CN108014824B - Halogen-containing hydrated alumina composition, molded body, preparation method and application of halogen-containing hydrated alumina composition, catalyst and preparation method of catalyst - Google Patents
Halogen-containing hydrated alumina composition, molded body, preparation method and application of halogen-containing hydrated alumina composition, catalyst and preparation method of catalyst Download PDFInfo
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- CN108014824B CN108014824B CN201610964032.2A CN201610964032A CN108014824B CN 108014824 B CN108014824 B CN 108014824B CN 201610964032 A CN201610964032 A CN 201610964032A CN 108014824 B CN108014824 B CN 108014824B
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- hydrated alumina
- composition
- halogen
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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 765
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 459
- 150000002367 halogens Chemical class 0.000 title claims abstract description 459
- 239000000203 mixture Substances 0.000 title claims abstract description 343
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 241
- 239000011240 wet gel Substances 0.000 claims abstract description 185
- 230000008569 process Effects 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 56
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 190
- 238000000926 separation method Methods 0.000 claims description 88
- 239000007788 liquid Substances 0.000 claims description 86
- 239000000499 gel Substances 0.000 claims description 74
- 238000002156 mixing Methods 0.000 claims description 63
- 239000012298 atmosphere Substances 0.000 claims description 60
- 238000005406 washing Methods 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000004519 manufacturing process Methods 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 43
- 238000000465 moulding Methods 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 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 32
- 229920000926 Galactomannan Polymers 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 24
- 229920003086 cellulose ether Polymers 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 23
- -1 galactan Polymers 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 150000004684 trihydrates Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 208000005156 Dehydration Diseases 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 230000002902 bimodal effect Effects 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 229920000609 methyl cellulose Polymers 0.000 claims description 10
- 239000001923 methylcellulose Substances 0.000 claims description 10
- 235000010981 methylcellulose Nutrition 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000057 Mannan Polymers 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 229940107816 ammonium iodide Drugs 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002683 Glycosaminoglycan Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002307 Dextran Polymers 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims 2
- 229920001503 Glucan Polymers 0.000 claims 1
- 238000002459 porosimetry Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 38
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000000428 dust Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003292 glue Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 62
- 238000009740 moulding (composite fabrication) Methods 0.000 description 42
- 238000001914 filtration Methods 0.000 description 31
- 239000000463 material Substances 0.000 description 30
- 238000001125 extrusion Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 21
- 238000004846 x-ray emission Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 241000219782 Sesbania Species 0.000 description 19
- 239000007790 solid phase Substances 0.000 description 19
- 239000012065 filter cake Substances 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 18
- 239000012265 solid product Substances 0.000 description 16
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 12
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 10
- 150000004676 glycans Chemical class 0.000 description 10
- 229920001282 polysaccharide Polymers 0.000 description 10
- 239000005017 polysaccharide Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 229940024545 aluminum hydroxide Drugs 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
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- 150000004682 monohydrates Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
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- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 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
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
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- 238000005119 centrifugation Methods 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 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
- 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
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, 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
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses a halogen-containing hydrated alumina composition and a preparation method thereof, and a formed body and a preparation method and application thereof
The value is 5 or less. The invention also discloses a catalyst with hydrogenation catalysis function and a preparation method thereof, and a hydrotreating method, wherein the catalyst takes a formed body formed by the halogen-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 initial raw material, omits the step of drying the hydrated alumina wet gel, simplifies the overall process flow, reduces the overall operation energy consumption and avoids the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material. The catalyst prepared by using the formed body formed by the hydrated alumina composition as a carrier shows higher catalytic activity in hydrocarbon oil hydrotreating.
Description
Technical Field
The invention relates to the technical field of alumina forming, in particular to a halogen-containing hydrated alumina composition and a preparation method thereof, a hydrated alumina forming body and an alumina forming body which are formed by the halogen-containing hydrated alumina composition, 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 halogen-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 halogen element into the molded body so as to meet the requirements of specific application occasions, such as: the hydrofining catalyst is prepared by adopting the halogen-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 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 halogen-containing compound shown in fig. 1) and an optional chemical peptizing agent (inorganic acid and/or organic acid) are added, and after kneading and molding, the molded 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 use industrial use requirements can be obtained.
Disclosure of Invention
The invention aims to simplify the preparation process flow of the alumina carrier, reduce the dust pollution in the preparation process of the alumina carrier and simultaneously ensure that the prepared carrier can meet the industrial use requirement.
Aiming at the problems of the preparation of alumina carriers of US4613585 and CN103769118A, the inventor of the present invention has a new approach to mix a compound containing at least two proton acceptor sites in the molecular structure with hydrated alumina wet gel directly from the synthesis reaction, and the formed mixture can be shaped, and the shaped body obtained by drying and optional roasting can have the strength meeting the industrial requirements. The present invention has been completed based on this finding.
According to a first aspect of the present invention there is provided a halogen-containing hydrated alumina composition comprising hydrated alumina, a halogen-containing compound and a compound having at least two proton acceptor sites,
of said composition
A value of 5 or less, 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 halogen-containing hydrated alumina composition, which process comprises mixing the components of a feedstock composition comprising a hydrated alumina wet gel, a halogen-containing compound and a compound having at least two proton acceptor sites, the hydrated alumina wet gel having an i value of not less than 60%, the compound having at least two proton acceptor sites being used in an amount such that the components are mixed to give the hydrated alumina compositionTo obtain the final prepared composition
The value of the amount of the organic acid is 5 or less,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the above-mentioned
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w1Is calculated by formula I
The value of the one or more of,
according to a third aspect of the present invention there is provided a halogen-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 halogen-containing hydrated alumina molded body formed from the halogen-containing hydrated alumina composition of the first aspect of the present invention or the halogen-containing hydrated alumina composition of the third aspect of the present invention.
According to a fifth aspect of the present invention, there is provided a method for producing a halogen-containing hydrated alumina molded body, which comprises molding the halogen-containing hydrated alumina composition according to the first aspect of the present invention or the halogen-containing hydrated alumina composition according to the third aspect of the present invention, and drying the resulting molded body.
According to a sixth aspect of the present invention, there is provided a halogen-containing hydrated alumina formed body produced by the method of the fifth aspect of the present invention.
According to a seventh aspect of the present invention, there is provided a halogen-containing alumina hydrate molded body formed from the halogen-containing alumina hydrate composition according to the first aspect of the present invention or the halogen-containing alumina hydrate composition according to the third aspect of the present invention.
According to an eighth aspect of the present invention, there is provided a method for producing a halogen-containing alumina hydrate molded body, which comprises molding the halogen-containing alumina hydrate composition according to the first aspect of the present invention or the halogen-containing alumina hydrate composition according to the third aspect of the present invention, and drying and firing the resulting molded body.
According to a ninth aspect of the present invention, there is provided a halogen-containing alumina molded body produced by the method according to the eighth aspect of the present invention.
According to a tenth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing halogen, 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 said 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 halogen-containing hydrated alumina composition;
(3) molding the halogen-containing hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;
(4) drying the halogen-containing hydrated alumina forming product to obtain a halogen-containing hydrated alumina forming product;
(5) optionally, roasting at least part of the halogen-containing hydrated alumina forming body to obtain a halogen-containing alumina forming body,
wherein the method further comprises mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.
According to an eleventh aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing halogen, 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 hydrated alumina wet gel was put in an air atmosphere at 120 deg.CDrying for 240 minutes, the mass of the dried sample is 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 halogen-containing hydrated alumina composition;
(4) molding the hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;
(5) drying the halogen-containing hydrated alumina forming product to obtain a halogen-containing hydrated alumina forming product;
(6) optionally, roasting at least part of the halogen-containing hydrated alumina forming body to obtain a halogen-containing alumina forming body;
wherein the method further comprises mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.
According to a twelfth aspect of the present invention, there is provided a molded body produced by the method according to the tenth or eleventh aspect of the present invention.
According to a thirteenth aspect of the invention, the invention provides a halogen-containing hydrated alumina shaped body and the use of a halogen-containing alumina shaped body according to the invention as a support or adsorbent.
According to a fourteenth aspect of the present invention, there is provided a catalyst having a hydrogenation catalytic action, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is a halogen-containing hydrated alumina molded body according to the present invention or a halogen-containing alumina molded body according to the present invention.
According to a fifteenth aspect of the present invention, there is provided a method for producing a catalyst having a hydrogenation catalytic action, the method comprising supporting a hydrogenation-active component on a support, wherein the support is a halogen-containing hydrated alumina compact according to the present invention or a halogen-containing alumina compact according to the present invention.
According to a sixteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting a hydrocarbon oil under hydrotreating conditions with a catalyst having hydrocatalytic action, wherein the catalyst having hydrocatalytic action is the catalyst according to the fourteenth aspect of the present invention or the catalyst prepared by the method according to the fifteenth aspect of the present invention.
Compared with the prior process method (as shown in figure 1) for preparing the alumina carrier containing halogen by taking the pseudoboehmite dry glue powder as the starting material, the invention directly takes the hydrated alumina wet gel prepared by the synthesis reaction as the starting material for forming, and has the following advantages:
(1) the step of drying the hydrated alumina wet gel in the prior art is omitted, and when the forming raw material is prepared, the pseudo-boehmite dry glue powder is prepared into a formable material without additionally introducing water, so that the overall process flow is simplified, and the overall operation energy consumption is reduced;
(2) avoids dust pollution caused by adopting the pseudo-boehmite dry glue powder as a raw material, and greatly improves the operation environment.
Compared with the prior art, such as US4613585 and CN103769118A, which directly takes the hydrated alumina wet gel as the starting material to prepare the carrier, the process of the invention is simpler and has stronger operability, and can effectively improve the strength of the finally prepared formed body, and simultaneously can adjust the pore size distribution of the finally prepared formed body, thereby meeting the requirements of various use occasions. The reason why the present invention can produce a molded body having a higher strength from a hydrated alumina wet gel as a starting material may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel interact to form hydrogen bonds to adsorb the free water in the hydrated alumina wet gel, and simultaneously, the compound with at least two proton acceptor sites and the hydroxyl in the molecular structure of the hydrated alumina can also perform hydrogen bond interaction to play a role of physical peptization, so that the hydrated alumina wet gel can be molded, and the finally prepared molded body has higher strength.
And, according to the hydrated alumina composition of the present invention, by adjusting it
The pore size distribution of the shaped bodies formed can be adjusted to give shaped bodies having a monomodal or bimodal distribution. Further, the catalyst prepared by using the molded body formed of the hydrated alumina composition according to the present invention as a carrier shows higher catalytic activity in hydrotreating of hydrocarbon oil.
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 halogen-containing hydrated alumina composition comprising hydrated alumina, a halogen-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 halogen-containing hydrated alumina composition according to this preferred embodiment is particularly suitable for preparing shaped bodies for use as catalyst supports.
According to the halogen-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" means an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for lowering its i value to 60% or less (preferably 62% or less). In the present invention, the value of i is determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the synthesis reaction refers to a reaction for preparing an aluminum hydroxide gel, and may be a synthesis reaction of a hydrated alumina gel commonly used in the art, and specifically, a precipitation method (including an acid method and an alkaline method), a hydrolysis method, an seeded precipitation method, and a rapid dehydration method may be mentioned. The synthesized hydrated alumina gel may be either a hydrated alumina gel that has not undergone aging or a hydrated alumina gel that has undergone aging. The specific operating methods and conditions for the precipitation, hydrolysis, seeding and flash dehydration processes may be routinely selected and will be described hereinafter. The hydrated alumina wet gel can be obtained by optionally aging the hydrated alumina gel obtained by the synthesis reaction, washing and performing solid-liquid separation, and collecting the solid phase.
Unlike hydrated alumina derived from dry gelatine powder, the hydrated alumina directly derived from hydrated alumina gel undergoes a phase change during storage. For example, the phase of the hydrated alumina in the composition after exposure to ambient temperature and under closed conditions may change for 72 hours. The ambient temperature depends on the environment in which it is placed and may typically be in the range of 5-50 deg.C, such as 20-40 deg.C. The closed condition means that the composition is placed in a closed container, which may be a closed container (such as a can, pail or box) or a closed flexible wrap (such as a lidded bag), which may be paper and/or a polymeric material, preferably a polymeric material such as plastic.
In one example, where the hydrated alumina directly derived from the hydrated alumina gel comprises pseudo-boehmite (e.g., the hydrated alumina directly derived from the hydrated alumina gel is pseudo-boehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after being left to stand being higher than the alumina trihydrate content in the composition before being left to stand. In this example, the alumina trihydrate content in the composition after placement is generally increased by at least 0.5%, preferably by at least 0.8%, more preferably by from 1% to 2%, based on the total amount of alumina trihydrate content in the composition before placement.
The halogen-containing hydrated alumina composition according to the present invention further contains a compound having at least two proton acceptor sites. The halogen-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 obtained molded article has a higher strength may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel generate hydrogen bond interaction, so that the free water is adsorbed, and simultaneously, the compound and the hydroxyl in the molecular structure of the hydrated alumina generate interaction to play a role in peptization.
In the compound having at least two proton acceptor sites, the proton acceptor site refers to a site capable of forming a hydrogen bond with water and a hydroxyl group in the molecular structure of the compound. Specific examples of the proton acceptor site include, but are not limited to, one or two or more of fluorine (F), oxygen (O), and nitrogen (N). Specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, compounds having one or more groups selected from hydroxyl groups, carboxyl groups, amino groups, ether linkages, aldehyde groups, carbonyl groups, amide groups, and fluorine atoms in the molecular structure, preferably hydroxyl groups and/or ether linkages.
The compound having at least two proton acceptor sites may be an organic compound, an inorganic compound, or a combination of an organic compound and an inorganic compound. An organic compound having at least two proton acceptor sites is employed, which can be removed by a calcination process. By using an inorganic compound having at least two proton acceptor sites, part of the elements in the inorganic compound can remain in the finally produced shaped body, whereby auxiliary elements can be introduced into the shaped body by means of the inorganic compound.
In a preferred embodiment of the present invention, the compound having at least two proton acceptor sites is a polymer having a plurality of (e.g., three or more) proton acceptor sites in a molecular structure. According to this preferred embodiment, a better physical peptization effect is obtained, which further increases the strength of the finally produced shaped body, in particular when shaping is carried out by an extrusion process. Preferably, the polymer is an organic polymer. According to the preferred embodiment, specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, one or more of polyhydroxy compounds, polyethers, and acrylic-type polymers.
The polyol compound may be exemplified by, but not limited to, polysaccharides, etherified polysaccharides and polyols.
The polysaccharide may beThe polysaccharide is homopolysaccharide, heteropolysaccharide, or a combination of homopolysaccharide and heteropolysaccharide. Specific examples of the polysaccharide and its etherified product include, but are not limited to, dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide. The cellulose ether is an ether derivative in which hydrogen atoms of partial hydroxyl groups in a cellulose molecule are substituted with hydrocarbon groups, and the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl and unsubstituted hydrocarbyl. The unsubstituted hydrocarbon group is preferably an alkyl group (e.g., C)1-C5Alkyl groups of (ii). In the present invention, C1-C5Specific examples of the alkyl group of (1) include C1-C5Straight chain alkyl of (2) and C3-C5The branched alkyl group of (a), may be, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl. The substituted hydrocarbon group may be, for example, an alkyl group substituted with a hydroxyl group, a carboxyl group, a cyano group or an aryl group (e.g., C)1-C5Alkyl substituted by hydroxy, C1-C5Alkyl substituted by carboxyl, C substituted by aryl1-C5Alkyl) which may be phenyl or naphthyl. Specific examples of the substituted hydrocarbon group may include, but are not limited to: cyano, benzyl, phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The polysaccharides and etherified products thereof may be provided in various forms, for example: the galactomannan may be derived from sesbania powder.
Specific examples of the polyol include, but are not limited to, one or more of polyvinyl alcohol, partially acetalized polyvinyl alcohol (the acetalization degree may be 95% or less, preferably 80% or less, more preferably 70% or less, and further preferably 50% or less), polyether polyol, and polyester polyol.
Specific examples of the polyether include, but are not limited to, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, and polytetrahydrofuran.
The acrylic acid-type polymer refers to a polymer containing acrylic acid-type monomer units, which may be specifically, but not limited to, acrylic acid monomer units and alkyl acrylic acid monomer units (preferably, C)1-C5More preferably a methacrylic acid monomer unit). Specific examples of the acrylic polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-methyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, methacrylic acid-methyl acrylate copolymer, and methacrylic acid-methyl methacrylate copolymer.
In this preferred embodiment, the compound having at least two proton acceptor sites more preferably contains a polysaccharide and/or an etherified polysaccharide, and still more preferably a polysaccharide and/or an etherified polysaccharide.
In a more preferred embodiment of the invention, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. According to this more preferred embodiment, the moulded body formed from the composition according to the invention has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.
In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.
The halogen-containing hydrated alumina composition according to the present invention contains a halogen-containing compound. The halogen element in the halogen-containing compound may be fluorine, chlorine, bromine or iodine, and is preferably fluorine, chlorine or iodine. The amount of halogen-containing compound may be selected depending on the end use application of the composition. In one embodiment, the composition may contain the halogen-containing compound in an amount of 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight, in terms of halogen element, relative to 100 parts by weight of hydrated alumina. 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 halogen element in the halogen-containing hydrated alumina composition is determined by X-ray fluorescence spectroscopy (XRF). In addition, the content of the halogen element in the halogen-containing hydrated alumina composition can also be calculated by the material charging amount, and the material charging amount is used for calculating the content of the halogen element in the halogen-containing hydrated alumina composition in the embodiment of the invention.
The halogen-containing compound may be a compound containing a halogen element in a molecular structure. When the compound having at least two proton acceptor sites contains a fluorine atom in its molecular structure, at least a part of the halogen-containing compound may be a compound having at least two proton acceptor sites. Preferably, at least a portion of the halogen-containing compound is different from the compound having at least two proton acceptor sites, such as a small molecule compound. More preferably, at least a part of the halogen-containing compound is ammonium halide, and specific examples thereof may include, but are not limited to, one or two or more of ammonium fluoride, ammonium chloride, ammonium bromide, and ammonium iodide. Further preferably, at least a part of the halogen-containing compound is one or two or more of ammonium fluoride, ammonium chloride and ammonium iodide.
Of the compositions according to the invention
The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, and further preferably 3.2 or less.
The value may be 1.2 or more, preferably 1.3 or more. In particular, of the halogen-containing hydrated alumina composition
The value may be 1.2 to 5, preferably 1.2 to 4, more preferably 1.3 to 3.5, and further preferably 1.3 to 3.2. In one embodiment, of the halogen-containing hydrated alumina composition
The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.85, for example, may be 1.85 to 3.5, for example, may be 1.85 to 3.2. The halogen-containing hydrated alumina composition according to this embodiment can produce a shaped body having a bimodal distribution of pore sizes. In another embodiment, of the halogen-containing hydrated alumina composition
The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. The halogen-containing hydrated alumina composition according to this embodiment can produce a shaped body having a monomodal distribution of pore diameters.
In the present invention,
the values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
the compound having at least two proton acceptor sites is contained in an amount enabling the composition according to the invention
The value meets the above requirements. Preferably, the alumina hydrate has at least two with respect to 100 parts by weight of the alumina hydrateThe amount of the compound having a proton acceptor site may be 1 to 25% by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, and still more preferably 3.5 to 17 parts by weight.
The composition according to the invention may or may not contain a peptizing agent. The peptizing agent may be an agent having a gelling effect, which is generally used in the technical field of preparation of alumina moldings, and specific examples thereof may include, but are not limited to, alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid, and trichloroacetic acid.
According to the composition of the present invention, the compound having at least two proton acceptor sites can perform a physical peptization effect, particularly when the compound having at least two proton acceptor sites is a polymer containing at least two proton acceptor sites, so that the amount of a peptizing agent can be reduced, and even the peptizing agent can be omitted.
In a preferred embodiment of the present invention, the content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, with respect to 100 parts by weight of the hydrated alumina.
In a particularly preferred embodiment of the invention, the composition according to the invention does not contain a peptizing agent. According to the composition of this particularly preferred embodiment, when used for the production of a shaped body, the produced hydrated alumina shaped body can be used as an adsorbent or a carrier even if it is converted into an alumina shaped body without calcination, because when the unfired hydrated alumina shaped body contains a peptizing agent, the peptizing agent is dissolved during adsorption and impregnation, and is lost in a large amount, so that the shaped body is dissolved, pulverized, and collapsed in the channels, and finally loses its shape, and thus cannot be used as an adsorbent or a carrier.
According to a second aspect of the present invention, there is provided a process for preparing a halogen-containing hydrated alumina composition, the process comprising mixing the components of a feedstock composition to obtain the halogen-containing hydrated alumina composition, i.e. the mixture obtained by mixing is the halogen-containing hydrated alumina composition.
According to the method for preparing a halogen-containing hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a halogen-containing compound and a compound having at least two proton acceptor sites. The types of compounds having at least two proton acceptor sites and halogen-containing compounds are 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 a halogen-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 pressure filtration and/or vacuum filtration. 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 halogen-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 halogen-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 halogen-containing hydrated alumina composition
The value is 5 or less, preferably 4 or less, more preferably 3.5 or less, and further preferably 3.2 or less. The compound having at least two proton acceptor sites is preferably used in an amount such that the final halogen-containing hydrated alumina composition is prepared
The value is 1.2 or more, preferably 1.3 or more. In particular, the compound having at least two proton acceptor sites is preferably used in an amount such that the final halogen-containing hydrated alumina composition is prepared
The value is 1.2 to 5, preferably 1.2 to 4, more preferably 1.3 to 3.5, and further preferably 1.3 to 3.2. In one embodiment, the compound having at least two proton acceptor sites is preferably used in an amount such that the final halogen-containing hydrated alumina composition is prepared
The value is not less than 1.8, for example, may be 1.8 to 5, preferably not less than 1.85, for example, may be 1.85 to 3.5, for example, may be 1.85 to 3.2. The halogen-containing hydrated alumina composition according to this embodiment can produce a shaped body having a bimodal distribution of pore sizes. In another embodiment, the compound having at least two proton acceptor sites is preferably used in an amount such that the final halogen-containing hydrated alumina composition is prepared
The value is less than 1.8, for example, may be from 1.2 to less than 1.8, preferably not higher than 1.7, and for example may be from 1.3 to 1.7. The halogen-containing hydrated alumina composition according to this embodiment can produce a shaped body having a monomodal distribution of pore diameters.
Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 18 parts by weight, and further preferably 3.5 to 17 parts by weight, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.
In a more preferred embodiment, the compound having at least two proton acceptor sites comprises galactomannan and cellulose ether. The molded body formed from the composition according to this more preferred embodiment has higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.
In this more preferred embodiment, the galactomannan may be present in an amount of from 10 to 70 wt.%, preferably from 15 to 68 wt.%, more preferably from 20 to 65 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 32 to 85 wt%, more preferably 35 to 80 wt%.
According to the method for producing a halogen-containing hydrated alumina composition of the present invention, when the compound having at least two proton acceptor sites contains a halogen element, at least a part of the halogen-containing compound is the compound having at least two proton acceptor sites. Preferably, at least a portion of the halogen-containing compound is different from the compound having at least two proton acceptor sites, such as a small molecule compound. More preferably, at least a part of the halogen-containing compound is ammonium halide, and specific examples thereof may include, but are not limited to, one or two or more of ammonium fluoride, ammonium chloride, ammonium bromide, and ammonium iodide. Further preferably, at least a part of the halogen-containing compound is one or two or more of ammonium fluoride, ammonium chloride and ammonium iodide.
The amount of halogen-containing compound in the feed mixture can be selected based on the amount of elemental halogen that is expected to be incorporated in the halogen-containing hydrated alumina composition. Generally, the raw material mixture contains a halogen-containing compound in an amount such that the finally prepared halogen-containing hydrated alumina composition can contain 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight of the halogen-containing compound in terms of halogen element, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.
According to the method for preparing the halogen-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 present in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less, relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, the method for producing a halogen-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 halogen-containing hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with the compound having at least two proton acceptor sites 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 halogen-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 halogen-containing hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the method of preparing the halogen-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 halogen-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 halogen-containing compound may be mixed during the preparation of the hydrated alumina wet gel, or the halogen-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, or a part of the halogen-containing compound may be mixed during the preparation of the hydrated alumina wet gel, and the remaining part of the halogen-containing compound may be added to the hydrated alumina wet gel obtained by the preparation, and the mixing of the halogen-containing compound may be performed at one, two, or three of the above-mentioned timings of addition. When the halogen-containing compound is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the halogen-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 halogen-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 halogen-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 halogen-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 halogen-containing compound; (3) simultaneously mixing a halogen-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 halogen-containing compound after the preparation of the hydrated alumina wet gel is completed.
According to the method for producing a halogen-containing hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the halogen-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 halogen-containing hydrated alumina composition prepared by the process of the second aspect of the present invention.
The halogen-containing hydrated alumina composition according to the present invention can be shaped by a conventional method to obtain a halogen-containing hydrated alumina support or a halogen-containing alumina support.
According to a fourth aspect of the present invention, there is provided a halogen-containing hydrated alumina molded body formed from the halogen-containing hydrated alumina composition of the first aspect of the present invention or the halogen-containing hydrated alumina composition of the third aspect of the present invention.
The halogen-containing hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain the halogen-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 halogen-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 halogen-containing hydrated alumina formed body according to the present invention has a rich pore structure and a pore size distribution that is adjustable.
In one embodiment, the halogen-containing hydrated alumina shaped bodies have a bimodal distribution of pore sizes as measured by mercury intrusion. Wherein the most probable pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and more than 20nm (e.g. 20.5-40nm, preferably 21-35 nm).
In another embodiment, the halogen-containing hydrated alumina shaped bodies have a monomodal distribution of pore sizes as determined by mercury intrusion. Of these, the most probable pore diameter is 4 to 30nm, preferably 8 to 28nm, and more preferably 12 to 25 nm.
According to the halogen-containing hydrated alumina molded body of the present invention, the halogen-containing hydrated alumina molded body has a high strength. In general, the halogen-containing hydrated alumina formed 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 method for producing a halogen-containing hydrated alumina molded body, which comprises molding the halogen-containing hydrated alumina composition according to the first aspect of the present invention or the halogen-containing hydrated alumina composition according to the third aspect of the present invention, and drying the obtained molded body to obtain the hydrated 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.
According to the method for producing a halogen-containing hydrated alumina molded body of the present invention, it is possible to modify the halogen-containing hydrated alumina composition
Values to obtain hydrated alumina shaped bodies with different pore size distributions.
In one embodiment of the invention, the halogen-containing hydrated alumina composition
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of said halogen-containing hydrated alumina composition
A value of not less than 1.85, for example, 1.85 to 3.5, for exampleIs 1.85-3.2. The pore size of the halogen-containing hydrated alumina shaped bodies prepared according to this embodiment is bimodal, as determined by mercury intrusion. The most probable pore diameters are 4 to 20nm (preferably 5 to 15nm, more preferably 6 to 10nm) and more than 20nm (e.g., 20.5 to 40nm, preferably 21 to 35nm), respectively.
In another embodiment of the present invention, the halogen-containing hydrated alumina composition
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of said halogen-containing hydrated alumina composition
The value is not higher than 1.7, and may be, for example, 1.3 to 1.7. The pore diameter of the halogen-containing hydrated alumina moldings produced according to this embodiment has a monomodal distribution, determined by mercury intrusion. The mode pore size is 4 to 30nm, preferably 8 to 28nm, more preferably 12 to 25 nm.
According to a sixth aspect of the present invention, there is provided a halogen-containing hydrated alumina formed body produced by the method according to the fifth aspect of the present invention.
The halogen-containing hydrated alumina formed body prepared by the method of the invention has higher strength. In general, the halogen-containing hydrated alumina formed body produced by the method of the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm is acceptable), and preferably 12N/mm or more (for example, 12 to 50N/mm is acceptable).
According to a seventh aspect of the present invention, there is provided a halogen-containing alumina hydrate molded body formed from the halogen-containing alumina hydrate composition according to the first aspect of the present invention or the halogen-containing alumina hydrate composition according to the third aspect of the present invention.
The halogen-containing hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and fired in sequence to obtain the halogen-containing alumina molded article.
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 the calcination temperature is preferably 450-. In another embodiment, the hydrated alumina is alumina trihydrate 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 halogen-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 halogen-containing alumina formed body according to the invention has a rich pore structure and a tunable pore size distribution.
In one embodiment, the halogen-containing alumina shaped bodies have a bimodal pore size distribution as determined by mercury intrusion. The most probable pore diameters are 4-20nm (preferably 6-19nm) and more than 20nm (e.g. 20.1-40nm, preferably 21-30nm), respectively.
In another embodiment, the halogen-containing aluminum oxide shaped bodies have a monomodal distribution of pore diameters, measured by mercury intrusion. The pore size of the most probable pore is 4 to 20nm, preferably 10 to 20 nm.
According to the halogen-containing alumina molded body of the present invention, the halogen-containing alumina molded body has high strength. In general, the halogen-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 an eighth aspect of the present invention, there is provided a method for producing a halogen-containing alumina hydrate molded body, which comprises molding the halogen-containing alumina hydrate composition according to the first aspect of the present invention or the halogen-containing alumina hydrate composition according to the third aspect of the present invention, and drying and firing the resulting molded body.
The methods and conditions for forming, drying and firing are the same as those described in the seventh aspect of the present invention and will not be described in detail herein.
According to the process for producing a halogen-containing alumina molded body of the present invention, the alumina composition can be changed
To obtain alumina shaped bodies with different pore size distributions.
In one embodiment of the invention, the halogen-containing hydrated alumina composition
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of said halogen-containing hydrated alumina composition
The value is not less than 1.85, for example, may be 1.85 to 3.5, for example, may be 1.85 to 3.2. The pore size of the halogen-containing alumina shaped bodies prepared according to this embodiment is bimodal, determined by mercury intrusion. The most probable pore diameters are 4-20nm (preferably 6-19nm) and more than 20nm (e.g. 20.1-40nm, preferably 21-30nm), respectively.
In another embodiment of the present invention, the halogen-containing hydrated alumina composition
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of said halogen-containing hydrated alumina composition
The value is not higher than 1.7,for example, it may be 1.3 to 1.7. The pore diameter of the halogen-containing aluminum oxide shaped bodies prepared according to this embodiment is unimodal as determined by mercury intrusion. The pore size of the most probable pore is 4 to 20nm, preferably 10 to 20 nm.
According to a ninth aspect of the present invention, there is provided a halogen-containing alumina molded body produced by the method according to the eighth aspect of the present invention.
The halogen-containing alumina formed body prepared by the method has higher strength. In general, the halogen-containing alumina molded product produced by the method of the present invention has a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm is acceptable), and preferably 12N/mm or more (for example, 12 to 50N/mm is acceptable).
According to a tenth aspect of the present invention, there is provided a method for producing and molding a hydrated alumina containing halogen, as shown in fig. 2 and 3, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
optionally (2), treating the first hydrated alumina wet gel with (2-1) or (2-2),
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel;
(3) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a halogen-containing hydrated alumina composition, the hydrated alumina wet gel being either the first hydrated alumina wet gel or the second hydrated alumina wet gel;
(4) molding the halogen-containing hydrated alumina composition to obtain a halogen-containing hydrated alumina molding;
(5) drying the halogen-containing hydrated alumina forming product to obtain a halogen-containing hydrated alumina forming product;
(6) optionally, roasting at least part of the halogen-containing hydrated alumina forming body to obtain a halogen-containing alumina forming body;
wherein the method further comprises mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.
The method for mixing the halogen-containing compound according to the 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 halogen-containing compound may be mixed in step (2). In the case of the method described in (2-1), the halogen-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 halogen-containing compound and a compound having at least two proton acceptor sites using the method according to the second aspect of the present invention to obtain a halogen-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 step (3), the halogen-containing hydrated alumina composition can be determined according to the desired pore size distribution of the halogen-containing hydrated alumina formed body or the halogen-containing alumina formed body
This is illustrated in the method according to the fifth aspect of the invention and in the method according to the eighth aspect of the invention and will not be described in detail here.
In the step (4), the halogen-containing hydrated alumina composition obtained in the step (3) is molded to obtain a halogen-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.
In the step (5), the halogen-containing hydrated alumina molded product obtained in the step (3) is dried to obtain a halogen-containing hydrated alumina molded product. The drying conditions for drying the shaped hydrated alumina product to obtain the halogen-containing shaped hydrated alumina product 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 halogen-containing hydrated alumina formed body obtained in step (5) may be fed to step (6) and calcined; it is also possible to feed part of the halogen-containing hydrated alumina formed body obtained in step (5) to step (6), so that the halogen-containing hydrated alumina formed body and the halogen-containing alumina formed 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 an eleventh aspect of the present invention, there is provided a halogen-containing hydrated alumina molded body or a halogen-containing alumina molded body produced by the method according to the tenth aspect of the present invention.
The halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body produced by the method according to the tenth aspect of the present invention have high strength. In general, the halogen-containing hydrated alumina molded body and the halogen-containing alumina molded body each have a radial crush strength of 10N/mm or more (for example, 10 to 55N/mm), preferably 12N/mm or more (for example, 12 to 50N/mm).
The method according to the tenth 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 mixing the hydrated alumina gelSolid-liquid separation and washing are carried out on the hydrated alumina gel water solution output by the production unit to obtain hydrated alumina wet gel
The value satisfies the requirement of being able to be mixed with a compound having at least two proton acceptor sites 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, such that the solid-liquid separation and washing unit obtains the solid phase material (i.e. water)Hydrated alumina wet gel) of
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.
In a preferred embodiment, the solid-liquid separation and washing unit may comprise a washing subunit, a diluting subunit, a conveying subunit and a second solid-liquid separation subunit, from the viewpoint of facilitating the transportation of the material, on the premise that the mixing unit is provided with the hydrated alumina gel satisfying the requirements,
the washing subunit is used for collecting and washing a solid phase in the hydrated alumina gel solution output by the hydrated alumina gel production unit;
the diluting subunit is used for diluting the solid phase output by the washing subunit with water to obtain slurry;
the conveying subunit is used for conveying the slurry output by the diluting subunit into a second solid-liquid separation subunit;
and the second solid-liquid separation subunit is used for carrying out solid-liquid separation on the slurry to obtain hydrated alumina wet gel.
As shown in fig. 2 and 3, a halogen-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 addition device for adding an auxiliary to the wet hydrated alumina gel, the auxiliary addition device adding at least a compound having at least two proton acceptor sites and optionally a halogen-containing compound to the wet hydrated alumina gel during operation of the production system.
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 firing unit may employ a conventional firing 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 halogen-containing hydrated alumina composition;
(4) molding the halogen-containing hydrated alumina composition in a molding unit to obtain a halogen-containing hydrated alumina molding;
(5) drying the halogen-containing hydrated alumina forming product in a drying unit to obtain a halogen-containing hydrated alumina forming product;
(6) roasting at least part of the halogen-containing hydrated alumina forming body in a roasting unit to obtain an alumina forming body;
wherein the addition of the halogen-containing compound is carried out in one, two or three of the steps (1), (2) and (3) so that the hydrated alumina composition contains the halogen-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 set forth in the second aspect of the invention to enable mixing with a compound having at least two proton acceptor sites to obtain a halogen-containing hydrated alumina composition.
In step (3), the compound having at least two proton acceptor sites is added in an amount such that the halogen-containing hydrated alumina composition obtained is prepared
The values are such that they satisfy the requirements stated above. As mentioned above, the halogen-containing hydrated alumina composition may or may not contain a peptizing agent, i.e., in step (3), a 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 added in an amount of preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the hydrated alumina wet gel. 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.
According to a twelfth aspect of the present invention, the present invention provides the use of the halogen-containing hydrated alumina formed body or the halogen-containing alumina formed body according to the present invention as a carrier or an adsorbent.
The halogen-containing hydrated alumina molded bodies and the halogen-containing alumina molded bodies according to the present invention are particularly suitable as a carrier for a supported catalyst. The supported catalyst may be any of various catalysts commonly used in the art that can have a halogen-containing hydrated alumina molded body and/or a halogen-containing alumina molded body as a support. Preferably, the catalyst is a catalyst having a hydrogenation catalytic effect. That is, the halogen-containing hydrated alumina formed body and the halogen-containing alumina formed body according to the present invention are particularly suitable as a support of a catalyst having a hydrogenation catalytic action.
The active component having a hydrocatalytic effect can be supported on the halogen-containing hydrated alumina shaped body or halogen-containing alumina shaped body according to the invention by various methods commonly used in the art (e.g. impregnation), for example: the catalyst having a hydrogenation catalytic action can be obtained by impregnating the shaped body of the invention with an aqueous solution containing the active component and then drying and optionally calcining the shaped body loaded with the active component.
According to a thirteenth aspect of the present invention, there is provided a catalyst having hydrogenation catalysis, comprising a carrier and a hydrogenation-active component supported on the carrier, wherein the carrier is a halogen-containing hydrated alumina molded body according to the present invention and/or a halogen-containing alumina molded body according to the present invention.
The hydrogenation active component may be of conventional choice. Preferably, the hydrogenation active components are VIB group metal elements and VIII group metal elements. The group VIII metal element and the group VIB metal element may be various elements having a hydrogenation catalytic action commonly used in the art. Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten. The contents of the group VIII metal elements and the group VIB metal elements may be appropriately selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for hydrotreating of hydrocarbon oil, the content of the support may be 64 to 95% by weight, preferably 66 to 89% by weight, more preferably 37.5 to 83% by weight, based on the total amount of the catalyst; the group VIII metal element may be contained in an amount of 0.5 to 6% by weight, preferably 1 to 5% by weight, more preferably 2 to 4.5% by weight, in terms of oxide; the group VIB metal element may be present in an amount of 4.5 to 30 wt.%, preferably 10 to 29 wt.%, more preferably 15 to 28 wt.%, calculated as oxide.
According to a fourteenth 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 halogen-containing hydrated alumina molded body and/or a halogen-containing alumina molded body 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 halogen-containing hydrated alumina molded body and/or a halogen-containing alumina molded body. In this step, a molded body is produced by the method according to the fifth aspect, the eighth aspect or the tenth 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 thirteenth 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. The roasting conditions comprise: the temperature can be 350-550 ℃, preferably 400-500 ℃, and more preferably 400-460 ℃; the duration may be 1 to 8 hours, preferably 2 to 6 hours.
According to a fifteenth aspect of the present invention, there is provided a hydrotreating process comprising contacting, under hydrotreating conditions, a hydrocarbon oil with a catalyst having hydrocatalytic action, wherein the catalyst having hydrocatalytic action is the catalyst of the thirteenth aspect of the present invention or the catalyst prepared by the method of the fourteenth aspect of the present invention.
The hydrotreating method of the present invention is not particularly limited with respect to the kind of hydrocarbon oil and the hydrotreating conditions, and may be a routine choice in the art. Specifically, the hydrocarbon oil may be various heavy mineral oils, synthetic oils, or mixed distillates of heavy mineral oils and synthetic oils, such as: the hydrocarbon oil may be one or more selected from crude oil, distillate oil (e.g., diesel oil), solvent refined oil, cerate, under-wax oil, fischer-tropsch oil, coal liquefied oil, light deasphalted oil, and heavy deasphalted oil. The hydrotreating conditions include: the temperature can be 300-380 ℃; the pressure may be 2-15MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 1-3h-1(ii) a The hydrogen oil volume ratio may be 200-.
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 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 radial crush strength of the molded articles prepared was measured by the method specified in RIPP 25-90. The mode pore size was determined using a Poremaster33 instrument from Congta, USA, with reference to the mercury intrusion method specified in GB/T21650.1-2008. The composition of the catalyst was measured by means of a 3271X-ray fluorescence spectrometer manufactured by Nippon mechanical and electric industries, Ltd. by referring to the method specified in the petrochemical analysis method RIPP 133-90.
Examples 1 to 16 are intended to illustrate the halogen-containing hydrated alumina composition, the molded body and the method of producing the same of the present invention.
Example 1
The hydrated alumina wet gel used in this example was a pseudoboehmite wet cake (the wet cake was designated as S L B-1) obtained by washing and filtering a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, obtained from the tommy of petrochemical, china, long-distance division), and the i value of the wet cake was determined to be 78.2%.
(1) 200g of the wet cake numbered S L B-1 was placed in a beaker, followed by the addition of 5g of NH4F. 5g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same below) and 3g of sesbania powder (having a galactomannan content of 80% by weight, purchased from Beijing chemical Co., Ltd., the same below) were mixed with a mechanical mixer for 10 minutes to obtain a mixture of the halogen-containing hydrated alumina composition of the present invention, the property parameters of which are shown in Table 1.
(2) Extruding the halogen-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 halogen-containing hydrated alumina dry strips HT-1, the property parameters of which are listed in Table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-1, wherein the property parameters are listed in Table 1.
Example 2
A halogen-containing alumina dry strip was prepared in the same manner as in example 1, except that, in the step (4), the hydrated alumina dry strip prepared in the step (3) was calcined at 980 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-2, the property parameters of which are shown in Table 1.
Example 3
(1) 5kg of the wet cake numbered S L B-1 was mixed with 500g of deionized water and beaten for 1 minute, and 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 to obtain a wet cake (numbered L B-1). The i value of the wet cake numbered L B-1 was determined to be 62%.
(2) 300g of the wet cake numbered L B-1 was placed in a beaker and 8g of NH was added4Cl, 4.5g hydroxyethyl methyl cellulose (available from Shanghai Huikang Fine chemical Co., Ltd., the same below) and 1.5g sesbania powder (galactomannan content of 85% by weight, available from Beijing chemical Co., Ltd.) were stirred with a mechanical stirrer for 10 minutes to obtain a halogen-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.
(3) And (3) extruding the halogen-containing hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(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 halogen-containing hydrated alumina dry strips HT-3, the property parameters of which are listed in table 1.
(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-3, wherein the property parameters are listed in Table 1.
Example 4
A shaped body was produced in the same manner as in example 3, except that sesbania powder was not used in step (2) and hydroxyethyl methylcellulose was used in an amount of 5.8g, and the properties of the halogen-containing hydrated alumina composition, halogen-containing hydrated alumina dry strip HT-4 and halogen-containing alumina dry strip OT-4 thus produced are shown in Table 1.
Example 5
A shaped body was produced in the same manner as in example 3, except that hydroxyethylmethylcellulose was not used in step (2) and that sesbania powder was used in an amount of 6.8g, and the properties of the halogen-containing hydrated alumina composition, halogen-containing hydrated alumina dry strip HT-5 and halogen-containing alumina dry strip OT-5 thus produced are shown in Table 1.
Example 6
A molded body was produced in the same manner as in example 3, except that 3g of nitric acid (HNO) was further added in the step (2) while adding hydroxyethyl methylcellulose and sesbania powder3Content of 65 wt.%), the properties of the prepared halogen-containing hydrated alumina composition, halogen-containing hydrated alumina dry strip HT-6 and halogen-containing alumina dry strip OT-6 are listed in table 1.
Comparative example 1
(1) 500g of the wet filter cake numbered L B-1 was dried at 80 ℃ for 2 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 50%, which was left to stand 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 standing.
(2) 228g of pseudo-boehmite powder prepared in the step (1) and 8g of NH4After mixing with Cl, the strands were extruded on a twin-screw extruder of type F-26 using a circular orifice plate 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 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-1, the property parameters of which are listed in Table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 8 hours in an air atmosphere to obtain a halogen-containing alumina dry strip DOT-1, wherein the property parameters are listed in Table 1.
Comparative example 2
(1) 500g of the wet filter cake numbered L B-1 was dried at 90 ℃ for 3 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 40%, which was left to stand at ambient temperature (25-30 ℃) under closed conditions (in a sealed plastic bag) for 72 hours, after which no formation of alumina trihydrate was detected.
(2) 190g of pseudo-boehmite powder prepared in the step (1) is put into a furnaceIn the cup, 8g NH was added4Cl, 4.5g of hydroxyethyl methylcellulose (same as in example 3) and 1.5g of sesbania powder (same as in example 3) were stirred for 10 minutes by a mechanical stirrer to obtain a pseudo-boehmite composition.
(3) And (3) extruding the pseudo-boehmite composition prepared in the step (2) into strips on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 2.0 mm. Wherein, the extruder frequently trips in the extrusion process, and the surface of the extruded material is smooth.
(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-2, the property parameters of which are listed in Table 1.
(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain a halogen-containing alumina dry strip DOT-2, wherein the property parameters are listed in Table 1.
Comparative example 3
(1) 190g of pseudo boehmite powder prepared by the same method as in step (1) of comparative example 2 was put in a beaker, and 8g of NH was added4Cl, 4.5g hydroxyethyl methylcellulose (same as example 3), 1.5g sesbania powder (same as example 3) and 6g 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 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth.
(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 ℃ for 2 hours in an air atmosphere to give halogen-containing alumina hydrate dry strips DHT-3, the property parameters of which are listed in Table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 480 ℃ for 8 hours in an air atmosphere to obtain the halogen-containing alumina dry strip DOT-3, wherein the property parameters are listed in Table 1.
Comparative example 4
A halogen-containing hydrated alumina composition was prepared by the same method as in example 3, except that hydroxyethylmethylcellulose and sesbania powder were not used, but 6.0g of paraffin was used. As a result, the halogen-containing hydrated alumina composition prepared cannot be extrusion molded.
Comparative example 5
A halogen-containing hydrated alumina composition was prepared by the same method as in example 3, except that hydroxyethyl methyl cellulose and sesbania powder were not used, and 6.0g of wood flour was used. As a result, the halogen-containing hydrated alumina composition prepared cannot be extrusion molded.
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 circular orifice plate of 2.0mm in phi, with the result that extrusion molding could not be carried out.
Example 7
(1) 300g of the wet cake numbered L B-1 was placed in a beaker and 10g of NH was added4I. 2.6g of hydroxypropylmethylcellulose (available from Hakka chemical Co., Ltd., Zhejiang, the same applies hereinafter) and 3.5g of sesbania powder (having a galactomannan content of 85% by weight) were stirred with a mechanical stirrer for 10 minutes to obtain a halogen-containing hydrated alumina composition of the present invention, the properties of which are shown in Table 1.
(2) The halogen-containing hydrated alumina composition prepared in the step (1) was extruded on a single screw extruder of the type SK132S/4 (manufactured by BONNT, USA) using a perforated plate composed of a circular shape having an outer diameter of φ 4.5mm and a cylindrical shape having a diameter of 1.5mm in the middle. Wherein, the extrusion process is smooth, and the surface of the extrusion material (Raschig ring) is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6mm, and the wet strips were dried at 60 ℃ for 2 hours in an air atmosphere, followed by drying at 110 ℃ for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-7, the property parameters of which are listed in Table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 950 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-7, wherein the property parameters are listed in Table 1.
Example 8
(1) 300g of the wet cake numbered L B-1 was placed inIn a beaker, 15g of NH was added4F. 2g of methylcellulose, 1.1g of hydroxypropylmethylcellulose and 4g of sesbania powder (galactomannan content 85% by weight) gave, after stirring for 10 minutes with a mechanical stirrer, a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.
(2) Extruding the halogen-containing hydrated alumina composition prepared in the step (1) into strips on an F-26 type double-screw extruder by using a clover-shaped orifice plate with the phi of 3.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 8mm, and the wet strips were dried at 110 ℃ for 4 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-8, the property parameters of which are listed in Table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 1050 ℃ for 1.5 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-8, wherein the property parameters are listed in Table 1.
Example 9
(1) 300g of the wet cake numbered L B-1 was placed in a beaker and 10g of NH was added4Cl, 2.2g hydroxyethyl methylcellulose and 2.1g hydroxypropyl methylcellulose, after stirring for 10 minutes with a mechanical stirrer, gave a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the halogen-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 1.8 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 260 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-9, the property parameters of which are listed in table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 850 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-9, wherein the property parameters are listed in Table 1.
Example 10
(1) 5kg of the wet cake numbered S L B-1 was fed into a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.5MPa and held for 20 minutes, then the cake in the plate and frame was swept with 0.5MPa of pressurized air for 10 minutes and the plate and frame was depressurized to give a wet cake (numbered L B-2) having an i value of 64.9%.
(2) 1000g of the wet cake numbered L B-2 was placed in a beaker and 30g of NH were added4F. After stirring for 10 minutes with a mechanical stirrer, 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (galactomannan content 85% by weight, available from Beijing Chemicals) gave the halogen-containing hydrated alumina composition of the present invention having the property parameters listed in Table 1.
(3) And (2) extruding the halogen-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 2.4 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-10, the property parameters of which are listed in table 1.
(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 700 ℃ for 2 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-10, wherein the property parameters are listed in Table 1.
Example 11
(1) 5kg of the wet cake numbered S L B-1 was mixed with 500g of deionized water, 33g of methylcellulose and 20g of sesbania powder (the content of galactomannan was 80% by weight) and beaten for 1 minute, and then the resulting slurry was fed to a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes, and the plate and frame was depressurized to obtain a wet cake.
(2) Mixing the wet filter cake prepared in the step (1) with 80g of NH4The Cl is stirred uniformly with a mechanical stirrer to obtain the halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in table 1.
The halogen-containing hydrated alumina composition was subjected to extrusion into strips on a F-26 type twin-screw extruder using a dished orifice plate of 1.5mm phi. 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 halogen-containing hydrated alumina dry strips HT-11 having the property parameters listed in table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-11, wherein the property parameters are listed in Table 1.
Example 12
The hydrated alumina wet gel used in this example was prepared by mixing CO2Method (sodium aluminate-CO)2The method is that the i value of the pseudo-boehmite wet filter cake (the wet filter cake is numbered as S L B-2) obtained by washing and filtering a hydrated alumina gel solution prepared by Xinghao catalyst new material Co., Ltd., Shanxi province) is measured to be 65.3%.
(1) 1000g of the wet cake numbered S L B-2 was placed in a beaker, then 30g of NH were added4Cl, 16g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the halogen-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 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-12, the property parameters of which are listed in table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-12, wherein the property parameters are listed in Table 1.
Example 13
The hydrated alumina wet gel used in this example was an alumina trihydrate wet cake (the wet cake was designated as S L B-3) obtained by washing and filtering a hydrated alumina gel solution prepared by a sodium aluminate fractionation method (available from Shandong division of aluminum industries, China), and the i value of the wet cake was determined to be 70%.
(1) 5000g of serial number S L B-3 and 1000g of water are mixed and pulped, the obtained slurry is pressed into a plate and frame filter press, the plate and frame pressure of the plate and frame filter press is adjusted to 0.9MPa and kept for 3 minutes, then filter cakes in the plate and frame are blown by pressurized air of 0.6MPa for 5 minutes, the plate and frame are decompressed to obtain 2.5kg of alumina trihydrate wet filter cakes, and the i value of the wet filter cakes is 60.8 percent by weight.
(2) 1000g of the wet cake obtained in step (1) are placed in a beaker, and 20g of NH are then added4F. 10g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight) were stirred for 10 minutes using a mechanical stirrer, and the resulting mixture was a halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(3) And (2) extruding the halogen-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 2.4 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strips having a length of about 6mm and the wet strips were dried at 150 c for 2 hours in an air atmosphere to give halogen-containing hydrated alumina dry strips HT-13, the property parameters of which are listed in table 1.
(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 1400 ℃ for 2 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-13, wherein the property parameters are listed in Table 1.
Example 14
The hydrated alumina wet gel used in this example is obtained from Shandong Zibo zimao catalyst Co., Ltd, 1000g of a dry pseudo-boehmite powder (dry basis is 70 wt%) prepared by an acid process (sodium aluminate-aluminum sulfate process) is calcined at 700 ℃ for 3 hours in an air atmosphere to obtain 700g of alumina, 700g of alumina is placed in a 10L high-pressure reaction kettle and is uniformly stirred with 5L deionized water, the high-pressure reaction kettle is sealed and reacted at 150 ℃ under an autogenous pressure for 6 hours, after the reaction is finished, the temperature of the high-pressure reaction kettle is reduced to room temperature (25 ℃), the slurry obtained by the reaction is sent into a plate and frame filter press, the plate and frame pressure of the plate and frame filter is adjusted to 0.5MPa and kept for 10 minutes, then the filter cake in the plate and frame is blown by 10MPa of compressed air for 3 minutes, the plate and frame is decompressed to obtain a hydrated alumina wet filter cake L B-3.
(1) 300g of the wet cake numbered L B-3 was placed in a beaker, followed by 9g NH4I. After stirring 3.8g of methylcellulose and 6g of sesbania powder (galactomannan content 85% by weight) for 10 minutes using a mechanical stirrer, the mixture obtained was a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in table 1.
(2) And (2) extruding the halogen-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 2.4 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 halogen-containing hydrated alumina dry strips HT-14, the property parameters of which are listed in table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 600 ℃ for 4 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-14, wherein the property parameters are listed in Table 1.
Example 15
The hydrated alumina wet gel used in this example was prepared by the method described in "new method for preparing alumina by hydrolyzing low-carbon alkoxy aluminum", test method ", in article" new method for preparing alumina by hydrolyzing low-carbon alkoxy aluminum ", published in" Petroleum institute (Petroleum processing) ", volume 10, 4, wherein the aging time was 12 hours, after the aging was completed and isopropanol and water were distilled out, 500g of water was added, the mixture was stirred for 1 minute with a mechanical stirrer, the slurry was pressed into a plate and frame filter, the pressure of the plate and frame filter was adjusted to 0.7MPa, the pressing time was 8 minutes, and then the filter cake in the plate and frame was blown with 7MPa of pressurized air for 4 minutes to obtain 200g of wet filter cake (No. L B-4), which was determined to be pseudo-boehmite and to have a wet i value of 65.2%.
(1) 200g of the wet cake numbered L B-4 was placed in a beaker, followed by the addition of 5g of NH4Cl, 2.8g of methylcellulose and 4.5g of sesbania powder (galactomannan content 80% by weight), the mixture obtained after stirring for 10 minutes with a mechanical stirrer is a halogen-containing hydrated alumina composition according to the invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the halogen-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 2.4 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 halogen-containing hydrated alumina dry strips HT-15, the property parameters of which are listed in table 1.
(4) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (3) at 580 ℃ for 6 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-15, wherein the property parameters are listed in Table 1.
Example 16
(1) 5kg of the wet cake numbered 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 the cake in the plate and frame was swept with pressurized air of 0.5MPa for 3 minutes, the plate and frame was depressurized to obtain a wet cake numbered L B-5. the i value of the wet cake numbered L B-5 was determined to be 75% by weight.
(2) 1000g of the wet cake numbered L B-5 was placed in a beaker and 25g of NH was added4F. After stirring for 10 minutes with a mechanical stirrer, 16g of hydroxypropylmethylcellulose and 20g of sesbania powder (content of galactomannan 85% by weight) gave the halogen-containing hydrated alumina composition of the present invention, the property parameters of which are listed in table 1.
(3) And (3) extruding the halogen-containing hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a circular 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 halogen-containing hydrated alumina dry strips HT-16, the property parameters of which are listed in table 1.
(5) And (3) roasting the halogen-containing hydrated alumina dry strip prepared in the step (4) at 950 ℃ for 2.5 hours in an air atmosphere to obtain a halogen-containing alumina dry strip OT-16, wherein the property parameters are listed in Table 1.
TABLE 1
1: the composition after standing was allowed to stand at ambient temperature (25-30 ℃) in a closed condition (in a sealed plastic bag) for 72 hours, and the content of alumina trihydrate in the composition after standing was increased more than before standing.
The results of examples 1-16 demonstrate that the hydrated alumina wet gel is not dried into dry gel powder or semi-dry gel powder, but is directly mixed with a halogen-containing compound and a compound having 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. And, the hydrated alumina composition according to the present invention is adjusted by
The pore size distribution of the shaped bodies produced can be adjusted to give shaped bodies having a monomodal or bimodal pore size distribution, respectively.
Experimental examples 1 to 9 are provided to illustrate a catalyst having a hydrogenation catalytic action according to the present invention, a preparation method thereof, and a hydrotreating method thereof.
Experimental example 1
(1) The catalyst of the present invention, CH-1, was obtained by dissolving 9.3g of nickel nitrate and 19.1g of ammonium heptamolybdate in water to prepare 153m L impregnated solution, impregnating 109.3g of the halogen-containing hydrated alumina dry strip prepared in example 1 at 25 ℃ for 4 hours, filtering, drying the obtained solid product at 115 ℃ for 5 hours, and calcining at 430 ℃ for 4 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 2.
(2) The catalyst of the present invention, CO-1, was obtained by dissolving 9.3g of nickel nitrate and 19.1g of ammonium heptamolybdate in water to prepare 129m L impregnation solution, impregnating 83.7g of the halogen-containing alumina dry strip prepared in example 1 in the obtained impregnation solution at 25 ℃ for 4 hours, filtering, drying the obtained solid product at 120 ℃ for 3 hours, and calcining at 440 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 3.
Experimental example 2
(1) The catalyst CH-2 of the present invention was obtained by dissolving 9.7g of nickel nitrate and 19.0g of ammonium heptamolybdate in water to prepare a 109m L impregnated solution, impregnating 105g of the halogen-containing hydrated alumina dry strip prepared in example 3 with the resultant impregnated solution at 30 ℃ for 6 hours, filtering, drying the resultant solid product at 135 ℃ for 5 hours, and then calcining at 460 ℃ for 4 hours, and the composition of the catalyst was measured by XRF, the results of which are shown in Table 2.
(2) The catalyst of the present invention, CO-2, was obtained by dissolving 9.7g of nickel nitrate and 19.0g of ammonium heptamolybdate in water to prepare 96m L impregnation solution, impregnating 85.4g of the halogen-containing alumina dry strip prepared in example 3 in the obtained impregnation solution at 30 ℃ for 8 hours, filtering, drying the obtained solid product at 110 ℃ for 7 hours, and then calcining at 410 ℃ for 6 hours, and the composition of the catalyst was measured 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 2, except that: (1) wherein the hydrated alumina dry strip is the halogen-containing hydrated alumina dry strip prepared in example 4, to obtain the catalyst CH-3 of the present invention. The composition of the catalyst was determined using XRF, with the results shown in table 2;
(2) in this example, the alumina dry strip was the halogen-containing alumina dry strip prepared in example 4, and the catalyst CO-3 of the present invention was obtained. 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 2, except that: (1) wherein the halogen-containing alumina hydrate dry strip is the halogen-containing alumina hydrate dry strip prepared in example 5, and the catalyst CH-4 of the present invention is obtained. The composition of the catalyst was determined using XRF, with the results shown in table 2;
(2) wherein the halogen-containing alumina dry strip is the halogen-containing alumina dry strip prepared in example 5, and the catalyst CO-4 of the present invention is obtained. 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 2, except that: (1) in the example, the halogen-containing hydrated alumina dry strip was the halogen-containing hydrated alumina dry strip prepared in example 6, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) wherein the halogen-containing alumina dry strip is the halogen-containing alumina dry strip prepared in example 6, and the catalyst CO-5 of the present invention is obtained. 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 2, except that: (1) in the above, the halogen-containing hydrated alumina dry strip was the halogen-containing hydrated alumina dry strip prepared in comparative example 1, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) in the above, the halogen-containing alumina dry strip was the halogen-containing alumina dry strip prepared in comparative example 1, to obtain catalyst DCO-1. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental comparative example 2
A catalyst was prepared in the same manner as in experimental example 2, except that: (1) in the above, the halogen-containing hydrated alumina dry strip was the halogen-containing hydrated alumina dry strip prepared in comparative example 3, and as a result, the phenomena of structural collapse and pulverization occurred during the impregnation process;
(2) in the above, the halogen-containing alumina dry strip was the halogen-containing alumina dry strip prepared in comparative example 3, to obtain the catalyst DCO-2. The composition of the catalyst was determined by XRF and the results are shown in table 3.
Experimental example 6
(1) The catalyst of the present invention, CH-6, was obtained by dissolving 14.8g of cobalt nitrate and 27.2g of ammonium heptamolybdate in water to prepare 108m L impregnated solution, impregnating 96g of the halogen-containing hydrated alumina dry strip prepared in example 10 with the obtained impregnated solution at 35 ℃ for 6 hours, filtering, drying the obtained solid product at 150 ℃ for 2 hours, and calcining at 420 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 2.
(2) 14.8g of cobalt nitrate and 27.2g of ammonium heptamolybdate were dissolved in water to prepare a 78m L impregnation solution, and the obtained impregnation solution was impregnated with 75.5g of the halogen-containing alumina dry strip prepared in example 10 at 35 ℃ for 3 hours, after filtration, the obtained solid product was dried at 120 ℃ for 4 hours and calcined at 450 ℃ for 2 hours to obtain the catalyst CO-6 of the present invention, and the composition of the catalyst was measured by XRF, and the results are shown in Table 3.
Experimental example 7
(1) The catalyst of the present invention, CH-7, was obtained by dissolving 16.0g of cobalt nitrate and 33.0g of ammonium heptamolybdate in water to prepare 126m L impregnated solution, impregnating 95.8g of the halogen-containing hydrated alumina dry strip prepared in example 11 with the resulting impregnated solution at 35 ℃ for 6 hours, filtering, drying the resulting solid product at 125 ℃ for 5 hours, and calcining at 400 ℃ for 4 hours, and the composition of the catalyst was measured by XRF, the results of which are shown in Table 2.
(2) The catalyst of the present invention, CO-7, was obtained by dissolving 16.0g of cobalt nitrate and 33.0g of ammonium heptamolybdate in water to prepare an 88m L impregnation solution, impregnating 71g of the halogen-containing alumina dry strip prepared in example 11 with the obtained impregnation solution at 35 ℃ for 6 hours, filtering, drying the obtained solid product at 110 ℃ for 4 hours, and then calcining at 450 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 3.
Experimental example 8
(1) The catalyst of the present invention, CH-8, was obtained by dissolving 9.3g of cobalt nitrate and 19.1g of ammonium heptamolybdate in water to prepare a 59m L-impregnated solution, impregnating 117g of the halogen-containing hydrated alumina dry strip prepared in example 12 with the obtained impregnated solution at 35 ℃ for 3 hours, filtering, drying the obtained solid product at 125 ℃ for 4 hours, and then calcining at 420 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, the results of which are shown in Table 2.
(2) The catalyst of the present invention, CO-8, was obtained by dissolving 9.3g of cobalt nitrate and 19.1g of ammonium heptamolybdate in water to prepare a 42m L impregnation solution, impregnating 85.4g of the halogen-containing alumina dry strip prepared in example 12 with the obtained impregnation solution at 35 ℃ for 5 hours, filtering, drying the obtained solid product at 135 ℃ for 4 hours, and then calcining at 440 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 3.
Experimental example 9
(1) The catalyst of the present invention, CH-9, was obtained by dissolving 10.9g of nickel nitrate and 27.2g of ammonium heptamolybdate in water to prepare 82m L impregnated solution, impregnating 96.2g of the halogen-containing hydrated alumina dry strip prepared in example 15 in the obtained impregnated solution at 35 ℃ for 4 hours, filtering, drying the obtained solid product at 120 ℃ for 4 hours, and calcining at 430 ℃ for 3 hours, and the composition of the catalyst was measured by XRF, and the results are shown in Table 2.
(2) 10.9g of nickel nitrate and 27.2g of ammonium heptamolybdate were dissolved in water to prepare a 63m L solution, and the obtained solution was impregnated at 35 ℃ with 78.1g of the halogen-containing alumina dry strip prepared in example 15 for 3 hours, filtered, and the obtained solid product was dried at 130 ℃ for 4 hours and then calcined at 430 ℃ for 3 hours to obtain the catalyst CO-9 of the present invention, and the composition of the catalyst was measured by XRF, and the results are shown in Table 3.
TABLE 2
| Numbering | Catalyst numbering | NiO (wt%) | CoO (% by weight) | MoO3(wt%) |
| Experimental example 1 | CH-1 | 2.3 | / | 15.5 |
| Experimental example 2 | CH-2 | 2.4 | / | 15.5 |
| Experimental example 3 | CH-3 | 2.4 | / | 15.5 |
| Experimental example 4 | CH-4 | 2.4 | / | 15.5 |
| Experimental example 6 | CH-6 | / | 3.8 | 22.2 |
| Experimental example 7 | CH-7 | / | 4.1 | 26.9 |
| Experimental example 8 | CH-8 | / | 2.4 | 15.6 |
| Experimental example 9 | CH-9 | 2.8 | / | 22.2 |
TABLE 3
| Numbering | Catalyst numbering | NiO (wt%) | CoO (% by weight) | MoO3(wt%) |
| Experimental example 1 | CO-1 | 2.2 | 15.2 | |
| Experimental example 2 | CO-2 | 2.4 | / | 15.3 |
| Experimental comparative example 1 | DCO-1 | 2.4 | / | 15.3 |
| Experimental comparative example 2 | DCO-2 | 2.3 | / | 15.2 |
| Experimental example 3 | CO-3 | 2.4 | / | 15.3 |
| Experimental example 4 | CO-4 | 2.4 | / | 15.3 |
| Experimental example 5 | CO-5 | 2.4 | / | 15.3 |
| Experimental example 6 | CO-6 | / | 3.6 | 21.8 |
| Experimental example 7 | CO-7 | / | 4.0 | 26.7 |
| Experimental example 8 | CO-8 | / | 2.3 | 15.5 |
| Experimental example 9 | CO-9 | 2.6 | / | 22.0 |
Test examples 1-9 are intended to illustrate the hydrotreating process according to the invention.
Test examples 1 to 9
The catalytic performance of the catalysts prepared in experimental examples 1-9 was evaluated on a 30 ml diesel hydrogenation unit using the following methodExperimental the catalytic performance of the catalyst prepared in comparative example 1 was used as a benchmark and the experimental results are listed in table 4. The raw material is middle east straight-run diesel oil. The S content is 9700wppm, and the N content is 97 wppm; the density (20 ℃ C.) was 0.8321g/cm3(ii) a A refractive index (20 ℃) of 1.4658;
the process operating conditions are as follows: the liquid hourly space velocity of the hydrocarbon oil is 2.0h-1(ii) a The volume ratio of hydrogen to oil is 300; the pressure is 3.2 MPa; the reaction temperature was 330 ℃.
Testing of comparative examples 1-2
The catalysts prepared in experimental comparative examples 1-2 were evaluated for their catalytic performance in the same manner as in test examples 1-9, respectively, and the results of the experiments are shown in Table 4.
TABLE 4
The results of test examples 1 to 9 confirmed that the catalysts prepared with the halogen-containing hydrated alumina molded body and the alumina molded body according to the present invention as a support show higher catalytic activity in the hydrotreating reaction.
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 (136)
1. A halogen-containing hydrated alumina composition comprising hydrated alumina, a halogen-containing compound and a compound having at least two proton acceptor sites, the compound having at least two proton acceptor sites being one or more of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide,
of said composition
A value of 1.2 or more and 5 or less
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 method for preparing the halogen-containing hydrated alumina composition comprises mixing the components of a raw material composition containing a hydrated alumina wet gel, a halogen-containing compound, and a compound having at least two proton acceptor sites, wherein the i value of the hydrated alumina wet gel is not less than 60%, and the compound having at least two proton acceptor sites is used in an amount such that the composition finally prepared is
A value of 1.2 or more and 5 or less,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2By using a meter of formula IIThe value of i is calculated,
2. the composition of claim 1, wherein the composition is
The value is 4 or less.
3. The composition of claim 2, wherein the composition is
The value is 3.5 or less.
4. The composition of claim 3, wherein the composition is
The value is 3.2 or less.
5. The composition of any one of claims 1-4, wherein the composition is administered to a subject in need thereof
The value is 1.3 or more.
6. The composition of claim 1, wherein the composition is
The value is 1.2-4.
7. The composition of claim 6, wherein the composition is a mixture of
The value is 1.3-3.5.
8. The composition of claim 7, wherein the composition is a mixture of
The value is 1.3-3.2.
9. The composition according to claim 1, 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.
10. The composition according to claim 9, wherein the compound having at least two proton acceptor sites is contained in an amount of 2 to 20 parts by weight with respect to 100 parts by weight of the hydrated alumina.
11. The composition according to claim 10, wherein the compound having at least two proton acceptor sites is contained in an amount of 3 to 18 parts by weight with respect to 100 parts by weight of the hydrated alumina.
12. The composition according to claim 11, wherein the compound having at least two proton acceptor sites is contained in an amount of 3.5 to 17 parts by weight with respect to 100 parts by weight of the hydrated alumina.
13. The composition of any of claims 1-4 and 6-12, wherein the compound having at least two proton acceptor sites is one or more of a galactan, mannan, galactomannan, and cellulose ether.
14. The composition of claim 13, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
15. The composition of any of claims 1-4 and 6-12, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
16. The composition of claim 15, wherein the galactomannan is present in an amount of 10 to 70 wt% and the cellulose ether is present in an amount of 30 to 90 wt%, based on the total amount of the compound having at least two proton acceptor sites.
17. The composition of claim 16, wherein the galactomannan is present in an amount of 15 to 68 wt% and the cellulose ether is present in an amount of 32 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.
18. The composition of claim 17, wherein the galactomannan is present in an amount of 20 to 65 wt% and the cellulose ether is present in an amount of 35 to 80 wt%, based on the total amount of the compound having at least two proton acceptor sites.
19. The composition as claimed in any one of claims 1 to 4 and 6 to 12, wherein the content of the halogen-containing compound is 0.1 to 12 parts by weight in terms of halogen element, relative to 100 parts by weight of hydrated alumina.
20. The composition as claimed in claim 19, wherein the content of the halogen-containing compound is 0.5 to 10 parts by weight in terms of halogen element, relative to 100 parts by weight of hydrated alumina.
21. The composition as claimed in claim 20, wherein the content of the halogen-containing compound is 1 to 8 parts by weight based on the halogen element with respect to 100 parts by weight of hydrated alumina.
22. The composition of any of claims 1-4 and 6-12, wherein the halogen element in the halogen-containing compound is fluorine, chlorine, or iodine.
23. The composition of claim 22, wherein the halogen-containing compound is selected from ammonium halides.
24. The composition as claimed in claim 23, wherein the halogen-containing compound is one or more selected from ammonium fluoride, ammonium chloride and ammonium iodide.
25. The composition of any of claims 1-4 and 6-12, wherein the hydrated alumina comprises pseudoboehmite.
26. The composition of claim 25, wherein the hydrated alumina is pseudoboehmite.
27. The composition of claim 26, wherein the composition is allowed to stand at ambient temperature and under closed conditions for 72 hours, and wherein the amount of alumina trihydrate in the composition after standing is greater than the amount of alumina trihydrate in the composition prior to standing.
28. The composition of claim 27, 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.
29. The composition of claim 28, wherein the alumina trihydrate content of the composition after placement is increased by at least 0.8% based on the total alumina trihydrate content of the composition before placement.
30. The composition of claim 29, wherein the alumina trihydrate content in the composition after placement is increased by 1% to 2% based on the total alumina trihydrate content in the composition before placement.
31. The composition of any of claims 1-4 and 6-12, wherein the hydrated alumina is directly derived from a hydrated alumina wet gel.
32. The composition of any of claims 1-4 and 6-12, wherein the composition is free of a peptizing agent.
33. The composition of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4 or less.
34. The composition of claim 33, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 3.5 or less.
35. The composition of claim 34, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 3.2 or less.
36. The composition of any of claims 33-35, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3 or more.
37. The composition of claim 1, wherein the composition is
The value is 1.2-4.
38. The composition of claim 37, wherein the composition is administered to a human in need thereof
The value is 1.3-3.5.
39. The composition of claim 38, wherein the composition is administered to a human in need thereof
The value is 1.3-3.2.
40. The composition of any of claims 1, 33-35, and 37-39, wherein the hydrated alumina wet gel has an i value of not less than 62%.
41. The composition of claim 40, wherein the hydrated alumina wet gel has an i value of not greater than 82%.
42. The composition of claim 41, wherein the hydrated alumina wet gel has an i value of not greater than 80%.
43. The composition of claim 42, wherein the hydrated alumina wet gel has an i value of not greater than 78.5%.
44. The composition of any of claims 1, 33-35, and 37-39, wherein the hydrated alumina wet gel has an i value of 60-82%.
45. The composition of claim 44, wherein the hydrated alumina wet gel has an i value of 62-80%.
46. The composition of claim 45, wherein the hydrated alumina wet gel has an i value of 62-78.5%.
47. The composition of any of claims 1, 33-35, and 37-39, 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.
48. The composition of any of claims 1, 33-35, and 37-39, 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.
49. The composition of claim 48, wherein the hydrated alumina gel solution is prepared by one or more of precipitation, hydrolysis, seeded precipitation, and flash dehydration.
50. The composition of any of claims 1, 33-35, and 37-39, wherein the feedstock composition is free of a peptizing agent.
51. The composition of any of claims 1, 33-35, and 37-39, wherein the raw mixture comprises the halogen-containing compound in an amount such that the hydrated alumina composition is prepared in an amount of from 0.1 to 12 parts by weight of the halogen-containing compound as a halogen element per 100 parts by weight of the hydrated alumina wet gel as a hydrated alumina.
52. A composition as claimed in claim 51, in which the content of halogen-containing compound in the raw material mixture is such that the hydrated alumina composition is produced in an amount of 0.5 to 10 parts by weight per 100 parts by weight of hydrated alumina wet gel calculated on an elemental basis of halogen.
53. A composition as claimed in claim 52, in which the halogen-containing compound is present in the raw material mixture in an amount such that the hydrated alumina composition produced has a halogen-containing compound content in the range of from 1 to 8 parts by weight per 100 parts by weight of hydrated alumina wet gel, calculated as elemental halogen, calculated as hydrated alumina.
54. The composition of any of claims 1, 33-35, and 37-39, wherein the method of mixing is stirring and/or kneading.
55. A halogen-containing hydrated alumina shaped body formed from the halogen-containing hydrated alumina composition of any one of claims 1 to 54.
56. The halogen containing hydrated alumina forming body of claim 55, wherein the halogen containing hydrated alumina forming body has a bimodal distribution of pore sizes, measured by mercury intrusion porosimetry, with a maximum probable pore size of 4 to 20nm and greater than 20nm, respectively; or
The halogen-containing hydrated alumina formed bodies have a monomodal distribution of pore diameters, measured by mercury intrusion, and a mode of pore diameter of 4 to 30 nm.
57. The halogen containing hydrated alumina forming body of any one of claims 55 to 56, wherein the radial crush strength of the halogen containing hydrated alumina forming body is from 10 to 55N/mm.
58. The halogen containing hydrated alumina forming body of claim 57, wherein the radial crush strength of the halogen containing hydrated alumina forming body is from 12 to 50N/mm.
59. A process for producing a halogen-containing hydrated alumina molding, which comprises molding the halogen-containing hydrated alumina composition as claimed in any one of claims 1 to 54, and drying the resulting molded article.
60. The method of claim 59, wherein the halogen-containing hydrated alumina composition
The value is 1.86-5.
61. The method of claim 59, wherein the halogen-containing hydrated alumina composition
The value is 1.85-3.5.
62. The method of claim 61, wherein the halogen-containing hydrated alumina composition
The value is 1.85-3.2.
63. The method of claim 59, wherein the halogen-containing hydrated alumina composition
Values of 1.2 to less than 1.8.
64. The method of claim 63, wherein the halogen-containing hydrated alumina composition
The value is not higher than 1.7.
65. The method of claim 64, wherein the halogen-containing hydrated alumina composition
The value is 1.3-1.7.
66. A halogen-containing hydrated alumina shaped body prepared by the method of any one of claims 59 to 65.
67. The halogen containing hydrated alumina forming body of claim 66, wherein the radial crush strength of the halogen containing hydrated alumina forming body is from 10 to 55N/mm.
68. The halogen containing hydrated alumina forming body of claim 67, wherein the radial crush strength of the halogen containing hydrated alumina forming body is from 12 to 50N/mm.
69. A halogen-containing alumina oxide shaped body formed from the halogen-containing hydrated alumina composition of any one of claims 1 to 54.
70. The halogen containing alumina forming body according to claim 69, wherein the halogen containing alumina forming body has a bimodal distribution of pore sizes with a maximum probable pore size of 4 to 20nm and greater than 20nm, respectively, as determined by mercury intrusion; or
The halogen-containing alumina shaped bodies have a monomodal distribution of pore diameters, measured by mercury intrusion, of from 4 to 20 nm.
71. The halogen containing alumina forming body according to any one of claims 69 to 70, having a radial crush strength of 10 to 55N/mm.
72. The halogen containing alumina forming body according to claim 71, wherein the halogen containing alumina forming body has a radial crush strength of from 12 to 50N/mm.
73. A process for producing a halogen-containing hydrated alumina molding, which comprises molding the halogen-containing hydrated alumina composition as claimed in any one of claims 1 to 54, drying and calcining the resulting molding.
74. The method of claim 73, wherein the halogen-containing hydrated alumina composition is
The value is 1.86-5.
75. The method of claim 73, wherein the halogen-containing hydrated alumina composition is
The value is 1.85-3.5.
76. The method of claim 75, wherein the halogen-containing hydrated alumina composition is
The value is 1.85-3.2.
77. The method of claim 73, wherein the halogen-containing hydrated alumina composition is
Values of 1.2 to less than 1.8.
78. The method of claim 77, wherein the halogen-containing hydrated alumina composition
The value is not higher than 1.7.
79. The method of claim 78, wherein the halogen-containing hydrated alumina composition is
The value is 1.3-1.7.
80. A halogen-containing alumina shaped body prepared by the method of any one of claims 73-79.
81. The halogen containing alumina forming body according to claim 80, wherein the halogen containing alumina forming body has a radial crush strength of 10 to 55N/mm.
82. The halogen containing alumina forming body according to claim 81, wherein the halogen containing alumina forming body has a radial crush strength of from 12 to 50N/mm.
83. A method for producing and molding hydrated alumina containing halogen 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: 36g of the hydrated alumina wet gel were dried at 120 ℃ for 760 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 to provide a hydrated oxidized gelAn aluminum composition, the compound having at least two proton acceptor sites being one or more of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, the compound having at least two proton acceptor sites being used in an amount such that the composition finally prepared is of a composition
A value of 1.2 or more and 5 or less
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
(3) 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 mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.
84. The method of claim 83 wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 62%.
85. The method of claim 83, wherein the conditions of solid-liquid separation are such that the i value of the first hydrated alumina wet gel is no greater than 82%.
86. The method of claim 85 wherein the conditions of solid-liquid separation are such that the i value of the first wet gel of hydrated alumina is not greater than 80%.
87. The method of claim 86 wherein the solid-liquid separation conditions are such that the i value of the first wet gel of hydrated alumina is no greater than 78.5%.
88. The method of claim 83, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 60-82%.
89. The method of claim 88, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 62-80%.
90. The method of claim 89 wherein the conditions of solid-liquid separation are such that the first wet gel of hydrated alumina has an i value of 62-78.5%.
91. The method according to claim 83, wherein in the step (2), the mixing is performed by stirring and/or kneading.
92. A method for producing and molding hydrated alumina containing halogen comprises the following steps:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel,
(2-1) and (2-2), the solid-liquid separation conditions being such that the second hydrated alumina wet gel has an i value of 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 of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound having at least two proton acceptor sites is used in an amount to obtain the final composition
A value of 1.2 or more and 5 or less
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
(4) 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 mixing a halogen-containing compound in step (1) and/or step (2) so that the hydrated alumina composition contains a halogen-containing compound.
93. The method of claim 92 wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 62%.
94. The method of claim 92 wherein the conditions of the solid-liquid separation in (2-1) and (2-2) are such that the second hydrated alumina wet gel has an i value of not greater than 82%.
95. The method of claim 94, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 80%.
96. The process of claim 95, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 78.5%.
97. The process of claim 92, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 60-82%.
98. The process of claim 97, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 62-80%.
99. The process of claim 98, wherein in (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 62-78.5%.
100. The method according to claim 92, wherein in step (3), the mixing is performed by stirring and/or kneading.
101. The process of any one of claims 83 to 100, 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.
102. The method of any of claims 83-100, wherein the hydrated alumina gel solution is aged or unaged and is prepared by one or more of precipitation, hydrolysis, seeded precipitation, and flash dehydration.
103. The method of any of claims 83-100, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4 or less.
104. The method of claim 103, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 3.5 or less.
105. The method of claim 104, whereinThe compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 3.2 or less.
106. The method of any of claims 83-100, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3 or more.
107. The method of any one of claims 83-100, wherein the method is performed in a wireless communication system
The value is 1.2-4.
108. The method of claim 107, wherein the
The value is 1.3-3.5.
109. The method of claim 108, wherein the
The value is 1.3-3.2.
110. The method of any one of claims 83-100, 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.
111. The method of claim 110, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
112. The method of any one of claims 83-100, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
113. The method of claim 112, 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.
114. The method of claim 113, 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.
115. The method of claim 114, 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.
116. The method of any of claims 83-100, wherein the halogen-containing compound is present in an amount to produce a hydrated alumina composition in an amount of from 0.1 to 12 parts by weight based on elemental halogen and based on hydrated alumina per 100 parts by weight of hydrated alumina wet gel.
117. The method of claim 116, wherein the halogen-containing compound is present in an amount to produce a hydrated alumina composition in an amount of from 0.5 to 10 parts by weight based on elemental halogen and based on hydrated alumina per 100 parts by weight of hydrated alumina wet gel.
118. A process as set forth in claim 117 wherein the halogen-containing compound is present in an amount of from 1 to 8 parts by weight based on elemental halogen and said hydrated alumina wet gel is based on hydrated alumina, relative to 100 parts by weight of hydrated alumina wet gel, in the hydrated alumina composition produced.
119. The method of any one of claims 83-100, wherein the elemental halogen of the halogen-containing compound is fluorine, chlorine, or iodine.
120. A process as set forth in claim 119 wherein said halogen-containing compound is selected from ammonium halides.
121. The method of claim 120 wherein the halogen containing compound is one or more selected from the group consisting of ammonium fluoride, ammonium chloride and ammonium iodide.
122. A shaped body prepared by the method of any one of claims 83-121.
123. The shaped body of claim 122, wherein the shaped body has a radial crush strength of 10-55N/mm.
124. The shaped body of claim 123, wherein the shaped body has a radial crush strength of from 12 to 50N/mm.
125. Use of a hydrated alumina halogen-containing shaped body as claimed in any one of claims 55 to 58 and 66 to 68, a hydrated alumina halogen-containing shaped body as claimed in any one of claims 69 to 72 and 80 to 82 or a shaped body as claimed in any one of claims 122 and 124 as a support or adsorbent.
126. The use according to claim 125, wherein the support is a support for a supported catalyst.
127. The use of claim 126, wherein the support is a support for a supported hydrogenation catalyst.
128. A catalyst having hydrogenation catalysis effect, which comprises a carrier and a hydrogenation active component loaded on the carrier, wherein the carrier is the halogen-containing hydrated alumina formed body in any one of claims 55-58 and 66-68, the halogen-containing alumina formed body in any one of claims 69-72 and 80-82 or the formed body in any one of claims 122-124.
129. The catalyst of claim 128, wherein the hydrogenation active components are group VIII metal elements and group VIB metal elements.
130. The catalyst of claim 129, wherein the support is present in an amount of from 64 to 95 wt.%, calculated as oxide, of the group VIII metal element in an amount of from 0.5 to 6 wt.%, calculated as oxide, of the group VIB metal element in an amount of from 4.5 to 30 wt.%, calculated as oxide, of the total catalyst.
131. The catalyst of claim 130, wherein the support is present in an amount of 64 to 95 wt.%, calculated as oxides, of the group VIII metal element and in an amount of 10 to 29 wt.%, calculated as oxides, of the group VIB metal element, based on the total amount of the catalyst.
132. A method for preparing a catalyst having hydrogenation catalysis, which comprises loading a hydrogenation active component on a carrier, wherein the carrier is a halogen-containing hydrated alumina molded body as defined in any one of claims 55 to 58 and 66 to 68, a halogen-containing alumina molded body as defined in any one of claims 69 to 72 and 80 to 82, or a molded body as defined in any one of claims 122 to 124.
133. The process of claim 132, wherein the hydrogenation active components are group VIB metal elements and group VIII metal elements.
134. The process of claim 133, wherein the loading of the hydrogenation active component on the support is such that the support is present in an amount of 64 to 95 wt.%, calculated as oxide, of the final catalyst, and the group VIII metal element is present in an amount of 0.5 to 6 wt.%, calculated as oxide, of the final catalyst, and the group VIB metal element is present in an amount of 4.5 to 30 wt.%, calculated as oxide.
135. The process of claim 134, wherein said hydrogenation active component is supported on a carrier, wherein the carrier is present in an amount of 66-89 wt%, calculated as oxide, said group VIII metal element is present in an amount of 1-5 wt%, calculated as oxide, and said group VIB metal element is present in an amount of 10-29 wt%, calculated as oxide, in the final catalyst.
136. A hydroprocessing method comprising contacting a hydrocarbon oil under hydroprocessing conditions with a hydrocatalytically effective catalyst, wherein the hydrocatalytically effective catalyst is the catalyst of any one of claims 128-131 or the catalyst prepared by the method of any one of claims 132-135.
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