrated alumina molded body and/or a phosphorus-containing alumina molded body as a support. Preferably, the catalyst is a catalyst having a hydrogenation catalytic effect. That is, the phosphorus-containing hydrated alumina formed body and the phosphorus-containing alumina formed body according to the present invention are particularly suitable as a carrier of a catalyst having a hydrogenation catalytic action.
According to a tenth 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 phosphorus-containing hydrated alumina molded body according to the present invention and/or a phosphorus-containing alumina molded body according to the present invention.
The hydrogenation active component may be of conventional choice. Preferably, the hydrogenation active component is selected from at least one group VIB metal element and at least one group VIII metal element. 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 carrier may be 55 to 94.5 wt%, preferably 62 to 92.5 wt%, more preferably 75 to 88 wt%, based on the total amount of the catalyst; the group VIII metal element may be contained in an amount of 0.5 to 10% by weight, preferably 1.5 to 8% by weight, more preferably 2 to 5% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 5 to 35 wt.%, preferably 6 to 30 wt.%, more preferably 10 to 20 wt.%, calculated as oxide.
According to an eleventh 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 phosphorus-containing hydrated alumina compact and/or a phosphorus-containing 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 phosphorus-containing hydrated alumina molded body and/or a phosphorus-containing alumina molded body. In this step, a molded body is produced by the method according to the sixth aspect or the eighth 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 are such that the contents of the group VIII metal element and the group VIB metal element in the finally prepared catalyst can satisfy the requirements of the tenth aspect of the present invention, based on the total amount of the prepared catalyst.
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 ℃, and 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 ℃, and 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 twelfth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having a hydrocatalytic action, wherein the catalyst having a hydrocatalytic action is the catalyst according to the tenth aspect of the present invention or the catalyst prepared by the method according to the eleventh 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. Preferably, the hydrocarbon oil may be one or more of various heavy mineral oils or heavy mineral oils, such as heavy deasphalted oil, atmospheric residue, and vacuum residue. The hydrotreating conditions include: the temperature can be 300-380 ℃; the pressure may be 4-15MPa in gauge pressure; 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 hydrated alumina composition are dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition is 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 mode pore size was determined using the Congta Poremaster33 instrument, USA, with reference to the mercury intrusion method specified in GB/T21650.1-2008. In the following examples and comparative examples, the dry content is determined by baking a sample to be tested at 600 ℃ for 4 hours, and is the percentage of the mass of the sample after baking to the mass of the sample before baking.
In the following examples and comparative examples, the composition of the catalyst was measured by using a 3271X-ray fluorescence spectrometer manufactured by Nippon mechanical electric machines Co., Ltd. in accordance with the method specified in the petrochemical analysis method RIPP 133-90.
Examples 1 to 8 illustrate the phosphorus-containing hydrated alumina composition, the molded article and the process for producing the same according to the present invention.
Example 1
The hydrated alumina wet gel used in this example was a pseudo-boehmite wet cake (the wet cake was designated as S L B-1) obtained by adding sodium phosphate to a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, available from the long-distance division of petrochemical, china) during aging, washing and filtering, and it was determined that the i value of the wet cake was 77.6% and P was used as the value of P2O5The phosphorus content was 4.5% by weight.
(1) 200g of the wet cake numbered S L B-1 was placed in a beaker, and 5g of methylcellulose (available from Zhejiang Haishi chemical Co., Ltd.) and 3g of sesbania powder (galactomannan content 80 wt%, available from Beijing chemical Co., Ltd.) were added and stirred with a mechanical stirrer for 10 minutes to obtain a mixture which was the phosphorus-containing hydrated alumina composition of the present invention having the property parameters listed in Table 1.
(2) And (2) extruding the phosphorus-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder (manufactured by general scientific and technical industries of southern China university, the same shall apply hereinafter) by using a disc-shaped orifice plate with the diameter of 1.5 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 having a length of about 6mm and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips HT-1, the property parameters of which are listed in Table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain a phosphorus-containing alumina dry strip OT-1, wherein the property parameters are listed in Table 1.
Example 2
A phosphorus-containing alumina dry strip was 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 a phosphorus-containing alumina dry strip OT-2, the property parameters of which are shown in Table 1.
Example 3
A molded body was produced in the same manner as in example 1, except that sesbania powder was not used in the step (2) and the amount of methylcellulose used was 7.4g, and that the properties of the phosphorus-containing hydrous alumina composition, the phosphorus-containing hydrous alumina dry strip HT-3 and the phosphorus-containing alumina dry strip OT-3 were as shown in Table 1.
Example 4
A molded body was produced in the same manner as in example 1, except that no methylcellulose was used in the step (2) and that the amount of sesbania powder used was 9.25g, and the properties of the phosphorus-containing hydrous alumina composition, the phosphorus-containing hydrous alumina dry strip HT-4 and the phosphorus-containing alumina dry strip OT-4 were as shown in Table 1.
Example 5
A shaped body was produced in the same manner as in example 1, except that,in the step (2), 2.6g of nitric acid (HNO) is also added when methyl cellulose and sesbania powder are added3In an amount of 65 wt.%), the properties of the prepared phosphorus-containing hydrated alumina composition, phosphorus-containing hydrated alumina dry strip HT-5 and phosphorus-containing alumina dry strip OT-5 are listed in table 1.
Comparative example 1
(1) 500g of the wet filter cake numbered S L B-1 was dried at 82 ℃ for 3 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 51%, which was left standing at ambient temperature (25-30 ℃) under a closed condition (in a sealed plastic bag) for 72 hours, and no formation of alumina trihydrate was detected after the standing.
(2) And (3) extruding 89g of the 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 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips DHT-1, the property parameters of which are listed in Table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) for 6 hours at 580 ℃ in an air atmosphere to obtain a phosphorus-containing alumina dry strip DOT-1, wherein the property parameters are listed in Table 1.
Comparative example 2
(1) 500g of wet filter cake No. S L B-1 was dried at 90 ℃ for 4 hours in an air atmosphere to obtain pseudo-boehmite powder with an i value of 38%, which was left to stand at ambient temperature (25-30 ℃) for 72 hours under closed conditions (in a sealed plastic bag) and no formation of alumina trihydrate was detected after standing.
(2) 70g of the pseudo-boehmite powder prepared in the step (1) was put in a beaker, 5g of methylcellulose (same as in example 1) and 3g of sesbania powder (same as in example 1) were added, and after stirring for 10 minutes with a mechanical stirrer, a pseudo-boehmite composition was obtained.
(3) And (3) extruding the pseudo-thin diasphore composition prepared in the step (2) into strips by using a disc-shaped orifice plate with the diameter of 1.5mm on an F-26 type double-screw extruder (manufactured by general scientific and technological industries of southern China university, the same shall apply below). 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 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips DHT-2, the property parameters of which are listed in Table 1.
(5) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (4) for 6 hours at 580 ℃ in an air atmosphere to obtain a phosphorus-containing alumina dry strip DOT-2, wherein the property parameters are listed in Table 1.
Comparative example 3
(1) 70g of pseudo-boehmite powder prepared in the same manner as in step (1) of comparative example 2 was put in a beaker, and 5g of methylcellulose (same as in example 1), 3g of sesbania powder (same as in example 1) and 5.2g of nitric acid (HNO) were added365 wt.%) was stirred with a mechanical stirrer for 10 minutes to obtain a pseudo-boehmite composition.
(2) Extruding the pseudo-thin diasphore composition prepared in the step (1) into strips on an F-26 type double-screw extruder (manufactured by general scientific and technical industries of southern China university, the same shall apply hereinafter) by using a disc-shaped orifice plate with the diameter of 1.5 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 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips DHT-3, the property parameters of which are listed in Table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) for 6 hours at 580 ℃ in an air atmosphere to obtain the phosphorus-containing alumina dry strip DOT-3, wherein the property parameters are listed in Table 1.
Comparative example 4
A phosphorus-containing hydrated alumina composition was prepared in the same manner as in example 1, except that methyl cellulose and sesbania powder were not used, and 7.4g of paraffin was used. As a result, the phosphorus-containing hydrated alumina composition prepared could not be subjected to extrusion molding.
Comparative example 5
A phosphorus-containing hydrated alumina composition was prepared in the same manner as in example 1, except that methyl cellulose and sesbania powder were not used, and 7.4g of wood flour was used instead. As a result, the phosphorus-containing hydrated alumina composition prepared could not be subjected to extrusion molding.
Comparative example 6
The wet cake No. L B-1 was fed directly into an F-26 type twin-screw extruder and extruded through a disk-shaped orifice plate of 1.5mm in phi, with the result that extrusion molding could not be carried out.
Comparative example 7
(1) 300g of dry pseudoboehmite powder (purchased from the division of Long Ling, petrochemical, China, dry basis 0.75), placed at ambient temperature (25-30 ℃) for 72 hours in a closed condition (in a sealed plastic bag) and no formation of alumina trihydrate is detected after placement), 5g of methylcellulose (same as in example 1), 3g of sesbania powder (same as in example 1) and 5.2g of nitric acid (HNO)365 wt%) was stirred with a mechanical stirrer for 10 minutes to obtain a pseudo-boehmite composition.
(2) Extruding the pseudoboehmite composition prepared in the step (1) on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 1.5 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 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips DHT-4, the property parameters of which are listed in Table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) for 6 hours at 580 ℃ in an air atmosphere to obtain a phosphorus-containing alumina dry strip DOT-4, wherein the property parameters are listed in Table 1.
Example 6
(1) 5kg of the wet cake numbered S L B-1 was mixed with 500g of deionized water, 33g of methylcellulose (available from Zhejiang Haishi chemical Co., Ltd.) and 20g of sesbania powder (having a galactomannan content of 80 wt%, available from Beijing chemical Co., Ltd.) 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 relief of the plate and frame was the phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the phosphorus-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 phi of 1.5 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 having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips HT-6, the property parameters of which are listed in table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 3 hours in an air atmosphere to obtain a phosphorus-containing alumina dry strip OT-6, wherein the property parameters are listed in Table 1.
Example 7
The hydrated alumina wet gel used in this example was prepared by mixing CO2Method (sodium aluminate-CO)2The method comprises the steps of taking hydrated alumina gel solution prepared from Shanxi province, Shaanxi county, Xinghao catalyst New Material Co., Ltd.), adding phosphoric acid in the aging process, washing and filtering to obtain pseudo-boehmite wet filter cake (the number of the wet filter cake is S L B-2), and measuring the value of i of the wet filter cake to be 75 percent, and taking P as the reference2O5The calculated phosphorus content was 3.2 wt.%.
(1) 1000g of the wet cake numbered S L B-2 was placed in a beaker, and then 15g of methylcellulose (available from Zhejiang Haishi chemical Co., Ltd.) and 20g of sesbania powder (galactomannan content 80 wt%, available from Beijing chemical Co., Ltd.) were added and stirred with a mechanical stirrer for 10 minutes to obtain a mixture which was the phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the phosphorus-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 2.4mm, 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 5mm and the wet strips were dried at 140 c for 3 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips HT-7, the property parameters of which are listed in table 1.
(4) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (3) for 4 hours at the temperature of 560 ℃ in an air atmosphere to obtain a phosphorus-containing alumina dry strip OT-7, wherein the property parameters are listed in Table 1.
Example 8
(1) 5kg of the wet cake No. S L B-1 was mixed with 700g of deionized water and beaten for 1 minute, the resulting slurry was fed to 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 blowing the cake in the plate and frame with pressurized air of 0.5MPa for 3 minutes, the plate and frame was depressurized to obtain a wet cake No. L B-5, and it was determined that the i value of the wet cake No. L B-5 was 75% by weight.
(2) 1000g of the wet cake numbered L B-5 was placed in a beaker, and 45g of sodium phosphate, 16g of hydroxypropyl methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd.) and 20g 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 phosphorus-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(3) And (3) extruding the phosphorus-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 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 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give dry phosphorus-containing hydrated alumina strips HT-8, the property parameters of which are listed in table 1.
(5) And (3) roasting the phosphorus-containing hydrated alumina dry strip prepared in the step (4) at 950 ℃ for 2.5 hours in an air atmosphere to obtain a phosphorus-containing alumina dry strip OT-8, 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.
2: the pore size distribution is unimodal.
The results of examples 1-8 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 phosphorus-containing compound and a compound with at least two proton acceptor sites, 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. Also, the hydrated alumina composition according to the present invention can prepare a shaped body having a bimodal distribution of pore diameters using only one hydrated alumina.
Experimental examples 1 to 8 are provided to illustrate catalysts having hydrogenation catalysis according to the present invention and a method for preparing the same.
Experimental example 1
(1) Molybdenum oxide and basic cobaltous carbonate are dispersed in deionized water to prepare an impregnating solution, wherein MoO3Was 162.4 g/L, the concentration of basic cobalt carbonate as CoO was 39.2 g/L. the obtained impregnation solution was impregnated with the phosphorus-containing hydrated alumina dry strip prepared in example 1 as a carrier by a saturated impregnation method for 5 hours, the impregnated mixture was dried at 125 ℃ for 3 hours and then calcined at 420 ℃ for 4 hours to obtain catalyst CH-1 of the present invention, and the results of the measurement of the catalyst composition by XRF are shown in Table 2.
(2) The catalyst was prepared by the same method as in step (1) except that MoO3Was 150.5 g/L, the cobalt hydroxycarbonate concentration calculated as CoO was 36.3 g/L, and the support was a dry, phosphorus-containing alumina strip prepared in example 1, giving the catalyst CO-1 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental example 2
A catalyst was prepared in the same manner as in Experimental example 1, except that (1) was not conducted, and in (2), MoO3Was 154.2 g/L, the cobalt hydroxycarbonate concentration was 37.2 g/L calculated as CoO, and the support was the phosphorus-containing alumina dry strip prepared in example 2, giving catalyst CO-2 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental example 3
A catalyst was prepared in the same manner as in experimental example 1, except that: (1) medium, MoO3156.9 g/L, a basic cobalt carbonate concentration of 37.9 g/L calculated as CoO, and a carrier which was a dry, phosphorus-containing hydrated alumina rod prepared in example 3 gave the catalyst CH-3 of the invention the composition of the catalyst was determined by XRF and the results are shown in Table 2;
(2) medium, MoO3143.4 g/L, a basic cobalt carbonate concentration of 34.6 g/L calculated as CoO, and a carrier which was a dry, phosphorus-containing alumina strip as prepared in example 3, gave catalyst CO-3 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental example 4
A catalyst was prepared in the same manner as in experimental example 1, except that: (1) medium, MoO3173.2 g/L, a basic cobalt carbonate concentration of 41.8 g/L calculated as CoO, and a carrier which is a dry, phosphorus-containing hydrated alumina strip as prepared in example 4, to give catalyst CH-4 according to the invention the composition of the catalyst was determined by XRF, the results of which are shown in Table 2;
(2) medium, MoO3187.3 g/L, cobalt hydroxycarbonate at a concentration of 45.2 g/L calculated as CoO, and the support is a dry strip of phosphorus-containing alumina prepared in example 4, giving the catalyst CO-4 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental example 5
A catalyst was prepared in the same manner as in experimental example 1, except that: (1) in the process, the carrier is the phosphorus-containing hydrated alumina dry strip prepared in example 5, and as a result, the phenomena of structural collapse and pulverization occur in the dipping process;
(2) medium, MoO3Was 159.6 g/L, the cobalt hydroxycarbonate concentration was 38.5 g/L calculated as CoO, and the support was a dry, phosphorus-containing alumina strip prepared in example 5, giving catalyst CO-5 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental comparative example 1
A catalyst was prepared in the same manner as in experimental example 1, except that: (1) in the above, the carrier was the dry alumina bar containing phosphorus prepared in comparative example 7, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) medium, MoO3Is 189.2 g/L, the cobalt hydroxycarbonate concentration, calculated as CoO, is 45.7 g/L, the support is a dry strip of phosphorus-containing alumina prepared in comparative example 7, giving catalyst DCO-1. the composition of the catalyst is determined by XRF, the results are shown in table 3.
Experimental example 6
(1) Dispersing basic nickel carbonate and molybdenum oxide in deionized water to prepare a steeping fluid, wherein MoO3180.0 g/L, and 43.4 g/L as NiO the resulting impregnation solution was impregnated with the dry phosphorus-containing hydrated alumina strip prepared in example 6 as a support by the saturated impregnation method for 3 hours, the impregnated mixture was dried at 120 ℃ for 5 hours, and then calcined at 450 ℃ for 4 hours to obtain the catalyst CH-6 of the present invention, and the composition of the catalyst was measured by XRF, the results of which are shown in table 2.
(2) The catalyst was prepared by the same method as in step (1) except that MoO3187.3 g/L, basic nickel carbonate as NiO at a concentration of 45.2 g/L, and a carrier which was a dry, phosphorus-containing alumina rod prepared in example 6, to obtain the catalyst CO-6 of the present invention the composition of the catalyst was determined by XRF, and the results are shown in Table 3.
Experimental example 7
(1) Dispersing basic nickel carbonate and molybdenum oxide in deionized water to prepare a steeping fluid, wherein MoO3Has a concentration of 120.6 g/L and a concentration of basic nickel carbonate (calculated as NiO) of 28.7 g/L. the obtained impregnation liquid is saturated and impregnatedThe dry strips of phosphorus-containing hydrated alumina prepared in example 7 as a support were impregnated for 6 hours. The impregnated mixture was dried at 140 ℃ for 3 hours and then calcined at 500 ℃ 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) The catalyst was prepared by the same method as in step (1) except that MoO3Was 111.0 g/L, the concentration of basic nickel carbonate was 26.4 g/L calculated as NiO, and the support was a dry, phosphorus-containing alumina strip as prepared in example 7 to give catalyst CO-7 according to the invention the composition of the catalyst was determined by XRF and the results are shown in Table 3.
Experimental example 8
(1) Dispersing basic nickel carbonate and ammonium molybdate in deionized water to prepare a steeping fluid, wherein MoO3206.1 g/L, and 49.2 g/L of basic nickel carbonate in terms of NiO the resulting impregnation solution was impregnated with the phosphorus-containing hydrated alumina dry strip prepared in example 8 as a support by a saturated impregnation method for 8 hours, the impregnated mixture was dried at 140 c for 3 hours and then calcined at 480 c for 4 hours to obtain the catalyst CH-8 of the present invention, and the composition of the catalyst was measured by XRF, the results of which are shown in table 2.
(2) The catalyst was prepared by the same method as in step (1) except that MoO3217.2 g/L, a basic nickel carbonate concentration of 51.9 g/L calculated as NiO, and a support which was a dry, phosphorus-containing alumina rod as prepared in example 8, to give catalyst CO-8 according to the invention the composition of the catalyst was determined by XRF, the results of which are shown in table 3.
TABLE 2
TABLE 3
Test examples 1-8 are intended to illustrate the hydrotreating process according to the invention.
The catalysts prepared in experimental examples 1 to 8 were evaluated for their catalytic performance by the following methods, and the results are shown in Table 4.
The adopted raw oil is light and normal pressure sieroze residual oil, the mass content of nickel is 11.7ppm, the mass content of vanadium is 31.7ppm, the sulfur content is 3.5 weight percent, the nitrogen content is 0.21 weight percent, and the carbon residue is 11.7 weight percent.
Crushing a catalyst into particles with the diameter of 2-3mm, loading the particles into a reactor, and introducing raw oil for reaction, wherein the reaction temperature is 380 ℃, the hydrogen partial pressure is 14MPa, and the volume space velocity of the raw oil is 2h-1。
The removal rate of impurities was calculated according to the following formula:
testing of comparative examples 1-3
The catalysts prepared in experimental comparative examples 1 to 3 were evaluated for their catalytic performance in the same manner as in test examples 1 to 8, respectively, and the results of the experiments are shown in Table 4.
TABLE 4
The results of test examples 1 to 8 confirmed that the catalysts prepared using the phosphorus-containing hydrated alumina molded body and the alumina molded body 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 (70)
1. A phosphorus-containing hydrated alumina composition comprising hydrated alumina, a phosphorus-containing compound and a compound having at least two proton acceptor sites, wherein the compound having at least two proton acceptor sites is one or more of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,
the phi value of the composition is 1.8-5, and the phi value is determined by 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 w1The value phi is calculated by adopting the formula I,
the preparation method of the phosphorus-containing hydrated alumina composition comprises the steps of mixing the components in a raw material composition to obtain the hydrated alumina composition, wherein the raw material composition contains a hydrated alumina wet gel, a phosphorus-containing compound and a compound with at least two proton acceptor sites, the i value of the hydrated alumina wet gel is not less than 60 percent, the compound with at least two proton acceptor sites is used in an amount to ensure that the phi value of the finally prepared composition is 1.8-5,
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 value of Φ is from 1.85 to 4.
3. The composition of claim 2 wherein the value of Φ is from 1.9 to 3.5.
4. The composition according to any one of claims 1 to 3, wherein the compound having at least two proton acceptor sites is contained in an amount of 1 to 25 parts by weight relative to 100 parts by weight of the hydrated alumina.
5. The composition according to claim 4, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 22 parts by weight relative to 100 parts by weight of the hydrated alumina.
6. The composition according to claim 5, wherein the compound having at least two proton acceptor sites is contained in an amount of 4 to 20 parts by weight with respect to 100 parts by weight of the hydrated alumina.
7. The composition according to any one of claims 1 to 3, wherein the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina2O5The content is 1.5-40 weight portions.
8. The composition of claim 7, wherein the phosphorus-containing compound is represented by P, relative to 100 parts by weight of the hydrated alumina2O5The content is 2-30 weight portions.
9. The composition of claim 8, wherein the amount of the hydrated alumina is 100 parts by weightThe phosphorus-containing compound is represented by P2O5The content is 3-25 weight portions.
10. The composition of any one of claims 1-3, 5-6, 8-9, 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.
11. The composition of claim 10, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
12. The composition of claim 10, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
13. The composition of claim 12, 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.
14. The composition of claim 13, 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.
15. The composition of claim 14, 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.
16. The composition of claim 15, wherein the galactomannan is present in an amount of 25 to 60 wt.% and the cellulose ether is present in an amount of 40 to 75 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 30 to 55 wt% and the cellulose ether is present in an amount of 45 to 70 wt%, based on the total amount of the compound having at least two proton acceptor sites.
18. The composition of any of claims 1-3, 5-6, 8-9, 11-17, wherein the hydrated alumina comprises pseudoboehmite.
19. The composition of claim 18, wherein the hydrated alumina is pseudoboehmite.
20. The composition of claim 18, 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.
21. The composition of claim 20, 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.
22. The composition of claim 21, 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.
23. The composition of claim 22, wherein the alumina trihydrate content in the composition after placement is increased by at least 1.1% to 2% based on the total alumina trihydrate content in the composition prior to placement.
24. The composition of any of claims 1-3, 5-6, 8-9, 11-17, 19-23, wherein the hydrated alumina is derived directly from a hydrated alumina wet gel.
25. The composition of any of claims 1-3, 5-6, 8-9, 11-17, 19-23, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, sodium phosphate, aluminum phosphate, ammonium hydrogen phosphate, and ammonium phosphate.
26. The composition of any one of claims 1-3, 5-6, 8-9, 11-17, 19-23, wherein the composition is free of a peptizing agent.
27. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of not less than 62%.
28. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of not greater than 82%.
29. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of not greater than 80%.
30. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of not greater than 78.5%.
31. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of 60-82%.
32. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of 62-80%.
33. The composition of claim 1, wherein the hydrated alumina wet gel has an i value of 62-78.5%.
34. The composition of any of claims 1-3, 5-6, 27-33, 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.
35. The composition of any of claims 1-3, 5-6, 27-33, wherein the hydrated alumina wet gel is obtained by washing and solid-liquid separation of at least one hydrated alumina gel solution, optionally after aging.
36. The composition of any one of claims 1-3, 5-6, and 27-33, wherein the hydrated alumina gel solution is prepared using a precipitation method, a hydrolysis method, an seeded precipitation method, and a flash dehydration method.
37. The composition of any one of claims 1-3, 5-6, 27-33, wherein the feedstock composition is free of a peptizing agent.
38. The composition of any of claims 1-3, 5-6, 27-33, wherein the mixing is by stirring and/or kneading.
39. A phosphorus-containing hydrated alumina molded body formed from the phosphorus-containing hydrated alumina composition described in any one of claims 1 to 3, 5 to 6, 8 to 9, 11 to 17, and 19 to 23.
40. The phosphorus-containing hydrated alumina forming body of claim 39, wherein the pore size distribution of the phosphorus-containing hydrated alumina forming body is bimodal with a maximum possible pore size of 4 to 20nm and greater than 20nm, respectively, as measured by mercury intrusion porosimetry.
41. A phosphorus-containing alumina hydrate formed body formed of the phosphorus-containing alumina hydrate composition according to any one of claims 1 to 3, 5 to 6, 8 to 9, 11 to 17, and 19 to 23.
42. The phosphorus-containing alumina hydrate according to claim 41, wherein the pore size distribution of the phosphorus-containing alumina hydrate is bimodal with a maximum possible pore size of 4 to 20nm and greater than 20nm, respectively, as determined by mercury intrusion.
43. A process for the preparation of a shaped body, which process comprises shaping a phosphorus-containing hydrated alumina composition as claimed in any one of claims 1 to 3, 5 to 6, 8 to 9, 11 to 17, 19 to 23, drying and optionally calcining the obtained shaped body.
44. A shaped body prepared by the method of claim 43.
45. The phosphorus-containing hydrated alumina molding as claimed in claim 39, wherein the radial crush strength of the molding is 10N/mm or more.
46. The phosphorus-containing hydrated alumina compact of claim 45, wherein the radial crush strength of the compact is 12N/mm or greater.
47. The phosphorus-containing hydrated alumina compact of claim 46, wherein the radial crush strength of the compact is 15N/mm or more.
48. The phosphorus-containing hydrated alumina forming body of claim 47, wherein the radial crush strength of the forming body is 15 to 35N/mm.
49. The phosphorus-containing hydrated alumina forming body of claim 48, wherein the radial crush strength of the forming body is 15 to 32N/mm.
50. A production and forming method of phosphorus-containing 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%;
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 with a phosphorus-containing compound and a compound having at least two proton acceptor sites to obtain a hydrated alumina composition, wherein the compound having at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,
the compound having at least two proton acceptor sites is used in an amount such that the finally prepared composition has a value of phi of 1.8 to 5, as determined by 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 w1The value phi is calculated by adopting the formula I,
(3) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(4) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(5) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the method further comprises performing an operation of mixing a phosphorus-containing compound in step (1) so that the hydrated alumina composition contains a phosphorus-containing compound.
51. The method of claim 50 wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 62%.
52. The method of claim 51 wherein the solid-liquid separation conditions are such that the i value of the first hydrated alumina wet gel is no greater than 82%.
53. The method of claim 52, wherein the solid-liquid separation conditions are such that the i value of the first hydrated alumina wet gel is not greater than 80%.
54. The method of claim 53, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 78.5%.
55. A production and forming method of phosphorus-containing 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 the step (2-1) 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;
(2-1), the solid-liquid separation conditions are such that the i value of the second hydrated alumina wet gel is not less than 60%,
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 the second hydrated alumina wet gel with a compound having at least two proton acceptor sites, wherein the compound having at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,
the compound having at least two proton acceptor sites is used in an amount such that the finally prepared composition has a value of phi of 1.8 to 5, as determined by 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 w1The value phi is calculated by adopting the formula I,
(4) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(5) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(6) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the method further comprises an operation of mixing a phosphorus-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a phosphorus-containing compound.
56. The method of claim 55 wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 62%.
57. The method of claim 55, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not greater than 82%.
58. The method of claim 57, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not greater than 80%.
59. The method of claim 58, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not greater than 78.5%.
60. The process of any one of claims 50 to 59, 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.
61. The method of any one of claims 50-59, wherein the hydrated alumina gel solution is an aged or unaged reaction mixture prepared by one or more of precipitation, hydrolysis, seeded precipitation, and flash dehydration.
62. A shaped body prepared by the method of any one of claims 50-59.
63. Shaped body according to claim 62, having a radial crush strength of from 10 to 35N/mm.
64. 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 phosphorus-containing hydrated alumina molded body according to claim 39.
65. The catalyst of claim 64, wherein the hydrogenation active component is selected from at least one group VIII metal element and at least one group VIB metal element.
66. The catalyst of claim 64, wherein the group VIII metal element is present in an amount of 0.5 to 10 wt.% on an oxide basis and the group VIB metal element is present in an amount of 5 to 35 wt.% on an oxide basis, based on the total amount of the catalyst.
67. 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 phosphorus-containing hydrated alumina molded body according to claim 39.
68. The process of claim 67, wherein said hydrogenation active component is selected from at least one group VIII metal element and at least one group VIB metal element.
69. The process of claim 68, wherein the group VIII metal element is present in an amount of from 0.5 to 10 wt.% as oxide and the group VIB metal element is present in an amount of from 5 to 35 wt.% as oxide, based on the total amount of the catalyst.
70. A hydroprocessing method comprising contacting, under hydroprocessing conditions, a hydrocarbon oil with a catalyst having a hydrocatalytic effect, wherein the catalyst having a hydrocatalytic effect is the catalyst of any one of claims 64-66 or the catalyst prepared by the method of any one of claims 67-69.
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| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
| CN104907103A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Preparation method of spherical alumina carrier |
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| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
| CN104907103A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Preparation method of spherical alumina carrier |
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