CN108014823A - The composition of hydrated alumina containing halogen and formed body and preparation method and catalyst and preparation method thereof - Google Patents
The composition of hydrated alumina containing halogen and formed body and preparation method and catalyst and preparation method thereof Download PDFInfo
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- CN108014823A CN108014823A CN201610961091.4A CN201610961091A CN108014823A CN 108014823 A CN108014823 A CN 108014823A CN 201610961091 A CN201610961091 A CN 201610961091A CN 108014823 A CN108014823 A CN 108014823A
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- Prior art keywords
- hydrated alumina
- composition
- compound
- formed body
- weight
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Links
- 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 657
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 313
- 150000002367 halogens Chemical class 0.000 title claims abstract description 313
- 239000000203 mixture Substances 0.000 title claims abstract description 217
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 212
- 150000001875 compounds Chemical class 0.000 claims abstract description 176
- 239000011240 wet gel Substances 0.000 claims abstract description 159
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 44
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 43
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 41
- 230000000694 effects Effects 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 71
- 239000000499 gel Substances 0.000 claims description 69
- 238000000926 separation method Methods 0.000 claims description 65
- 239000007787 solid Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000012298 atmosphere Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000004411 aluminium Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 238000007493 shaping process Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 17
- -1 ammonium halide Chemical class 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 229920000926 Galactomannan Polymers 0.000 claims description 16
- 229920003086 cellulose ether Polymers 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 15
- 229910001679 gibbsite Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 206010013786 Dry skin Diseases 0.000 claims description 12
- 150000004676 glycans Chemical class 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229920000609 methyl cellulose Polymers 0.000 claims description 12
- 229920001282 polysaccharide Polymers 0.000 claims description 12
- 239000005017 polysaccharide Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000001923 methylcellulose Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 230000002902 bimodal effect Effects 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 230000036571 hydration Effects 0.000 claims description 9
- 238000006703 hydration reaction Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000007789 sealing Methods 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
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 229940107816 ammonium iodide Drugs 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-RWOPYEJCSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 37
- 239000003292 glue Substances 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 239000000428 dust Substances 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 68
- 230000008569 process Effects 0.000 description 31
- 238000001125 extrusion Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000465 moulding Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 239000007790 solid phase Substances 0.000 description 17
- 238000004846 x-ray emission Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 15
- 241000219782 Sesbania Species 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 230000008859 change Effects 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 235000010981 methylcellulose Nutrition 0.000 description 10
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 9
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002803 maceration Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 235000010980 cellulose Nutrition 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 235000015424 sodium Nutrition 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010410 dusting Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 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 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002683 Glycosaminoglycan Polymers 0.000 description 2
- 229920000869 Homopolysaccharide Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 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
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229940097789 heavy mineral oil Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- 238000003828 vacuum filtration Methods 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
- 125000006527 (C1-C5) alkyl group Chemical group 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920003139 Eudragit® L 100 Polymers 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100063942 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dot-1 gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229940009493 gel-one Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 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 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000014612 sandwich biscuits Nutrition 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/027—Compounds of F, Cl, Br, I
-
- 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
- B01J20/06—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
- B01J20/22—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
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of composition of hydrated alumina containing halogen and preparation method thereof and formed body and its preparation method and application, said composition contains hydrated alumina, halogen contained compound and the compound with least two proton acceptor sites, said compositionIt is worth for not less than 1.8.The invention also discloses using by the formed body that the composition of hydrated alumina containing halogen is formed as carrier have hydrogenation catalyst effect catalyst and preparation method and hydrotreating method.The formed body with higher-strength is prepared by starting material of hydrated alumina wet gel in the present invention, eliminate for the step of drying hydrated alumina wet gel, simplify overall craft flow, overall operation energy consumption is reduced, avoids the dust pollution due to triggering using boehmite dry glue powder as raw material.The formed body formed by the aqua oxidation compositions shows the catalytic activity of higher as catalyst prepared by carrier in the hydrotreating of hydrocarbon ils.
Description
Technical field
The present invention relates to aluminium oxide field shaping technique, in particular it relates to a kind of group of hydrated alumina containing halogen
Compound and preparation method thereof, the invention further relates to the hydrated alumina shaping formed by the composition of hydrated alumina containing halogen
Body and aluminium oxide formed body, the invention further relates to a kind of shaping to be formed by the composition of hydrated alumina containing halogen
The catalyst with hydrogenation catalyst effect of body as carrier and preparation method thereof and the hydrotreating method using the catalyst.
Background technology
In conventional methods where, aluminium oxide formed body, particularly gama-alumina formed body, because its with preferable pore structure,
Suitable ratio surface and higher heat-resistant stability, use frequently as the carrier of adsorbent or loaded catalyst.By into
The carry out modulation that auxiliary agent halogens can be to aluminium oxide is introduced in type body, so that it meets wanting for some specific use occasions
Ask, such as：Hydrobon catalyst is prepared as carrier using the formed body of aluminium oxide containing halogen, can be to the hydrogenation essence of catalyst
Performance processed carries out modulation.This aluminium oxide is usually by dried hydrated alumina, and such as boehmite is through being molded, drying
Afterwards, high-temperature roasting obtains again.
Based on above-mentioned cognition, as shown in Figure 1, the hydrated alumina wet gel being prepared needs to be dried, intended
Boehmite dry glue powder, then using boehmite dry glue powder as starting point, adds extrusion aid, auxiliary agent (contains as shown in Figure 1
Halogen compounds) and optional chemical peptizing agent (inorganic acid and/or organic acid), through kneading aftershaping, molding is through overdrying
Used after dry and optional roasting as adsorbent or carrier.The main problem of this preparation method is that dust pollution is larger and energy
Consumption is high.
In order to reduce dust pollution, improve operating environment, researcher recognizes that shaping raw material used should be changed, opens
Begin to attempt hydrated alumina wet gel or semiarid boehmite preparing aluminium oxide molding as raw material.
US4613585 discloses a kind of method for preparing alumina catalyst carrier, and this method comprises the following steps：
(a) aluminum sulfate solution and sodium aluminate solution are poured into the container equipped with deionized water at the same time, makes aluminum sulfate solution
Reacted with sodium aluminate solution, reaction condition pH6.0-8.5, temperature is 50-65 DEG C, thus prepares first containing amorphous
The aqueous slurry of aluminium hydroxide；
(b) sodium aluminate aqueous solution is added into the first aqueous slurry, the additive amount of the sodium aluminate aqueous solution is enough to neutralize institute
The first aqueous slurry is stated, the total amount of the sodium aluminate solution used in step (a) and step (b) is equivalent to the sulphur used in step (a)
Stoichiometric 0.95-1.05 of the amount of sour aluminium, thus prepares the second aqueous slurry, the Al of second aqueous slurry2O3Concentration is
7wt% or higher；
(c) amorphous hydroted alumina in the second aqueous slurry is filtered out, filter cake is obtained, is obtained first with dilute ammonia scrubbing
Filter cake, then washed with dilute nitric acid solution, finally washed again with dilute ammonium hydroxide, with remove sulfate anion and
Sodium cation impurity, while the pH of filter cake is adjusted in the range of 7.5-10.5；
(d) then, without the aging filter cake, on a filter press by the cake dewatering, and by its Al2O3Content improve to
28-35wt%, and in the range of pH is 7.5-10.5, mediate the filter cake in the mixer of a self-cleaning type, during stop
Between be 10s or longer, boehmite particle is grown up in a short time, thus obtain the dough containing these particles；
(e) dough for obtaining step (d) is extruded into extrudate, and then dry and roasting obtains extrudate.
From the point of view of method disclosed in US4613585, although hydrated alumina wet gel can be molded by this method, from
The preparation condition of amorphous hydroted alumina is all restricted to kneader device and kneading conditions, causes complex operation.Also, by
Carrier prepared by this method should be unable to have very high intensity, it is difficult to meet the requirement of commercial Application, its reason is by this
The content of Free water is high in extrudate prepared by method, and the extrudate obtained through dry and roasting is loose.Meanwhile using this method
Carrier is prepared, it is difficult to regulate and control to the pore structure of carrier, so as to it is difficult to meet the needs of a variety of use occasions.
CN103769118A discloses a kind of heavy-oil hydrogenation catalyst, including carrier and active ingredient, and carrier is aluminium oxide,
Active component is group VIII and/or the metal of group vib, and wherein group VIII metal is Co or Ni, and group vib metal is Mo or W, its
In, it is prepared by the boehmite shaping that the alumina support contents on dry basis is less than 50%.The contents on dry basis is 50%
The preparation process of following boehmite includes：(1) aluminum salt solution carries out neutralizing plastic reaction with precipitating reagent；(2) filter back
The solid product of harvest glue reaction；(3) solid product obtains contents on dry basis as less than 50% after drying.
CN103769118A uses contents on dry basis to prepare alumina support, contents on dry basis for less than 50% boehmite
Boehmite for less than 50% is then to be done the solid product separated from the mixture that plastic is reacted
Obtained from dry, in actual mechanical process, it is difficult the method carried out that this, which is one, and main cause is as follows：
(1) the boehmite viscosity not being completely dried is stronger, and transfer is difficult, easily causes secondary dust to pollute；
(2) dry all since surface, to the wet solid separated from the mixture that plastic is reacted
The drying that product carries out belongs to endless white drying, therefore there are sandwich biscuits phenomenon, the i.e. surface of part boehmite to be done
Dry (that is, Free water being substantially free of by dry surface), and internal wet state is still maintained (that is, for not by dry
Portion, the content of Free water keep dry substantially before level), since surface is dried, form hard particles, to it is this not
Peptizing agent and/or binding agent are added in the boehmite parched completely when through mediating aftershaping, is formed in drying process
Hard particles easily cause to block during extrusion, influence production efficiency；
(3) it is difficult to which the butt of stability contorting boehmite, butt is unstable to cause very big interference to shaping, make into
Type process is also highly unstable, causes the increase of substandard product amount, and production efficiency is low；
(4) CN103769118A in shaping using conventional moulding process, the boehmite used yet with it
Butt (for 35%-50%) far below conventional contents on dry basis (for 70% or so), i.e. water content height, in extrusion molding process
Extrusion pressure will not be substantially produced, therefore the carrier that extrudate obtains after drying and roasting does not have mechanical strength substantially, as long as
Apply some external force, will dusting, do not possess the possibility of commercial Application, this is the greatest problem that the technology faces.
In conclusion how on the premise of guaranteeing to be met the alumina support of industrial application requirement, simplify oxygen
Change the preparation process flow of alumina supporter and reduce operation energy consumption, while mitigate the dirt of the dust in alumina support preparation process
Dye is still a technical problem urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to simplify the preparation process flow of alumina support, mitigate carrying alumina preparation process mistake
Dust pollution in journey, while the carrier prepared can also meet industrial application requirement.
For US4613585 and CN103769118A when preparing alumina support problem encountered, hair of the invention
A person of good sense is off the beaten track, by the compound containing at least two proton acceptor sites in molecular structure and arises directly from synthetic reaction
The mixing of hydrated alumina wet gel, the mixture of formation can not only be molded, and be obtained through dry and optional roasting
To shaping physical efficiency have and meet the intensity of industrial requirements.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of composition of hydrated alumina containing halogen, the combination
Thing contains hydrated alumina, halogen contained compound and the compound with least two proton acceptor sites,
The compositionIt is worth for 1.8-5, it is describedValue is measured using following methods：By composition described in 10g 120
It is 240 minutes dry DEG C in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
According to the second aspect of the invention, the present invention provides a kind of preparation side of the composition of hydrated alumina containing halogen
Method, this method include mixing each component in a kind of feedstock composition, obtain the hydrated alumina composition, the raw material
Composition contains hydrated alumina wet gel, halogen contained compound and the compound with least two proton acceptor sites, institute
The i values for stating hydrated alumina wet gel are the use of the compound with least two proton acceptor sites not less than 60%
Amount causes the composition finally preparedIt is worth for 1.8-5,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will
Quality through dry composition is denoted as w1, calculated using Formulas IValue,
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention
The standby composition of hydrated alumina containing halogen.
According to the fourth aspect of the present invention, the present invention provides a kind of formed body of hydrated alumina containing halogen, the hydration
Aluminium oxide formed body is as the composition of hydrated alumina containing halogen described in the first aspect of the present invention or the 3rd side of the invention
The composition of hydrated alumina containing halogen described in face is formed.
According to the fifth aspect of the present invention, the present invention provides a kind of formed body of aluminium oxide containing halogen, this contains halogen oxygen
Change aluminium formed body as the composition of hydrated alumina containing halogen or third aspect of the present invention described in the first aspect of the present invention
The composition of hydrated alumina containing halogen is formed.
According to the sixth aspect of the invention, the present invention provides a kind of preparation method of formed body, this method includes will
Contain halogen described in the composition of hydrated alumina containing halogen or third aspect of the present invention described in the first aspect of the present invention
Hydrated alumina composition is molded, and obtained molding is dried and is optionally roasted.
According to the seventh aspect of the present invention, the present invention provides a kind of method system as described in the 6th aspect of the present invention
Standby formed body.
According to the eighth aspect of the present invention, the present invention provides a kind of production shaping side of hydrated alumina containing halogen
Method, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and solid-liquid
Separation, obtains the first hydrated alumina wet gel, the condition of the separation of solid and liquid causes the first hydrated alumina wet gel
I values be not less than 60%, be preferably not lower than 62%, more preferably not above 82%, more preferably not higher than 80%,
Still more preferably it is not higher than 78.5%；
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(2) using the method described in second aspect of the present invention by the first hydrated alumina wet gel and with least
The compound mixing in two proton acceptor sites, obtains the composition of hydrated alumina containing halogen；
(3) composition of hydrated alumina containing halogen is molded, obtains hydrated alumina forming matter containing halogen；
(4) hydrated alumina forming matter containing halogen is dried, obtains the formed body of hydrated alumina containing halogen；
(5) alternatively, at least part formed body of hydrated alumina containing halogen is roasted, obtains aoxidizing containing halogen
Aluminium formed body,
Wherein, this method is additionally included in the operation that mixing halogen contained compound is carried out in step (1) and/or step (2), with
So that the hydrated alumina composition contains halogen contained compound.
According to the ninth aspect of the present invention, the present invention provides a kind of production shaping side of hydrated alumina containing halogen
Method, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains the second aqua oxidation
Aluminium wet gel,
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid
Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are
Not less than 60%, 62%, more preferably not above 82% are preferably not lower than, more preferably not higher than 80%, more into one
Step is preferably not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(3) using the method described in second aspect of the present invention by the second hydrated alumina wet gel and with least two
The compound mixing in proton acceptor site, obtains the composition of hydrated alumina containing halogen；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter containing halogen；
(5) hydrated alumina forming matter containing halogen is dried, obtains the formed body of hydrated alumina containing halogen；
(6) alternatively, at least part formed body of hydrated alumina containing halogen is roasted, obtains aoxidizing containing halogen
Aluminium formed body；
Wherein, this method is additionally included in the operation that mixing halogen contained compound is carried out in step (1) and/or step (2), with
So that the hydrated alumina composition contains halogen contained compound.
According to the tenth aspect of the present invention, the present invention provides one kind by the 8th aspect of the present invention or the 9th side
Formed body prepared by the method described in face.
According to the eleventh aspect of the present invention, should the present invention provides a kind of catalyst with hydrogenation catalyst effect
Catalyst contains the hydrogenation active component of carrier and load on the carrier, wherein, the carrier is according to the present invention's
The formed body of hydrated alumina containing halogen or the according to the present invention formed body of aluminium oxide containing halogen.
According to the twelfth aspect of the present invention, the present invention provides a kind of system of the catalyst with hydrogenation catalyst effect
Preparation Method, this method are included in supported on carriers hydrogenation active component, wherein, the carrier is the water containing halogen according to the present invention
Close aluminium oxide formed body or the according to the present invention formed body of aluminium oxide containing halogen.
13rd aspect according to the present invention, the present invention provides a kind of hydrotreating method, this method, which is included in, to be added
Under hydrogen treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, it is described to have what hydrogenation catalyst acted on
Catalyst is prepared for the catalyst described in the tenth one side of the invention or as the method described in the 12nd aspect of the present invention
Catalyst.
With the existing process that the alumina support containing halogen is prepared using boehmite dry glue powder as starting material
(technique as shown in Figure 1) is compared, and the present invention is directly used as shaping using the hydrated alumina wet gel that synthetic reaction is prepared
Starting material, have the advantage that：
(1) the step of being used to dry hydrated alumina wet gel in existing process is eliminated, and is preparing shaping raw material
When, boehmite dry glue powder is modulated into plastic material without additionally introducing water, simplifies overall craft flow, is reduced
Overall operation energy consumption；
(2) dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, is greatly improved
Operating environment.
Existing process, such as US4613585 with directly preparing carrier using hydrated alumina wet gel as starting material
Compared with CN103769118A, technical process of the invention is more succinct, and operability is stronger, and can effectively improve final
The intensity of the formed body of preparation.The present invention can prepare the shaping with higher-strength by starting material of hydrated alumina wet gel
The reason for body, may is that：Compound with least two proton acceptor sites and the Free water in hydrated alumina wet gel
Interaction forms hydrogen bond, adsorbs the Free water in hydrated alumina wet gel, while have at least two proton acceptor sites
Compound also can with hydrated alumina molecular structure hydroxyl occur interaction of hydrogen bond, play the role of physics peptization,
So that hydrated alumina wet gel can not only be molded, and can be so that the formed body finally prepared has higher intensity.
What is prepared using formed body according to the present invention as carrier has the catalyst of hydrogenation catalyst effect in hydrocarbon oil hydrogenation
Higher catalyst activity is shown in processing.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is moulding process flow process usually used in current commercial Application.
Fig. 2 is a kind of preferred embodiment for the method for preparing hydrated alumina composition according to the present invention.
Fig. 3 is a kind of preferred embodiment of moulding process flow process according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of composition of hydrated alumina containing halogen, the combination
Thing contains hydrated alumina, halogen contained compound and the compound with least two proton acceptor sites.
The hydrated alumina can be more than one or both of gibbsite and a water aluminium oxide.It is described
Hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.The instantiation of the hydrated alumina can be with
Including but not limited to boehmite, gibbsite, unformed hydrated alumina and boehmite.In a kind of excellent of the present invention
In the embodiment of choosing, the hydrated alumina contains boehmite, more preferably boehmite.According to the preferable reality
The composition of hydrated alumina containing halogen of mode is applied particularly suitable for preparing the formed body as catalyst carrier.
The composition of hydrated alumina containing halogen according to the present invention, the hydrated alumina are directed to hydrated alumina
Wet gel, is not originating from hydrated alumina dry glue powder.In the present invention, term " hydrated alumina wet gel " refers to pass through synthesis
Reaction obtains and does not live through that its i value is reduced to the dehydrated of less than 60% (preferably less than 62%, more preferably less than 64%)
The aqueous alumina hydrate gel of journey.In the present invention, i values are measured using following methods：10g hydrated alumina wet gels are existed
120 DEG C 240 minutes dry in air atmosphere, and the quality through dry sample is denoted as w2, i values are calculated using Formula II,
The synthetic reaction refers to the reaction for preparing gel aluminum hydroxide, can be aqua oxidation commonly used in the art
Alumina gel synthetic reaction, specific examples thereof include the precipitation method (including acid system and alkaline process), Hydrolyze method, kind point-score and fast dewatering
Method.The alumina hydrate gel of synthesis can be the alumina hydrate gel without going through aging, or live through aging
Alumina hydrate gel.The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method concrete operation method and condition can be with
For conventional selection, will hereinafter illustrate.The hydrated alumina wet gel can be by the hydration that obtains synthetic reaction
After alumina gel alternatively carries out aging, carry out washing and separation of solid and liquid and collect solid phase and obtain.
It is different from the hydrated alumina from dry glue powder, it is directed to the aqua oxidation of alumina hydrate gel
Aluminium thing of hydrated alumina in storage process, which is met, to change.For example, it is small that 72 are placed under environment temperature and sealing condition
When, the thing of hydrated alumina, which is met, in the composition after placement changes.Depending on the environment temperature is with environment is placed, generally
It can be 5-50 DEG C, such as 20-40 DEG C.The sealing condition refers to the composition being placed in closure container, the closed appearance
Device can be closure container (such as tank, bucket or case), or the flexible coating (such as sealed bag) of sealing, the flexible bag
It can be paper and/or polymeric material to cover thing, be preferably polymeric material, such as plastics.
In an example, the hydrated alumina for being directed to alumina hydrate gel contains boehmite (as directly
It is boehmite to fetch and come from the hydrated alumina of alumina hydrate gel) when, by the composition in environment temperature and envelope
When placement 72 is small under the conditions of closing, the gibbsite content in the composition after placement is higher than three water in the composition before placing
Alumina content.In this example, on the basis of the total amount of the content of the gibbsite in the composition before placement, after placement
Composition in gibbsite content generally at least improve 0.5%, preferably at least improve 1%, more preferably improve 1.1% to
2%.
The composition of hydrated alumina containing halogen according to the present invention, also contains the change with least two proton acceptor sites
Compound.The composition of hydrated alumina containing halogen according to the present invention, without being used as starting material using dry glue powder, you can for being molded
(particularly extrusion molding), and there is obtained formed body the reason for higher intensity may is that：It is described to have at least two
With the Free water in hydrated alumina wet gel interaction of hydrogen bond occurs for the compound in proton acceptor site, so as to adsorb freedom
Water, while interact with the hydroxyl in hydrated alumina molecular structure, play the role of peptization.
In the compound with least two proton acceptor sites, proton acceptor site refers to point of the compound
The position of hydrogen bond can be formed in minor structure with water and hydroxyl.The instantiation in the proton acceptor site can include but unlimited
More than one or both of fluorine (F), oxygen (O) and nitrogen (N).The compound with least two proton acceptor sites
Instantiation can include but is not limited to contain selected from hydroxyl, carboxyl, amino, ehter bond, aldehyde radical, carbonyl, acid amides in molecular structure
The compound of group more than one or both of base and fluorine atom, is preferably hydroxyl and/or ehter bond.
The compound with least two proton acceptor sites can be organic compound, or inorganic chemical
Thing, can also be the combination of organic compound and inorganic compound.Using organising with least two proton acceptor sites
Compound, the organic compound can be removed by roasting process.Using the inorganic chemical with least two proton acceptor sites
Thing, the Partial Elements in the inorganic compound can be retained in the formed body finally prepared, it is possible thereby to inorganization by this
Compound introduces auxiliary element in formed body.
In a kind of preferred embodiment of the present invention, it is described there are at least two proton acceptor sites compound be
There is the polymer in multiple (such as more than three) proton acceptor sites in molecular structure.According to the preferred embodiment, can obtain
Physically better peptization is obtained, so that the intensity of the formed body finally prepared is further improved, particularly using extrusion work
When skill is molded, the intensity of the formed body finally prepared can be further improved.Preferably, the polymer is organic polymer
Thing.According to the preferred embodiment, the instantiation of the compound with least two proton acceptor sites can wrap
Include but be not limited to polyol, is more than one or both of polyethers and acrylic acid polymer.
The polyol can include but be not limited to polysaccharide, the etherate and polyalcohol of polysaccharide.
The polysaccharide can be homopolysaccharide, or heteroglycan, can also be the combination of homopolysaccharide and heteroglycan.It is described
Polysaccharide and its etherate specific examples thereof include but be not limited to glucan, galactan, mannosan, galactomannans, fibre
Dimension plain ether, starch, chitin, glycosaminoglycan and glycosaminoglycan.The cellulose ether refers to the part of hydroxyl in cellulosic molecule
On hydrogen atom substituted by alkyl after the ether system derivative that is formed, wherein, multiple alkyl can be identical, or no
Together.The alkyl is selected from the alkyl of substitution and unsubstituted alkyl.The unsubstituted alkyl be preferably alkyl (such as：C1-C5
Alkyl).In the present invention, C1-C5The instantiation of alkyl include C1-C5Straight chained alkyl and C3-C5Branched alkyl, can be with
For but be not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and uncle penta
Base.The substituted alkyl for example can be substituted by hydroxyl, carboxyl, cyano group or aryl alkyl (such as：C1-C5By hydroxyl
Alkyl, the C of base substitution1-C5The alkyl substituted by carboxyl, the C that is substituted with aryl1-C5Alkyl), the aryl can be benzene
Base or naphthyl.The instantiation of the substituted alkyl can include but is not limited to：Cyano group, benzyl, phenethyl, hydroxyl first
Base, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.The instantiation of the cellulose ether can include
But it is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzylcellulose, ethoxy
Cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose, carboxymethyl hydroxyl second
Base cellulose and benzyl cellulose.The polysaccharide and its etherate can provide in a variety of manners, such as：Galactomannans can
With from sesbania powder.
The polyalcohol specific examples thereof include but be not limited to polyvinyl alcohol, part acetalation polyvinyl alcohol (acetalizing degree
Can be less than 95%, be preferably less than 80%, more preferably less than 70%, more preferably less than 50%), polyether polyols
It is more than one or both of alcohol and polyester polyol.
The polyethers specific examples thereof include but be not limited to polyethylene oxide, polypropylene oxide, epoxy ethane-epoxy propane
Copolymer and PolyTHF.
The acrylic acid polymer refers to the polymer containing acrylic monomer unit, the acrylic monomer list
Member be specifically as follows but be not limited to acrylic monomer units and acrylate monomer units (be preferably C1-C5Alkyl acrylic
Monomeric unit, more preferably methacrylic acid monomer units).Specific examples thereof include polypropylene for the acrylic acid polymer
Acid, polymethylacrylic acid, copolymer of acrylic acid and methyl acrylate, acryl acid-methyl methacrylate copolymer, metering system
Acid-methyl acrylate copolymer and EUDRAGIT L100.
In the preferred embodiment, it is described there are at least two proton acceptor sites compound it is further preferably more
The etherate of sugar and/or polysaccharide, the more preferably etherate of polysaccharide and/or polysaccharide.
In a kind of embodiment being more highly preferred to of the present invention, the chemical combination with least two proton acceptor sites
Thing contains galactomannans and cellulose ether.The embodiment being more highly preferred to according to this, by composition shape according to the present invention
Into formed body have higher intensity.It is further preferred that it is described there are at least two proton acceptor sites compound it is excellent
Elect galactomannans and cellulose ether as.
In the embodiment that this is more highly preferred to, with the total amount of the compound with least two proton acceptor sites
On the basis of, the content of the galactomannans can be 10-70 weight %, be preferably 15-68 weight %, more preferably 20-
65 weight %, more preferably 25-60 weight %, are still more preferably 30-55 weight %；The content of the cellulose ether
It can be 30-90 weight %, be preferably 32-85 weight %, more preferably 35-80 weight %, more preferably 40-75 weights
% is measured, is still more preferably 45-70 weight %.
The composition of hydrated alumina containing halogen according to the present invention, contains halogen contained compound.The halogen contained compound
In halogens can be fluorine, chlorine, bromine either iodine be preferably fluorine, chlorine or iodine.The content of the halogen contained compound can be with
Made choice according to the final application occasion of said composition.In one embodiment, in said composition, relative to 100 weight
Part hydrated alumina, the content of the halogen contained compound can be 0.1-10 parts by weight, be preferably 0.5-5 parts by weight, described
Halogen contained compound is in terms of halogens.Acted on according to the composition of the embodiment particularly useful for making with hydrogenation catalyst
Catalyst carrier.The content of halogens uses x ray fluorescence spectrometry in the composition of hydrated alumina containing halogen
(XRF) measure.Alternatively, it is also possible to be calculated by inventory, water containing halogen is calculated using inventory in the embodiment of the present invention
Close the content of halogens in alumina composition.
The halogen contained compound can be the compound containing halogens in molecular structure.Have at least two described
When containing fluorine atom in the molecular structure of the compound in a proton acceptor site, at least part halogen contained compound can be with
The compound at least two proton acceptor sites.Preferably, at least partly described halogen contained compound is to have different from described
The compound at least two proton acceptor sites, such as micromolecular compound.It is highly preferred that at least partly described halogen contained compound
For ammonium halide, its instantiation can include but is not limited to one or both of ammonium fluoride, ammonium chloride, ammonium bromide and ammonium iodide
More than.It is further preferred that at least partly described halogen contained compound is one kind or two in ammonium fluoride, ammonium chloride and ammonium iodide
More than kind.
Composition according to the present inventionIt is worth for 1.8-5, is preferably not lower than 1.85, such as can is 1.85-4, it is more excellent
Elect as not less than 1.9, such as can be 1.9-3.5, be preferably 1.9-3.2.This, which contains halogen hydrated alumina composition, to make
Standby aperture is in the formed body of bimodal distribution.
In the present invention,Value is measured using following methods：By composition described in 10g in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
Composition according to the present invention, the content of the compound with least two proton acceptor sites is can make institute
State compositionValue meets subject to above-mentioned requirements.Preferably, it is described to have extremely relative to hydrated alumina described in 100 parts by weight
The content of the compound in few two proton acceptor sites can be 1-25 parts by weight, be preferably 3-22 parts by weight, more preferably 4-
20 parts by weight.
Composition according to the present invention, can contain peptizing agent, can not also contain peptizing agent.The peptizing agent can be
The usually used reagent with gelatification of aluminium oxide formed body preparing technical field, its instantiation can include but unlimited
In Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.
Composition according to the present invention, the compound with least two proton acceptor sites, particularly described
It is described when compound with least two proton acceptor sites is containing polymer with least two proton acceptor sites
The compound with least two proton acceptor sites can play physics peptization, so as to reduce the use of peptizing agent
Amount, it might even be possible to without using peptizing agent.
In a kind of preferred embodiment of the present invention, relative to 100 parts by weight hydrated aluminas, the peptizing agent
Content is below 5 parts by weight.
In a kind of particularly preferred embodiment of the present invention, composition according to the present invention does not contain peptizing agent.Root
According to the composition of the particularly preferred embodiment, when being used to prepare formed body, even if the hydrated alumina formed body of preparation
Without roasting, aluminium oxide formed body is transformed into, can also be used as adsorbent or carrier to use, because unfired water
When conjunction aluminium oxide formed body contains peptizing agent, peptizing agent is being adsorbed and dissolved in dipping process, a large amount of to be lost in so that formed body goes out
Now dissolving, dusting and duct are caved in phenomenon, finally lose shape, thus adsorbent and carrier can not be used as to use.
According to the second aspect of the invention, the present invention provides a kind of preparation side of the composition of hydrated alumina containing halogen
Method, this method include mixing each component in a kind of feedstock composition, obtain the composition of hydrated alumina containing halogen, i.e.,
The mixture being mixed to get is the composition of hydrated alumina containing halogen.
The preparation method of the composition of hydrated alumina containing halogen, the raw mixture contain hydration oxygen according to the present invention
Change aluminium wet gel, halogen contained compound and the compound with least two proton acceptor sites.It is described that there are at least two matter
Detailed description has been carried out above for the compound of sub- acceptor site and the species of halogen contained compound, no longer superfluous herein
State.
The hydrated alumina wet gel can use conventional method to synthesize, for example with the precipitation method (including acid system and alkali
Method), Hydrolyze method, kind one or both of point-score and rapid dehydration method more than method be made.Usually by hydrated alumina
After gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from.
The precipitation method include acid system and alkaline process.The acid system is that aluminium salt is carried out precipitation reaction with alkali compounds.Institute
It is that aluminate is carried out precipitation reaction with acid compound to state alkaline process.In the precipitation method, the mixture that precipitation reaction obtains is optional
After ground carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, the solid phase isolated is washed, obtains the hydration
Aluminium oxide wet gel.
The aluminium salt and the species of the aluminate can be conventional selection.The instantiation of the aluminium salt can include but
It is not limited to more than one or both of aluminum sulfate, aluminium chloride and aluminum nitrate.The instantiation of the aluminate can include but
It is not limited to more than one or both of sodium metaaluminate, potassium metaaluminate and meta-aluminic acid magnesium.
The alkali compounds and the acid compound can be conventional selection.The alkali compounds can be common
It is various can make water in alkalescence compounds, ammonium hydroxide, hydroxide and basic salt can be selected from.The hydroxide can be normal
The water soluble hydroxide seen, such as alkali metal hydroxide.The basic salt can be that common decomposition in water make it that water is in
The salt of alkalescence, such as meta-aluminate, carbonate and bicarbonate.The instantiation of the alkali compounds can include but is not limited to
Ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, sodium carbonate, carbonic acid
It is more than one or both of hydrogen potassium and potassium carbonate.The acid compound can be the common various changes that can make water in acidity
Compound, can be inorganic acid and/or organic acid.The instantiation of the acid compound can include but is not limited to sulfuric acid, salt
It is more than one or both of acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid.The carbonic acid can be by leading
Enter carbon dioxide and generation in situ.
The precipitation reaction can carry out under normal conditions, this is not particularly limited in the present invention.Usually, the alkali
The dosage of the property compound either acid compound causes the pH of the aluminum salt solution or the aluminate solution to be 6-10,
Preferably 7-9.The precipitation reaction can carry out at a temperature of 30-90 DEG C, preferably 40-80 DEG C.
The method of hydrated alumina wet gel is prepared using Hydrolyze method to be included：Aluminum contained compound is hydrolyzed instead
Should, after the mixture that hydrolysis is obtained alternatively carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, will be isolated
Solid phase washed, so as to obtain the hydrated alumina wet gel.
The aluminum contained compound can prepare the calorize that contains usually used in alumina hydrate gel technique for Hydrolyze method and close
Thing.The aluminum contained compound is preferably the organo-aluminum compound that hydrolysis can occur, more preferably aluminium alcoholates.It is described to contain calorize
The instantiation of compound can include but is not limited to aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and different
It is more than one or both of octanol aluminium.
The present invention is not particularly limited for the actual conditions of hydrolysis, can carry out under normal conditions.Usually,
The hydrolysis can be 3-11 in pH, be carried out under conditions of preferably 6-10.The hydrolysis can 30-90 DEG C,
It is preferred that carried out at a temperature of 40-80 DEG C.
In the precipitation method and Hydrolyze method, the condition of the aging is not particularly limited, and can carry out under normal conditions.One
As, the aging can carry out at a temperature of 35-98 DEG C, preferably 40-80 DEG C.The duration of the aging can be
When 0.2-6 is small.
The method of hydrated alumina wet gel is prepared using kind of point-score to be included：Added into supersaturated aluminate solution
Crystal seed, decomposes and produces aluminium hydroxide, and the mixture that decomposition is obtained carries out separation of solid and liquid, and the solid phase isolated is washed,
So as to obtain the hydrated alumina wet gel.The instantiation of the aluminate can include but is not limited to sodium metaaluminate, partially
It is more than one or both of potassium aluminate and meta-aluminic acid magnesium.
The method of hydrated alumina wet gel is prepared using rapid dehydration method to be included：By hydrated alumina in 600-
Roasted at a temperature of 950 DEG C, preferably 650-800 DEG C, product of roasting carries out hydro-thermal process, the mixing that hydro-thermal process is obtained
Thing carries out separation of solid and liquid, so as to obtain hydrated alumina wet gel.When the duration of the roasting can be 1-6 small, preferably
For 2-4 it is small when.The hydro-thermal process can carry out at a temperature of 120-200 DEG C, preferably 140-160 DEG C.The hydro-thermal process
Usually in closed container, carried out under self-generated pressure.
The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method in, the separation of solid and liquid can use conventional method into
OK, it is specifically as follows the combination of filtering, centrifugation or both.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, the i of the hydrated alumina wet gel
It is worth not less than 60%, to be preferably not lower than 62%.The i values of the hydrated alumina wet gel are preferably not higher than 82%, more
Preferably not higher than 80%, more preferably not higher than 78.5%.Specifically, the i values of the hydrated alumina wet gel can
Think 60-82%, be preferably 62-80%, more preferably 62-78.5%.
Can be by carrying out separation of solid and liquid during separation of solid and liquid to the solution containing alumina hydrate gel being prepared
Condition is controlled, so as to obtain the hydrated alumina wet gel that i values meet above-mentioned requirements.In one embodiment of the present invention
In, separation of solid and liquid is more than once or twice, at least last time separation of solid and liquid is pressure filtration and/or vacuum filter.At this
In embodiment, by adjusting the pressure of application and/or the size of vacuum, carried out to obtaining hydrated alumina wet gel i values
Control.The instantiation for the device that the pressure filtration uses can include but be not limited to plate and frame type filter-press, belt type filter
The combination of machine or both.In order to control the i values of the hydrated alumina wet gel of acquisition, natural wind or with pressure can also be used
Wind purges isolated solid phase, so as to improve the efficiency of moisture abjection.The pressure of the wind with pressure can be conventional
Selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, the hydrated alumina that separation of solid and liquid obtains
Wet gel does not live through the dehydration that its i value is reduced to less than 60% (preferably less than 62%) generally.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, it is described that there are at least two proton acceptors
The dosage of the compound in site enables to the composition of hydrated alumina containing halogen finally preparedIt is worth for 1.8-5, is preferably
It not less than 1.85, such as can be 1.85-4, more preferably not less than 1.9, such as can be 1.9-3.5, be preferably 1.9-
3.2.The formed body that aperture is in bimodal distribution can be prepared by said composition.
Usually, it is described that there are at least two proton acceptor sites relative to 100 parts by weight hydrated alumina wet gels
The dosage of compound can be 1-25 parts by weight, be preferably 3-22 parts by weight, more preferably 4-20 parts by weight, the aqua oxidation
Aluminium wet gel is in terms of hydrated alumina.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, in a kind of embodiment being more highly preferred to
In, the compound with least two proton acceptor sites contains galactomannans and cellulose ether.By according to this more
The formed body formed for the composition of preferred embodiment has the intensity of higher.It is further preferred that described have at least
The compound in two proton acceptor sites is preferably galactomannans and cellulose ether.
In the embodiment that this is more highly preferred to, with the total amount of the compound with least two proton acceptor sites
On the basis of, the content of the galactomannans can be 10-70 weight %, be preferably 15-68 weight %, more preferably 20-
65 weight %, more preferably 25-60 weight %, are still more preferably 30-55 weight %；The content of the cellulose ether
It can be 30-90 weight %, be preferably 32-85 weight %, more preferably 35-80 weight %, more preferably 40-75 weights
% is measured, is still more preferably 45-70 weight %.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, it is described have at least two protons by
When the compound of position point contains halogens, at least partly the halogen contained compound for it is described have at least two protons by
The compound of position point.Preferably, at least partly the halogen contained compound be different from it is described have at least two protons by
The compound of position point, such as micromolecular compound.It is highly preferred that at least partly described halogen contained compound is ammonium halide, it has
Body example can include but is not limited to more than one or both of ammonium fluoride, ammonium chloride, ammonium bromide and ammonium iodide.It is further excellent
Selection of land, at least partly described halogen contained compound are more than one or both of ammonium fluoride, ammonium chloride and ammonium iodide.
The content of halogen contained compound can be according to it is contemplated that hydrated alumina containing halogen combines in the raw mixture
The content of the halogens introduced in thing makes choice.Usually, the content of halogen contained compound makes in the raw mixture
Obtain in the composition of hydrated alumina containing halogen finally prepared, relative to 100 parts by weight hydrated aluminas, the chemical combination containing halogen
The content of thing can be 0.1-10 parts by weight, be preferably 0.5-5 parts by weight, the halogen contained compound is in terms of halogens.
The preparation method of the composition of hydrated alumina containing halogen, the raw mixture can contain glue according to the present invention
Solvent, can not also contain peptizing agent.Preferably, contain relative to 100 parts by weight hydrated alumina wet gels, the peptizing agent
Measure as below 5 parts by weight, the hydrated alumina wet gel is in terms of hydrated alumina.It is highly preferred that the raw mixture is not
Contain peptizing agent.That is, the preparation method of the composition of hydrated alumina containing halogen does not include to described more preferably according to the present invention
The step of peptizing agent is added in raw mixture.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, can use conventional method to be hydrated oxygen
Change aluminium wet gel to mix with the compound with least two proton acceptor sites.Can be under shear action by hydrated alumina
Wet gel is mixed with the compound with least two proton acceptor sites.In one embodiment, the mode of the mixing
For stirring.Can be by hydrated alumina wet gel and the compound with least two proton acceptor sites with agitating device
Container in, the two is uniformly mixed by stirring, so as to obtain the composition of hydrated alumina containing halogen according to the present invention.Institute
Stating stirring can carry out in the container with agitating device, can also be carried out in beater.In another embodiment,
The mode of the mixing is kneading.Can be by hydrated alumina wet gel and the compound with least two proton acceptor sites
Mediated in kneader, so as to obtain the composition of hydrated alumina containing halogen according to the present invention.The class of the kneader
Type is not particularly limited.The preparation method of the composition of hydrated alumina containing halogen according to the present invention, can be by stirring and mixing
It is applied in combination, hydrated alumina wet gel is mixed with the compound with least two proton acceptor sites.At this time, preferably
First it is stirred, then is mediated.
The preparation method of hydrated alumina composition according to the present invention, can use various order by merging will be described halogen
Plain compound, the compound with least two proton acceptor sites and the mixing of hydrated alumina wet gel.
In one embodiment, halogen contained compound can be mixed during hydrated alumina wet gel is prepared,
Halogen contained compound can also be added in the hydrated alumina wet gel being prepared, hydrated alumina can also prepared
Mixing portion halogen contained compound during wet gel, remainder halogen contained compound are added to the hydration oxygen being prepared
Change in aluminium wet gel, the operation for mixing halogen contained compound can be in one of above-mentioned addition opportunity, both or three
Carry out., can be in precipitation reaction process, aging when mixing halogen contained compound during preparing hydrated alumina wet gel
One of process, separation of solid and liquid process and washing process, both, carry out mixing halogen contained compound in three or four
Operation.It can choose whether that mixing contains halogen during hydrated alumina wet gel is prepared according to the type of precipitation reaction
Compound and the opportunity of mixing.
In another embodiment, halogen contained compound is mixed after the completion of the preparation of hydrated alumina wet gel.At this
In embodiment, it can carry out one of in the following ways：(1) first halogen contained compound and hydrated alumina wet gel are mixed
Close, then compound of the mixing with least two proton acceptor sites；(2) first by with least two proton acceptor sites
Compound is mixed with hydrated alumina wet gel, then mixes halogen contained compound；(3) while by halogen contained compound and have
The compound at least two proton acceptor sites is mixed with hydrated alumina wet gel.
The preparation method of hydrated alumina composition according to the present invention, preferably prepares in hydrated alumina wet gel and completes
After mix halogen contained compound.
The preparation method of the composition of hydrated alumina containing halogen according to the present invention, in mixed process, can supplement and add
Add water, addition water can not also be supplemented, as long as can cause the composition of hydrated alumina containing halogen of preparationValue meets above-mentioned want
Ask.Usually, from the angle for the uniformity for improving mixing, addition water can be supplemented in mixed process.Usually,
The water and the weight ratio of the compound with least two proton acceptor sites for supplementing addition can be 5-15：1, it is preferably 8-
12：1.
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention
The standby composition of hydrated alumina containing halogen.
The composition of hydrated alumina containing halogen can use conventional method to be molded according to the present invention, so as to obtain
The carrier of hydrated alumina containing halogen or alumina support containing halogen.
According to the fourth aspect of the present invention, the present invention provides a kind of formed body of hydrated alumina containing halogen, this is halogen
Plain hydrated alumina formed body is as the composition of hydrated alumina containing halogen described in the first aspect of the present invention or the present invention the
The composition of hydrated alumina containing halogen described in three aspects is formed.
The composition of hydrated alumina containing halogen according to the present invention can be molded, obtained molding is done
It is dry, so as to obtain the formed body of hydrated alumina containing halogen according to the present invention.
The molding mode is not particularly limited, and can use various molding modes commonly used in the art, such as：Squeeze
Bar, spraying, round as a ball, tabletting or combinations thereof.The present invention a kind of preferred embodiment in, by way of extrusion come
Shaping.
The temperature that the molding is dried can be the conventional selection of this area.Usually, the temperature of the drying
Degree can be more than 60 DEG C and be not higher than 350 DEG C, preferably 80-300 DEG C, be more preferably 110-260 DEG C.The time of the drying
It can be made appropriate choice according to dry temperature, so as to so that volatile matter in the hydrated alumina formed body finally obtained
Content meets subject to requirement.Usually, when the duration of the drying can be 1-48 small, when being preferably 2-24 small,
When more preferably 2-12 is small, when more preferably 2-4 is small.The drying can in oxygen-containing atmosphere (such as air atmosphere) into
OK, can also be carried out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), preferably in oxygen-containing atmosphere into
OK.
The formed body of hydrated alumina containing halogen according to the present invention, according to specifically used requirement can with variously-shaped,
Such as：Spherical, bar shaped, piece shape, bird-nest-shaped or honeycombed, the instantiation of the bar shaped can include but is not limited to：Three leaves
Careless shape, dish, cylinder and Rasching ring.
The formed body of hydrated alumina containing halogen has abundant pore structure according to the present invention.Measured by mercury injection method, it is halogen
The pore-size distribution of plain hydrated alumina formed body is in bimodal distribution.Wherein, most probable pore size is respectively that 4-20nm (is preferably 6-
18nm) and more than 20nm (such as 20.5-35nm).
The formed body of hydrated alumina containing halogen according to the present invention, this contains halogen hydrated alumina formed body with higher
Intensity.Usually, according to the present invention the radial direction crushing strength of the formed body of hydrated alumina containing halogen for more than 10N/mm (such as
Can be 10-55N/mm), it is preferably more than 12N/mm (such as can be 12-50N/mm).In the present invention, using RIPP 25-
The radial direction crushing strength of method measure formed body specified in 90.
According to the fifth aspect of the present invention, the present invention provides a kind of formed body of aluminium oxide containing halogen, this contains halogen oxygen
Change aluminium formed body as the composition of hydrated alumina containing halogen or third aspect of the present invention described in the first aspect of the present invention
The composition of hydrated alumina containing halogen is formed.
The composition of hydrated alumina containing halogen according to the present invention can be molded, obtained molding is first laggard
Row is dry and roasts, so as to obtain the formed body of aluminium oxide containing halogen.
The shaping and the 4th aspect of dry method and condition and the present invention are described identical, are no longer described in detail herein.
The present invention is not particularly limited for the condition of roasting, can be the conventional selection of this area.Specifically, the roasting
The temperature of burning can be 450-1500 DEG C.Furthermore it is also possible to the temperature of roasting is optimized according to the species of hydrated alumina.
In one embodiment, the hydrated alumina is a water aluminium oxide, such as boehmite and/or boehmite, described
The temperature of roasting is preferably 450-1100 DEG C, more preferably 460-1000 DEG C, more preferably 500-950 DEG C.In another kind
In embodiment, the hydrated alumina is gibbsite, and the temperature of the roasting is preferably 800-1500 DEG C, more preferably
900-1400℃.When the duration of the roasting can be 1-8 small.The roasting can be at oxygen-containing atmosphere (such as air atmosphere)
Middle progress, can also carry out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), preferably in oxygen-containing atmosphere
Middle progress.
The formed body of aluminium oxide containing halogen according to the present invention, according to specifically used requirement can with variously-shaped, such as：
Spherical, bar shaped, piece shape, bird-nest-shaped or honeycombed, the instantiation of the bar shaped can include but is not limited to：Cloverleaf pattern,
Dish, cylinder and Rasching ring.
The formed body of aluminium oxide containing halogen has abundant pore structure according to the present invention.Measured by mercury injection method, water containing halogen
The pore-size distribution for closing aluminium oxide formed body is in bimodal distribution.Wherein, most probable pore size is respectively 4-20nm (being preferably 6-18nm)
With more than 20nm (such as 20.5-35nm).
The formed body of aluminium oxide containing halogen according to the present invention, this, which contains halogen aluminium oxide formed body, has higher intensity.One
As, the radial direction crushing strength of the formed body of aluminium oxide containing halogen is that more than 10N/mm (such as can be 10- according to the present invention
55N/mm), it is preferably more than 12N/mm (such as can be 12-50N/mm).
According to the sixth aspect of the invention, the present invention provides a kind of preparation method of formed body, this method includes will
Contain halogen described in the composition of hydrated alumina containing halogen or third aspect of the present invention described in the first aspect of the present invention
Hydrated alumina composition is molded, and obtained molding is dried and is optionally roasted.Obtained molding warp
It can be roasted after drying, so as to obtain the formed body of aluminium oxide containing halogen, can not also be roasted, so as to obtain containing halogen
Hydrated alumina formed body.
The shaping, dry and roasting method and the 4th aspect of condition and the present invention and the 5th aspect phase
Together, details are not described herein again.
The aperture of the formed body prepared by the preparation method of the formed body of the present invention is in bimodal distribution.Specifically, by pressure mercury
Method measures, and the pore-size distribution of the formed body of hydrated alumina containing halogen is in bimodal distribution.Wherein, most probable pore size is respectively 4-20nm
(being preferably 5-15nm) and more than 20nm (such as 20.5-35nm, is preferably 21-30nm).
According to the seventh aspect of the present invention, the present invention provides a kind of method system as described in the 6th aspect of the present invention
Standby formed body.The formed body has higher intensity.Usually, prepared as the method described in the 6th aspect of the present invention
The radial direction crushing strength of formed body is more than 10N/mm (such as can be 10-55N/mm), preferably more than 12N/mm (such as can
Think 12-50N/mm).
According to the eighth aspect of the present invention, the present invention provides a kind of production shaping side of hydrated alumina containing halogen
Method, as shown in Fig. 2, this method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
Optionally (2), are handled the first hydrated alumina wet gel using (2-1) or (2-2),
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid
Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel；
(3) by hydrated alumina wet gel and there are at least two protons using the method described in second aspect of the present invention
The compound mixing of acceptor site, obtains the composition of hydrated alumina containing halogen, and the hydrated alumina wet gel is described the
Monohydrate alumina wet gel or the second hydrated alumina wet gel；
(4) composition of hydrated alumina containing halogen is molded, obtains hydrated alumina forming matter containing halogen；
(5) hydrated alumina forming matter containing halogen is dried, obtains the formed body of hydrated alumina containing halogen；
(6) alternatively, at least part formed body of hydrated alumina containing halogen is roasted, obtains aoxidizing containing halogen
Aluminium formed body；
Wherein, this method is additionally included in the operation that mixing halogen contained compound is carried out in step (1) and/or step (2), with
So that the hydrated alumina composition contains halogen contained compound.
Production forming method according to the present invention, mixes institute in second aspect of method and the present invention of halogen contained compound
The method stated is identical with order, is no longer described in detail herein.
In step (1), the alumina hydrate gel solution refers to alumina hydrate gel synthetic reaction obtains, process
Or the solution containing alumina hydrate gel without aging.The alumina hydrate gel solution can be prepared in situ
Alumina hydrate gel solution that is obtaining or coming from the transport of other production scenes.Preferably, the aqua oxidation
Alumina gel solution is the hydrated alumina wet gel solution being prepared in situ.The synthetic method and condition of alumina hydrate gel
Have been carried out being described in detail above, details are not described herein again.
Since the alumina hydrate gel solution that synthetic reaction obtains has an acid-base property, to hydrated alumina in step (1)
Wet gel is washed, and to remove acidic materials and alkaline matter therein, avoids the presence pair of acidic materials and alkaline matter
The adverse effect that alumina hydrate gel produces, while improve the solid content of alumina hydrate gel solution.Described in step (1)
Washing can carry out under normal conditions, as long as can be by the acidic materials and the amount of alkaline matter in alumina hydrate gel solution
Satisfaction is reduced to usually require that.
In step (1), separation of solid and liquid is directed in washing process, washings are extruded, obtain the first aqua oxidation
Aluminium wet gel.The i values of the first hydrated alumina wet gel can be meet the present invention second aspect described in with
The i values of the hydrated alumina wet gel of the compound mixing at least two proton acceptor sites, or higher than of the invention the
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in two aspects.
In one embodiment, the i values of the first hydrated alumina wet gel meet second aspect institute of the present invention
The i values for the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites stated, i.e., described first
The i values of hydrated alumina wet gel are not less than 60%, are preferably not lower than 62%.In this embodiment, first water
The i values for closing aluminium oxide wet gel are preferably not higher than 82%, more preferably not above 80%, are more preferably not higher than
78.5%.Specifically, the i values of the hydrated alumina wet gel can be 60-82%, be preferably 62-80%, more preferably
62-78.5%.
According to the embodiment, the first hydrated alumina wet gel can be sent directly into step (3), and with extremely
The compound mixing in few two proton acceptor sites.This is especially suitable for meeting occasion claimed below：(A) in wash mill
Solid-liquid separating equipment has preferable separating capacity, it is sufficient to which the i values control of the first hydrated alumina wet gel is above-mentioned to meet
Scope；(B) wash mill compact can be set with mixing arrangement so that the discharging of wash mill can be directly entered mixing dress
Put.
According to the embodiment, the first hydrated alumina wet gel can also be sent into step (2), using (2-1)
Handled.This is especially suitable for meeting occasion claimed below：(A) solid-liquid separating equipment in wash mill has preferable
Separating capacity, it is sufficient to control the i values of the first hydrated alumina wet gel to meet above range；(B) wash mill is with mixing
Device compact can not be set, so that the discharging of wash mill can not be directly entered mixing arrangement.
In another embodiment, the i values of the first hydrated alumina wet gel are higher than 82%, can not meet the present invention
The requirement mixed with the compound with least two proton acceptor sites described in second aspect.According to the embodiment,
The first hydrated alumina wet gel is sent into step (2), is handled using (2-1) or (2-2).
The embodiment especially suitable for the solid-liquid separating equipment in wash mill separating capacity or operating condition not
Be enough by the control of the i values of the first hydrated alumina wet gel for meet the occasion of the requirement described in second aspect of the present invention, with
And wash mill and mixing arrangement can not compact setting occasion.
In step (2), the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains second
Hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water, slurries is formed, can so improve aqua oxidation
Aluminium wet gel transports performance.In (2-1), the additive amount of water, which is subject to the slurries to be formed, can meet to transport requirement, Ke Yigen
Made choice according to specific conveying equipment.
The i values for the second hydrated alumina wet gel that step (2) obtains meet described in second aspect of the present invention
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites, i.e., described aqua oxidation
The i values of aluminium wet gel are not less than 60%, are preferably not lower than 62%.The i values of the second hydrated alumina wet gel are preferred
Not higher than 82%, 80% to be more preferably not above, more preferably not higher than 78.5%.Specifically, the aqua oxidation
The i values of aluminium wet gel can be 60-82%, be preferably 62-80%, more preferably 62-78.5%.
As shown in Figures 2 and 3, at least part halogen contained compound can be mixed in step (2).For using (2-1) institute
When the mode stated carries out, as shown in Figures 2 and 3, chemical combination containing halogen can be mixed in dilution operation and/or separation of solid and liquid operation
Thing.
The second water that i values meet above-mentioned requirements can be obtained by the condition of separation of solid and liquid described in rate-determining steps (2)
Close aluminium oxide wet gel.The side of the i values of hydrated alumina wet gel is adjusted by selecting method and its condition of separation of solid and liquid
Method has been carried out being described in detail above, is no longer described in detail herein.
In step (3), using the method described in second aspect of the present invention by the first hydrated alumina wet gel or the
Two hydrated alumina wet gels are with halogen contained compound and the compound with least two proton acceptor sites mixes, so that
Obtain the composition of hydrated alumina containing halogen.It is sent into the first hydrated alumina wet gel and the second hydrated alumina of step (3)
The i values of wet gel meet being mixed with the compound with least two proton acceptor sites described in second aspect of the present invention
The i values of hydrated alumina wet gel.
In step (4), the composition of hydrated alumina containing halogen that step (3) obtains is molded, obtains water containing halogen
Close aluminium oxide molding.The shape of the molding method and molding is referred to hereinbefore retouch on molding correlation
State, details are not described herein again.
In step (5), the hydrated alumina forming matter containing halogen that step (3) obtains is dried, obtains water containing halogen
Close aluminium oxide formed body.Hydrated alumina forming matter is dried to obtain the dried strip of the formed body of hydrated alumina containing halogen
Part, has been carried out being described in detail, details are not described herein again in the method described in the 5th aspect of the present invention.
According to the type of expected formed body, step (6) can be carried out, step (6) can not also be carried out.Carrying out step
(6) when, all hydrated aluminas containing the halogen formed body that can obtain step (5) is sent into step (6), is roasted；
The part formed body of hydrated alumina containing halogen that step (5) can be obtained is sent into step (6), so can at the same time be prepared and be contained
Halogen hydrated alumina formed body and the formed body of aluminium oxide containing halogen.The condition of the roasting is described in the 8th aspect of the present invention
Method in have been carried out being described in detail, details are not described herein again.
According to the ninth aspect of the present invention, the present invention provides a kind of method system as described in the 8th aspect of the present invention
The standby formed body of hydrated alumina containing halogen or the formed body of aluminium oxide containing halogen.
Aoxidized as the formed body of hydrated alumina containing halogen of the method preparation described in the 8th aspect of the present invention and containing halogen
Aluminium formed body has higher intensity.Usually, the footpath of the formed body of hydrated alumina containing halogen and the formed body of aluminium oxide containing halogen
It can be each more than 10N/mm (such as can be 10-55N/mm) to crushing strength, be preferably that more than 12N/mm (such as can be with
For 12-50N/mm).
The method described according to the eighth aspect of the present invention can a kind of hydrated alumina produce formation system in into
OK, which includes alumina hydrate gel production unit, separation of solid and liquid and washing unit, mixed cell, shaping
Unit, drying unit and optional roasting unit,
The alumina hydrate gel solution output port of the alumina hydrate gel production unit and the separation of solid and liquid
And the washing material input port to be separated of washing unit is connected, the solid-phase material output of the separation of solid and liquid and washing unit
Port is connected with the solid-phase material input port of the mixed cell, the mixed material output port of mixed cell with it is described into
The raw material input port of type unit is connected, the material to be dried input port of the drying unit and the forming unit into
Type thing output port is connected, and the dried material of the material input port to be roasted and the drying unit of the roasting unit is defeated
Exit port is connected.
The alumina hydrate gel production unit is used to generate alumina hydrate gel solution by synthetic reaction.Synthesis
The method of alumina hydrate gel can be conventional method, the precipitation method as previously described, Hydrolyze method, kind point-score and quick de-
Water law, is not described in detail herein.
The alumina hydrate gel production unit can use conventional reactor to carry out synthetic reaction, so as to obtain water
Alumina gel solution is closed, this is not particularly limited in the present invention.
The separation of solid and liquid and washing unit are used for the aqua oxidation for exporting the alumina hydrate gel production unit
Alumina gel aqueous solution carries out separation of solid and liquid and washing, obtains hydrated alumina wet gel, the hydrated alumina wet gelValue
Meet the requirement that can be mixed with the compound with least two proton acceptor sites described in second aspect of the present invention.
The separation of solid and liquid and washing unit can use common various methods to carry out separation of solid and liquid and washing, so that
ArriveValue meets to mix desired alumina hydrate gel with the compound with least two proton acceptor sites.The solid-liquid
Separation and washing unit can use conventional equipment for separating liquid from solid, such as：The group of filtration apparatus, centrifugal device or both
Close.When separation of solid and liquid and washing unit include filtration apparatus, the filtration apparatus can be gravity filter device, pressure filtration
One or more kinds of combinations in device and vacuum apparatus.Preferably, the filtration apparatus includes at least pressurization
Filtration apparatus.The instantiation of the pressure filter can include but be not limited to plate and frame type filter-press, band filter
Or both combination.In order to control the hydrated alumina wet gel of acquisitionValue, the separation of solid and liquid and washing unit are also
It can include blow device, isolated solid phase is purged using natural wind or wind with pressure, is taken off so as to improve moisture
The efficiency gone out.The pressure of the wind with pressure can be conventional selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.
The separation of solid and liquid and washing unit can include one or more separation of solid and liquid subelement, preferably at least one
A separation of solid and liquid subelement and last separation of solid and liquid subelement are pressure filter and/or vacuum apparatus, so that
Obtain the solid-phase material (that is, hydrated alumina wet gel) that separation of solid and liquid and washing unit obtainValue can meet the present invention second
The requirement mixed with the compound with least two proton acceptor sites described in a aspect.By adjusting application pressure or
The size of person's vacuum, can be to the hydrated alumina wet gel finally obtainedValue is adjusted.The separation of solid and liquid and wash
When washing unit includes two or more separation of solid and liquid subelement, except last separation of solid and liquid subelement preferably use using pressure as
Outside the solid-liquid separation method of motive force, remaining separation of solid and liquid separation subelement can use pressure filter and/or vacuum
Filtration apparatus, can not also use pressure filter and vacuum apparatus, it is preferred to use pressure filter and/or vacuum
Filtration apparatus.
The separation of solid and liquid and washing unit can use conventional wash mill to wash the solid phase isolated.
It is for instance possible to use washings are sprayed to the solid phase surface isolated by spray equipment.In order to improve washing effect and washing
Efficiency, shearing and/or vibration can be applied to solid phase during the spray or after the completion of spray, by shower water with it is solid
Mix uniformly, the shearing is for example stirred.
On the basis of the trend of alumina hydrate gel material flow, separation of solid and liquid and washing unit are arranged on hydrated alumina
Between gel production unit and mixed cell, the gel solution for alumina hydrate gel production unit to be exported is divided
From obtainingValue meets the hydrated alumina wet gel that mixing requires, and raw material is provided for mixed cell.
On the premise of the alumina hydrate gel met the requirements being provided for mixed cell, from the conveying easy to material
Angle is set out, and in a preferred embodiment, the separation of solid and liquid and washing unit can include washing subelement, dilution
Subelement, conveying subelement and the second separation of solid and liquid subelement,
The washing subelement is used for the alumina hydrate gel for collecting the alumina hydrate gel production unit output
Solid phase in solution is simultaneously washed；
The dilution subelement is used to the solid phase of the washing subelement output being diluted with water, obtains slurries；
The conveying subelement is used to the slurries of the dilution subelement output being sent into the second separation of solid and liquid subelement；
The second separation of solid and liquid subelement is used to the slurries carrying out separation of solid and liquid, and it is wet solidifying to obtain hydrated alumina
Glue.
As shown in Figures 2 and 3, can be in one of washing subelement, dilution subelement and conveying subelement, Liang Zhehuo
Halogen contained compound is added in three.
The conveying subelement can use conventional various conveying devices, such as conveyer belt.The conveying subelement and institute
Stating washing subelement can integrate, such as integrate in one apparatus, so as to be washed during conveying, carry
High efficiency.Such as：Using the conveyer belt with solid-liquid separation function, while spray is set above the solid-phase material of conveyer belt
Shower device, so as to be washed during transporting and separation of solid and liquid.
The mixed cell includes the assistant feeding device that auxiliary agent is added into hydrated alumina wet gel, in the production system
During system operation, the assistant feeding device adds at least into hydrated alumina wet gel has at least two proton acceptor sites
Compound and optional halogen contained compound.
The mixed cell can use conventional mixing arrangement, such as common various mixers, kneader or two
The combination of person.The forming unit can use conventional molding machine, such as：Extrusion device, spraying device, circle rolling device,
Preforming device or two or more combinations.The drying unit can use conventional drying device, and the present invention does not have this
It is particularly limited to.The roasting unit can use conventional calciner, this is also not particularly limited in the present invention.
On the basis of the flow direction of alumina hydrate gel, the production formation system is in separation of solid and liquid and the solid phase of washing unit
Material discharging port is wet by hydrated alumina to being not provided with being enough between the hydrated alumina wet gel input port of mixed cell
The i values of gel are reduced to the dewatering unit of less than 60% (preferably less than 62%).
In the actual production process, mixing can be added on the basis of existing alumina hydrate gel process units
Unit, forming unit, drying unit and roasting unit, production and molding one so as to fulfill alumina hydrate gel
Change.
When producing shaping system production formed body using the hydrated alumina, it may comprise steps of：
(1) will be sent into for the raw material for producing alumina hydrate gel solution in alumina hydrate gel production unit, into
Row reaction, obtains alumina hydrate gel solution；
(2) the alumina hydrate gel solution is sent into progress separation of solid and liquid in separation of solid and liquid and washing unit and obtains water
Close aluminium oxide wet gel；
(3) it is using the method described in second aspect of the present invention that the hydrated alumina is wet in the mixed cell
Gel is mixed with the compound with least two proton acceptor sites in mixed cell, obtains the group of hydrated alumina containing halogen
Compound；
(4) composition of hydrated alumina containing halogen is molded in forming unit, is obtained containing halogen hydration oxygen
Change aluminium molding；
(5) hydrated alumina forming matter containing halogen is dried in drying unit, obtained containing halogen hydration oxygen
Change aluminium formed body；
(6) at least part formed body of hydrated alumina containing halogen is roasted in roasting unit, is aoxidized
Aluminium formed body；
Wherein, the behaviour of halogen contained compound is added in one of step (1), (2) and (3), both or three
Make, so that hydrated alumina composition contains halogen contained compound.
In step (1), the method for preparing alumina hydrate gel solution is described in detail above, herein
No longer it is described in detail.
In step (2), hydrated alumina wet gel that the condition of separation of solid and liquid causesValue meets the present invention second
Requirement described in a aspect, so as to be mixed with the compound with least two proton acceptor sites, obtains and is hydrated containing halogen
Alumina composition.
In step (3), have at least two proton acceptor sites compound additive amount to be prepared it is halogen
Plain hydrated alumina compositionValue can meet subject to previously described requirement.As it was noted above, the aqua oxidation containing halogen
Aluminium composition can contain peptizing agent, can not also contain peptizing agent, i.e., can be wet solidifying to hydrated alumina in step (3)
Peptizing agent is added in glue, peptizing agent can not also be added into hydrated alumina wet gel.In a kind of preferable real of the present invention
Apply in mode, relative to 100 parts by weight hydrated alumina wet gels, the additive amount of the peptizing agent is preferably below 5 parts by weight,
The hydrated alumina wet gel is in terms of hydrated alumina.In a kind of particularly preferred embodiment of the present invention, not to institute
State in hydrated alumina wet gel and add peptizing agent.
Roast described in shaping described in step (4), drying described in step (5) and step (6) and be referred to respectively
Associated description above, details are not described herein again.
The formed body of hydrated alumina containing halogen and the formed body of aluminium oxide containing halogen according to the present invention are particularly suitable as bearing
The carrier of supported catalyst.The loaded catalyst can be it is commonly used in the art it is various can be with hydrated alumina containing halogen
The catalyst of formed body and/or the formed body of aluminium oxide containing halogen as carrier.Preferably, the catalyst is with hydrogenation catalyst
The catalyst of effect.That is, the formed body of hydrated alumina containing halogen and the formed body of aluminium oxide containing halogen are especially suitable according to the present invention
In the carrier as the catalyst acted on hydrogenation catalyst.
According to the tenth aspect of the present invention, the present invention provides a kind of catalyst with hydrogenation catalyst effect, this is urged
Agent contains the hydrogenation active component of carrier and load on the carrier, wherein, the carrier is containing according to the present invention
Halogen hydrated alumina formed body and/or the according to the present invention formed body of aluminium oxide containing halogen.
The hydrogenation active component can be conventional selection.Preferably, the hydrogenation active component is selected from least one the
Group vib metallic element and at least one group VIII metallic element.The group VIII metallic element and the vib metals
Element can be the various elements with hydrogenation catalyst effect commonly used in the art.Preferably, the group VIII metallic element
For cobalt and/or nickel, the vib metals element is molybdenum and/or tungsten.The group VIII metallic element and vib metals
The content of element can make appropriate choice according to the concrete application occasion of catalyst.For example, it is being catalyzed according to the present invention
When agent is used for the hydrotreating of hydrocarbon ils, on the basis of the total amount of the catalyst, the content of the carrier can be 55-94.5 weights
% is measured, is preferably 62-92.5 weight %, more preferably 75-88 weight %；In terms of oxide, the group VIII metallic element
Content can be 0.5-10 weight %, be preferably 1.5-8 weight %, more preferably 2-5 weight %；It is described in terms of oxide
The content of vib metals element can be 5-35 weight %, be preferably 6-30 weight %, more preferably 10-20 weight %.
According to the eleventh aspect of the present invention, the present invention provides a kind of system of the catalyst with hydrogenation catalyst effect
Preparation Method, this method are included in supported on carriers hydrogenation active component, wherein, the carrier is the water containing halogen according to the present invention
Close aluminium oxide formed body and/or the formed body of aluminium oxide containing halogen.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, preferably further includes and prepares formed body
Step, the formed body are the formed body of hydrated alumina containing halogen and/or the formed body of aluminium oxide containing halogen.In this step, adopt
Formed body is prepared with the method described in the 6th aspect of the present invention or the 8th aspect.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, the hydrogenation active component can be
Conventional selection.Preferably, the hydrogenation active component is vib metals element and group VIII metallic element.Described
Group VIII metal element is preferably cobalt and/or nickel, and the vib metals element is preferably molybdenum and/or tungsten.The hydrogenation activity
Load capacity of the component on carrier can make appropriate choice according to the concrete application occasion of catalyst.For example, in preparation
Catalyst be used for hydrocarbon ils hydrotreating when, on the basis of the total amount of the catalyst of preparation, the group VIII metallic element and
The load capacity of vib metals element on the carrier causes group VIII metallic element and in the catalyst that finally prepares
The content of group vib metallic element disclosure satisfy that the requirement described in the tenth aspect of the present invention.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can use commonly used in the art each
Kind method loads the hydrogenation active component on the carrier, such as：Dipping.The dipping can be that saturation impregnates,
It can be excessive dipping.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be at the same time by hydrogenation active component
Load on the carrier, by several times can also load hydrogenation active component on the carrier.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be in condition commonly used in the art
The lower carrier for obtaining dipping is dried and optionally roasts.Usually, the condition of the drying includes：Temperature can be
100-200 DEG C, be preferably 120-150 DEG C；When duration can be 1-15 small, when being preferably 2-10 small, more preferably 2-4 is small
When.The condition of the roasting includes：Temperature can be 350-550 DEG C, be preferably 400-500 DEG C；Duration can be that 1-8 is small
When, when being preferably 2-6 small, when more preferably 2-3 is small.
According to the twelfth aspect of the present invention, the present invention provides a kind of hydrotreating method, this method, which is included in, to be added
Under hydrogen treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, it is described to have what hydrogenation catalyst acted on
What catalyst was prepared for the catalyst described in the tenth aspect of the present invention or as the method described in the tenth one side of the invention
Catalyst.
The hydrotreating method of the present invention is not particularly limited for the species and hydroprocessing condition of hydrocarbon ils, can be this
The conventional selection in field.Preferably, the hydrocarbon ils can be various heavy mineral oil or heavy mineral oil, such as depitching again
It is more than one or both of oil, reduced crude, decompression residuum.The condition of the hydrotreating includes：Temperature can be 300-
380℃；In terms of gauge pressure, pressure can be 4-15MPa；When volume space velocity can be 1-3 small during the liquid of hydrocarbon ils-1；Hydrogen to oil volume ratio
Can be 200-1000.
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, the radial direction of the molding prepared using method measure specified in RIPP 25-90
Crushing strength.
In following embodiments and comparative example, measured using following methodsValue：By 10g hydrated aluminas composition at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
In following embodiments and comparative example, i values are measured using following methods：By 10g hydrated aluminas wet gel at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
In following embodiments and comparative example, the water absorption rate of the formed body prepared using following methods measure：By shaping to be measured
Then body is sieved with 40 the polished standard screens when 120 DEG C of dryings 4 are small, weighs 20g oversizes and (be denoted as sample to be tested
w3), sample to be tested 50g deionized waters are soaked 30 minutes, after filtering, solid phase are drained 5 minutes, what then weighing drained consolidates
The weight of phase (is denoted as w4), calculate water absorption rate with the following formula：
In following embodiments and comparative example, using Kang Ta companies of U.S. Poremaster33 instruments, with reference to GB/T
Mercury injection method specified in 21650.1-2008 measures most probable pore size.
In following embodiments and comparative example, butt measures sample to be tested when 600 DEG C of roastings 4 are small, for roasting
The percentage of sample quality before rear sample quality and roasting.
In following embodiments and comparative example, using the 3271 type x-ray fluorescence light of Japanese mechanics electric machine industry Co., Ltd.
Spectrometer, the composition of method measure catalyst with reference to specified in Petrochemical Engineering Analysis method RIPP133-90.
Embodiment 1-8 is used to illustrate the composition of hydrated alumina containing halogen, formed body of the present invention and preparation method thereof.
Embodiment 1
The hydrated alumina wet gel used in the present embodiment is that (sodium metaaluminate-aluminum sulfate method, is derived from Chinese stone by acid system
Change Chang Ling branch company) prepare alumina hydrate gel solution washed and be obtained by filtration boehmite wet cake (will
Wet cake numbering is SLB-1), after measured, the i values of the wet cake are 78.2%.
(1) wet cake that 200g numberings are SLB-1 is placed in beaker, then adds 0.6g NH4F, 5g methylcellulose
(content of galactomannans is 80 weight %, purchased from Beijing for (being purchased from Zhejiang Hai Shen Chemical Co., Ltd.s) and 3g sesbania powders
Learn Reagent Company), using mechanical agitator stirring after ten minutes, obtained mixture is hydrated alumina containing halogen of the invention
Composition, its nature parameters are listed in table 1.
(2) composition of hydrated alumina containing halogen for preparing step (1) is in F-26 types double screw extruder (south China science and engineering
On university's science and technology industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.5mm.Wherein, extrusion process is smooth, squeezes
Go out thing surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
The dry bar HT-1 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 580 DEG C, air atmosphere 6 it is small when, obtain
To the bar OT-1 of alumina dry containing halogen, its nature parameters is listed in table 1.
Embodiment 2
The bar of alumina dry containing halogen is prepared using method same as Example 1, unlike, in step (4), through step
(3) prepare the dry bar of hydrated alumina roasted in 980 DEG C, air atmosphere 3 it is small when, obtain the bar OT-2 of alumina dry containing halogen,
Its nature parameters is listed in table 1.
Embodiment 3
Formed body is prepared using method same as Example 1, unlike, without using sesbania powder, methyl in step (2)
The dosage of cellulose is 7.4g, the dry bar HT-3 of the composition of hydrated alumina containing halogen, hydrated alumina containing halogen of preparation and
The property of the bar of alumina dry containing halogen OT-3 is listed in table 1.
Embodiment 4
Formed body is prepared using method same as Example 1, unlike, without using methylcellulose in step (2),
The dosage of sesbania powder is 9.3g, the dry bar HT-4 of the composition of hydrated alumina containing halogen, hydrated alumina containing halogen of preparation and
The property of the bar of alumina dry containing halogen OT-4 is listed in table 1.
Embodiment 5
Formed body is prepared using method same as Example 1, unlike, in step (2), in addition methylcellulose
During with sesbania powder, 2.6g nitric acid (HNO is also added3Content be 65 weight %), the composition of hydrated alumina containing halogen of preparation,
The property of the dry bar HT-5 of hydrated alumina containing halogen and the bar of alumina dry containing halogen OT-5 are listed in table 1.
Comparative example 1
(1) by 500g numberings be SLB-1 wet cake in 82 DEG C, air atmosphere it is dry 3 it is small when, obtain boehmite
Powder, the i values of the boehmite powder are 51%.The boehmite powder (is placed in environment temperature (25-30 DEG C) and sealing condition
In sealed plastic bag) under place 72 it is small when, do not detected after placement and form gibbsite.
(2) by boehmite powder prepared by 89g steps (1) and 0.6g NH4After F mixing, in F-26 type twin-screw extrusions
On machine extrusion is carried out using the circular orifice of Ф 2.0mm.Wherein, extruder caloric value is larger during extrusion (shows as banded extruder machine
Body is hot, has a large amount of hot gas to emerge), and extruder Frequent trip during extrusion, extrudate surface are jagged.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
The dry bar DHT-1 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 580 DEG C, air atmosphere 6 it is small when, obtain
To the bar DOT-1 of alumina dry containing halogen, its nature parameters is listed in table 1.
Comparative example 2
(1) by the wet cake that 500g numberings are SLB-1 at a temperature of 90 DEG C, in air atmosphere it is dry 4 it is small when, intended
Boehmite powder, the i values of the boehmite powder are 38%.The boehmite powder is in environment temperature (25-30 DEG C) and closes
When placement 72 is small under condition (being placed in sealed plastic bag), is not detected after placement and form gibbsite.
(2) boehmite powder prepared by 70g steps (1) is placed in beaker, adds 0.6g NH4F, 5g Methyl celluloses
Plain (with embodiment 1) and 3g sesbania powders (with embodiment 1), using mechanical agitator stirring after ten minutes, obtain boehmite
Composition.
(3) the boehmite composition for preparing step (2) is in F-26 types double screw extruder (section of South China Science ＆ Engineering University
On skill industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.5mm.Wherein, extruder is frequently jumped during extrusion
Lock, extrudate surface are smooth.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
The dry bar DHT-2 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare the dry bar of hydrated alumina containing halogen roasted in 580 DEG C, air atmosphere 6 it is small when, obtain
To the bar DOT-2 of alumina dry containing halogen, its nature parameters is listed in table 1.
Comparative example 3
(1) 70g is placed in beaker using boehmite powder prepared by the method identical with 2 step of comparative example (1), added
Enter 0.6g NH4F, 5g methylcellulose (with embodiment 1), 3g sesbania powders (with embodiment 1) and 5.2g nitric acid (HNO3Concentration be
65 weight %), using mechanical agitator stirring after ten minutes, obtain boehmite composition.
(2) the boehmite composition for preparing step (1) is in F-26 types double screw extruder (section of South China Science ＆ Engineering University
On skill industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.5mm.Wherein, extrusion process is smooth, extrudate table
Face is smooth.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
The dry bar DHT-3 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 580 DEG C, air atmosphere 6 it is small when, obtain
To the bar DOT-3 of alumina dry containing halogen, its nature parameters is listed in table 1.
Comparative example 4
The composition of hydrated alumina containing halogen is prepared using method same as Example 1, unlike, without using methyl
Cellulose and sesbania powder, but with 7.4g paraffin.As a result the composition of hydrated alumina containing halogen prepared can not be extruded into
Type.
Comparative example 5
The composition of hydrated alumina containing halogen is prepared using method same as Example 1, unlike, without using hydroxyl second
Ylmethyl cellulose and sesbania powder, but with 7.4g wood powders.As a result the composition of hydrated alumina containing halogen prepared can not carry out
Extrusion molding.
Comparative example 6
Will number be LB-1 wet cake be sent directly into F-26 type double screw extruders utilize Ф 1.5mm dish-shaped orifice plate
Extrusion is carried out, as a result can not carry out extrusion molding.
Comparative example 7
(1) 44g boehmites dry glue powder (is purchased from Sinopec Chang Ling branch company, butt 0.75, in environment temperature
When placement 72 is small under (25-30 DEG C) and sealing condition (being placed in sealed plastic bag), is not detected after placement and form three water
Aluminium oxide), add 0.6g NH4F, 5g methylcellulose (with embodiment 1), 3g sesbania powders (with embodiment 1) and 5.2g nitric acid
(HNO3Concentration be 65 weight %) aqueous solution 320mL, using mechanical agitator stirring after ten minutes, obtain boehmite
Composition.
(2) the boehmite composition for preparing step (1) utilizes Ф 1.5mm's on F-26 type double screw extruders
Circular orifice carries out extrusion.Wherein, extrusion process is smooth, and extrudate surface is smooth.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
The dry bar DHT-4 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 580 DEG C, air atmosphere 6 it is small when, obtain
To the bar DOT-4 of alumina dry containing halogen, its nature parameters is listed in table 1.
Embodiment 6
(1) wet cake that 5kg numberings are SLB-1 (is purchased from Zhejiang Hai Shen with 500g deionized waters, 33g methylcellulose
Chemical Co., Ltd.) and 20g sesbania powders (content of galactomannans is 80 weight %, purchased from Beijing chemical reagents corporation) it is mixed
Mashing 1 minute is closed, then obtained slurries are sent into plate and frame type filter-press, the pressure of sheet frame is adjusted to 0.7MPa and is kept
15 minutes, the wet cake that sheet frame pressure release obtains.
(2) by wet cake prepared by step (1) and 16g NH4Cl is stirred evenly with mechanical agitator, obtains the present invention's
The composition of hydrated alumina containing halogen, its nature parameters are listed in table 1.
The composition of hydrated alumina containing halogen is obtained utilizing on F-26 type double screw extruders to the dish-shaped hole of Ф 1.5mm
Plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere,
The dry bar HT-6 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 600 DEG C, air atmosphere 3 it is small when, obtain
To the bar OT-6 of alumina dry containing halogen, its nature parameters is listed in table 1.
Embodiment 7
The hydrated alumina wet gel used in the present embodiment is by CO2Method (sodium aluminate-CO2Method, is derived from Shanxi Province Shan County
Emerging great catalyst new material Co., Ltd) the alumina hydrate gel solution thin water aluminium of plan that is washed and be obtained by filtration for preparing
Stone wet cake (being SLB-2 by wet cake numbering), after measured, the i values of the wet cake are 65.3%.
(1) wet cake that 1000g numberings are SLB-2 is placed in beaker, then adds 4g NH4Cl, 15g Methyl cellulose
(content of galactomannans is 80 weight %, purchased from Beijing for plain (being purchased from Zhejiang Hai Shen Chemical Co., Ltd.s) and 20g sesbania powders
Chemical reagents corporation), using mechanical agitator stirring after ten minutes, obtained mixture is aqua oxidation containing halogen of the invention
Aluminium composition, its nature parameters are listed in table 1.
(2) composition of hydrated alumina containing halogen prepared by step (1) is utilized into Ф on F-26 type double screw extruders
The dish-shaped orifice plate of 2.4mm carries out extrusion, and extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 5mm, when by wet bar, drying 3 is small in 140 DEG C, air atmosphere,
The dry bar HT-7 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare the dry bar of hydrated alumina containing halogen roasted in 560 DEG C, air atmosphere 4 it is small when, obtain
To the bar OT-7 of alumina dry containing halogen, its nature parameters is listed in table 1.
Embodiment 8
(1) wet cake that 5kg numberings are SLB-1 is mixed with beating 1 minute with 700g deionized waters, the slurry that then will be obtained
Liquid is sent into plate and frame type filter-press, and the pressure of sheet frame is adjusted to 0.5MPa and is kept for 3 minutes, then with the wind with pressure of 0.5MPa
The filter cake in sheet frame is purged after 3 minutes, sheet frame pressure release obtains wet cake (numbering LB-5).After measured, numbering is the wet of LB-5
The i values of filter cake are 75 weight %.
(2) wet cake that 1000g numberings are LB-5 is placed in beaker, adds 14.5g NH4F, 16g hydroxypropyl methyls are fine
(content of galactomannans is 85 weight %, purchased from north for dimension plain (being purchased from Zhejiang Hai Shen Chemical Co., Ltd.s) and 20g sesbania powders
Capital chemical reagents corporation), using mechanical agitator stirring after ten minutes, obtain the combination of hydrated alumina containing halogen of the present invention
Thing, its nature parameters are listed in table 1.
(3) composition of hydrated alumina containing halogen prepared by step (2) is utilized into Ф on F-26 type double screw extruders
The circular orifice of 3.0mm carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere,
The dry bar HT-8 of hydrated alumina containing halogen is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare the dry bar of hydrated alumina containing halogen roasted in 950 DEG C, air atmosphere 2.5 it is small when,
The bar OT-8 of alumina dry containing halogen is obtained, its nature parameters is listed in table 1.
Table 1
1：When placement 72 is small under environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag), after placement
The content of gibbsite in composition is compared with the increase rate before placement.
2：Aperture is Unimodal Distribution
Embodiment 1-8's as a result, it was confirmed that the present invention by hydrated alumina wet gel without being dried to dry glue powder or partial desiccation
Rubber powder, but mix, obtain directly with halogen contained compound and with the compound at least two proton acceptor sites
Mixture is used directly for being molded, and obtained formed body has the intensity of higher, so as to avoid it is existing with dry glue powder or
Existing operating environment is severe when the semiarid rubber powder of person prepares formed body as starting material, high energy consumption and the formed body prepared
The problem of intensity is not high.Also, a kind of hydrated alumina, which is used only, in hydrated alumina composition according to the present invention to prepare
Aperture is the formed body of bimodal distribution.
EXPERIMENTAL EXAMPLE 1-8 is used to illustrate the catalyst and its preparation side according to the present invention with hydrogenation catalyst effect
Method.
EXPERIMENTAL EXAMPLE 1
(1) molybdenum oxide and basic cobaltous carbonate are disperseed in deionized water, to be configured to maceration extract, wherein, MoO3Concentration
For 162.4g/L, the concentration of basic cobaltous carbonate is counted as 39.2g/L using CoO.Obtained maceration extract is used into saturation impregnation
The dry bar of hydrated alumina containing halogen prepared by the embodiment 1 as carrier, when dip time is 5 small.Obtained mixing will be impregnated
After thing is when 125 DEG C of dryings 3 are small, when 420 DEG C of roastings 4 are small, the catalyst CH-1 of the present invention is obtained.Measured and be catalyzed using XRF
The composition of agent, is as a result shown in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, MoO3Concentration be 150.5g/L, with
The concentration of CoO meter basic cobaltous carbonates is 36.3g/L, and carrier is the bar of alumina dry containing halogen prepared by embodiment 1, so as to obtain this
The catalyst CO-1 of invention.The composition of catalyst is measured using XRF, as a result shown in table 3.
EXPERIMENTAL EXAMPLE 2
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, without (1), and in (2), MoO3Concentration
For 154.2g/L, the concentration of basic cobaltous carbonate is counted as 37.2g/L using CoO, carrier is alumina dry containing halogen prepared by embodiment 2
Bar, obtains the catalyst CO-2 of the present invention.The composition of catalyst is measured using XRF, as a result shown in table 3.
EXPERIMENTAL EXAMPLE 3
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike：(1) in, MoO3Concentration be
156.9g/L, the concentration of basic cobaltous carbonate is counted as 37.9g/L using CoO, and carrier is hydrated alumina containing halogen prepared by embodiment 3
Dry bar, obtains the catalyst CH-3 of the present invention.Using the composition of XRF measure catalyst, as a result it is shown in table 2；
(2) in, MoO3Concentration be 143.4g/L, the concentration of basic cobaltous carbonate is counted as 34.6g/L using CoO, carrier is real
The bar of alumina dry containing halogen of the preparation of example 3 is applied, obtains the catalyst CO-3 of the present invention.Using the composition of XRF measure catalyst, knot
Fruit is shown in table 3.
EXPERIMENTAL EXAMPLE 4
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike：(1) in, MoO3Concentration be
173.2g/L, the concentration of basic cobaltous carbonate is counted as 41.8g/L using CoO, and carrier is hydrated alumina containing halogen prepared by embodiment 4
Dry bar, obtains the catalyst CH-4 of the present invention.Using the composition of XRF measure catalyst, as a result it is shown in table 2；
(2) in, MoO3Concentration be 187.3g/L, the concentration of basic cobaltous carbonate is counted as 45.2g/L using CoO, carrier is real
The bar of alumina dry containing halogen of the preparation of example 4 is applied, obtains the catalyst CO-4 of the present invention.Using the composition of XRF measure catalyst, knot
Fruit is shown in table 3.
EXPERIMENTAL EXAMPLE 5
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike：(1) in, carrier is made for embodiment 5
The dry bar of standby hydrated alumina containing halogen, as a result in dipping process recurring structure cave in, the phenomenon of dusting；
(2) in, MoO3Concentration be 159.6g/L, the concentration of basic cobaltous carbonate is counted as 38.5g/L using CoO, carrier is real
The bar of alumina dry containing halogen of the preparation of example 5 is applied, obtains the catalyst CO-5 of the present invention.Using the composition of XRF measure catalyst, knot
Fruit is shown in table 3.
Experimental comparison's example 1
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike：(1) in, carrier is made for comparative example 7
The dry bar of standby hydrated alumina containing halogen, as a result in dipping process recurring structure cave in, the phenomenon of dusting；
(2) in, MoO3Concentration be 189.2g/L, the concentration of basic cobaltous carbonate is counted as 45.7g/L using CoO, carrier for pair
The bar of alumina dry containing halogen prepared by ratio 7, obtains catalyst DCO-1.Using the composition of XRF measure catalyst, as a result in table 3
In show.
EXPERIMENTAL EXAMPLE 6
(1) basic nickel carbonate and molybdenum oxide are disperseed in deionized water, to be configured to maceration extract, wherein, MoO3Concentration
For 180.0g/L, the concentration of basic nickel carbonate is counted as 43.4g/L using NiO.Obtained maceration extract is used into saturation impregnation
The dry bar of hydrated alumina containing halogen prepared by the embodiment 6 as carrier, when dip time is 3 small.Obtained mixing will be impregnated
After thing is when 120 DEG C of dryings 5 are small, when 450 DEG C of roastings 4 are small, the catalyst CH-6 of the present invention is obtained.Measured and be catalyzed using XRF
The composition of agent, is as a result shown in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, MoO3Concentration be 187.3g/L, with
The concentration of NiO meter basic nickel carbonates is 45.2g/L, and carrier is the bar of alumina dry containing halogen prepared by embodiment 6, so as to obtain this
The catalyst CO-6 of invention.The composition of catalyst is measured using XRF, as a result shown in table 3.
EXPERIMENTAL EXAMPLE 7
(1) basic nickel carbonate and molybdenum oxide are disperseed in deionized water, to be configured to maceration extract, wherein, MoO3Concentration
For 120.6g/L, the concentration of basic nickel carbonate is counted as 28.7g/L using NiO.Obtained maceration extract is used into saturation impregnation
The dry bar of hydrated alumina containing halogen prepared by the embodiment 7 as carrier, when dip time is 6 small.Obtained mixing will be impregnated
After thing is when 140 DEG C of dryings 3 are small, when 500 DEG C of roastings 3 are small, the catalyst CH-7 of the present invention is obtained.Measured and be catalyzed using XRF
The composition of agent, is as a result shown in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, MoO3Concentration be 111.0g/L, with
The concentration of NiO meter basic nickel carbonates is 26.4g/L, and carrier is the bar of alumina dry containing halogen prepared by embodiment 7, so as to obtain this
The catalyst CO-7 of invention.The composition of catalyst is measured using XRF, as a result shown in table 3.
EXPERIMENTAL EXAMPLE 8
(1) basic nickel carbonate and ammonium molybdate are disperseed in deionized water, to be configured to maceration extract, wherein, MoO3Concentration
For 206.1g/L, the concentration of basic nickel carbonate is counted as 49.2g/L using NiO.Obtained maceration extract is used into saturation impregnation
The dry bar of hydrated alumina containing halogen prepared by the embodiment 8 as carrier, when dip time is 8 small.Obtained mixing will be impregnated
After thing is when 140 DEG C of dryings 3 are small, when 480 DEG C of roastings 4 are small, the catalyst CH-8 of the present invention is obtained.Measured and be catalyzed using XRF
The composition of agent, is as a result shown in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, MoO3Concentration be 217.2g/L, with
The concentration of NiO meter basic nickel carbonates is 51.9g/L, and carrier is the bar of alumina dry containing halogen prepared by embodiment 8, so as to obtain this
The catalyst CO-8 of invention.The composition of catalyst is measured using XRF, as a result shown in table 3.
Table 2
Table 3
Testing example 1-8 is used to illustrate hydrotreating method according to the present invention.
Testing example 1-8
The catalytic performance of the EXPERIMENTAL EXAMPLE 1-8 catalyst prepared is evaluated using following methods, experimental result exists
Listed in table 4.
The feedstock oil used is the light reduced crude of Xi Taisha, and the mass content of its nickel is 11.7ppm, and the mass content of vanadium is
31.7ppm, sulfur content are 3.5 weight %, and nitrogen content is 0.21 weight %, and carbon residue is 11.7 weight %.
The particle of catalyst breakage into diameter 2-3mm are fitted into reactor, feedstock oil is passed through and is reacted, wherein, instead
It is 380 DEG C, hydrogen dividing potential drop 14MPa to answer temperature, and the volume space velocity of feedstock oil is 2h-1。
The removal efficiency of impurity is calculated according to the following formula：
Test comparison example 1
The catalytic performance of the catalyst prepared respectively to Experimental comparison's example 1 using the method identical with testing example 1-8
Evaluated, experimental result is listed in table 4.
Table 4
Testing example 1-8's as a result, it was confirmed that with the formed body of hydrated alumina containing halogen according to the present invention and aluminium oxide
The catalyst that formed body is prepared as carrier, shows the catalytic activity of higher in hydrocarbon oil hydrogenation processing.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (40)
1. a kind of composition of hydrated alumina containing halogen, said composition contains hydrated alumina, halogen contained compound and with extremely
The compound in few two proton acceptor sites,
The compositionIt is worth for 1.8-5, it is describedValue is measured using following methods：By composition described in 10g at 120 DEG C in sky
It is 240 minutes dry in gas atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
2. composition according to claim 1, wherein, it is describedIt is worth for 1.85-4, preferably 1.9-3.5.
3. composition according to claim 1 or 2, wherein, relative to hydrated alumina described in 100 parts by weight, the tool
The content for having the compound at least two proton acceptor sites is 1-25 parts by weight, is preferably 3-22 parts by weight, more preferably 4-
20 parts by weight.
4. according to the composition described in any one in claim 1-3, wherein, it is described that there are at least two proton acceptor sites
Compound in, proton acceptor site is can form more than one or both of F, O and N of hydrogen bond with water；
Preferably, the compound with least two proton acceptor sites is the compound containing hydroxyl in molecular structure；
It is highly preferred that the compound with least two proton acceptor sites is polyhydroxy organic compound；
It is further preferred that the compound with least two proton acceptor sites is polysaccharide and/or the etherate of polysaccharide；
It is further preferred that the compound with least two proton acceptor sites is galactan, mannosan, half
More than one or both of newborn mannosan and cellulose ether, the cellulose ether is preferably methylcellulose, ethoxy fibre
It is more than one or both of dimension element and hydroxypropyl cellulose；
It is particularly preferred that the compound with least two proton acceptor sites is galactomannans and cellulose ether,
Preferably, on the basis of the total amount of the compound with least two proton acceptor sites, the galactomannans
Content is 10-70 weight %, is preferably 15-68 weight %, more preferably 20-65 weight %, more preferably 25-60 weights
% is measured, is still more preferably 30-55 weight %；The content of the cellulose ether is 30-90 weight %, is preferably 32-85 weights
%, more preferably 35-80 weight %, more preferably 40-75 weight % are measured, is still more preferably 45-70 weight %.
5. according to the composition described in any one in claim 1-4, wherein, in said composition, relative to 100 parts by weight water
Aluminium oxide is closed, the content of the halogen contained compound is 0.1-10 parts by weight, is preferably 0.5-5 parts by weight, described containing halogenated
Compound is in terms of halogens.
6. according to the composition described in any one in claim 1-5, wherein, the halogens in the halogen contained compound
For fluorine, chlorine or iodine；
Preferably, the halogen contained compound is one kind being preferably selected from ammonium fluoride, ammonium chloride and ammonium iodide selected from ammonium halide
It is or two or more.
7. according to the composition described in any one in claim 1-6, wherein, the hydrated alumina, which contains, intends thin water aluminium
Stone；
Preferably, the hydrated alumina is boehmite.
8. composition according to claim 7, wherein, the composition is placed 72 under environment temperature and sealing condition
Hour, the content of the gibbsite in composition after placement is higher than containing for the gibbsite in the composition before placing
Amount；
Preferably, on the basis of the total amount of the content of the gibbsite in the composition before placement, in the composition after placement
Gibbsite content at least improve 0.5%；
It is highly preferred that on the basis of the total amount of the content of the gibbsite in the composition before placement, the composition after placement
In the content of gibbsite at least improve 1%, preferably improve 1.1% to 2%.
9. according to the composition described in any one in claim 1-8, wherein, the hydrated alumina is directed to hydration
Aluminium oxide wet gel.
10. according to the composition described in any one in claim 1-9, wherein, the composition is free of peptizing agent.
11. a kind of preparation method of the composition of hydrated alumina containing halogen, this method includes will be each in a kind of feedstock composition
Component mixes, and obtains the hydrated alumina composition, the feedstock composition contains hydrated alumina wet gel, containing halogenated
Compound and the compound with least two proton acceptor sites, the i values of the hydrated alumina wet gel for not less than
60%, the dosage of the compound with least two proton acceptor sites is so that the composition finally preparedIt is worth and is
1.8-5
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will be through dry
The quality of dry composition is denoted as w1, calculated using Formulas IValue,
12. according to the method for claim 11, wherein, the use of the compound with least two proton acceptor sites
Amount causes the hydrated alumina composition preparedIt is worth for 1.85-4, preferably 1.9-3.5.
13. the method according to claim 11 or 12, wherein, the i values of the hydrated alumina wet gel be not less than
62%；
Preferably, the i values of the hydrated alumina wet gel are not higher than 82%, are preferably not higher than 80%, more preferably not
Higher than 78.5%；
It is highly preferred that the i values of the hydrated alumina wet gel are 60-82%, and it is preferably 62-80%, more preferably 62-
78.5%.
14. according to the method described in any one in claim 11-13, wherein, the hydrated alumina wet gel be without
Go through the hydrated alumina wet gel for the dehydration for making its i value be less than 60%.
15. according to the method described in any one in claim 11-14, wherein, the hydrated alumina wet gel is near
After a kind of few alumina hydrate gel solution alternatively carries out aging, obtained from carrying out washing and separation of solid and liquid；
Preferably, the alumina hydrate gel solution is using one kind in the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method
Or two or more methods are prepared.
16. according to the method described in any one in claim 11-15, wherein, the feedstock composition is free of peptizing agent.
17. according to the method described in any one in claim 11-16, wherein, it is described that there are at least two proton acceptor positions
In the compound of point, proton acceptor site is to be formed with water more than one or both of F, O and N of hydrogen bond；
Preferably, the compound with least two proton acceptor sites is the compound containing hydroxyl in molecular structure；
It is highly preferred that the compound with least two proton acceptor sites is polyhydroxy organic compound；
It is further preferred that the compound with least two proton acceptor sites is polysaccharide and/or the etherate of polysaccharide；
It is further preferred that the compound with least two proton acceptor sites is galactan, mannosan, half
More than one or both of newborn mannosan and cellulose ether, the cellulose ether is preferably methylcellulose, ethoxy fibre
It is more than one or both of dimension element and hydroxypropyl cellulose；
It is particularly preferred that the compound with least two proton acceptor sites is galactomannans and cellulose ether,
Preferably, on the basis of the total amount of the compound with least two proton acceptor sites, the galactomannans
Content is 10-70 weight %, is preferably 15-68 weight %, more preferably 20-65 weight %, more preferably 25-60 weights
% is measured, is still more preferably 30-55 weight %；The content of the cellulose ether is 30-90 weight %, is preferably 32-85 weights
%, more preferably 35-80 weight %, more preferably 40-75 weight % are measured, is still more preferably 45-70 weight %.
18. according to the method described in any one in claim 11-17, wherein, chemical combination containing halogen in the raw mixture
The content of thing causes in the hydrated alumina composition of preparation, relative to 100 parts by weight hydrated aluminas, the chemical combination containing halogen
The content of thing is 0.1-10 parts by weight, is preferably 0.5-5 parts by weight, the halogen contained compound is in terms of halogens.
19. according to the method described in any one in claim 11-18, wherein, it is wet relative to 100 parts by weight hydrated aluminas
Gel, the dosage of the compound with least two proton acceptor sites is 1-25 parts by weight, is preferably 3-22 parts by weight,
More preferably 4-20 parts by weight, the hydrated alumina wet gel is in terms of hydrated alumina.
20. according to the method described in any one in claim 11-19, wherein, the halogen member in the halogen contained compound
Element is fluorine, chlorine or iodine；
Preferably, the halogen contained compound is one kind being preferably selected from ammonium fluoride, ammonium chloride and ammonium iodide selected from ammonium halide
It is or two or more.
21. according to the method described in any one in claim 11-20, wherein, the method for the mixing for stirring and/or is pinched
Close.
22. the composition of hydrated alumina containing halogen prepared by a kind of method in 11-21 as claim described in any one.
23. a kind of formed body of hydrated alumina containing halogen, this contains halogen hydrated alumina formed body by appointing in claim 1-10
The composition of hydrated alumina containing halogen described in meaning one or the composition of hydrated alumina containing halogen described in claim 22
Formed.
24. the formed body of hydrated alumina containing halogen according to claim 23, wherein, measured by mercury injection method, this contains halogen
The pore-size distribution of hydrated alumina formed body is in bimodal distribution, and most probable pore size is respectively 4-20nm and more than 20nm.
25. a kind of formed body of aluminium oxide containing halogen, the aluminium oxide formed body is as containing described in any one in claim 1-10
The composition of hydrated alumina containing halogen described in halogen hydrated alumina composition or claim 22 is formed.
26. the formed body of aluminium oxide containing halogen according to claim 25, wherein, measured by mercury injection method, this contains halogen hydration
The pore-size distribution of aluminium oxide formed body is in bimodal distribution, and most probable pore size is respectively 4-20nm and more than 20nm.
27. a kind of preparation method of formed body, this method includes the water containing halogen described in by any one in claim 1-10
The composition of hydrated alumina containing halogen described in conjunction alumina composition or claim 22 is molded, the shaping that will be obtained
Thing is dried and optionally roasts.
A kind of 28. formed body prepared by method as described in claim 27.
29. the formed body of hydrated alumina containing halogen, 25 and of claim according to any one in claim 23 and 24
The formed body of aluminium oxide containing halogen described in any one, the formed body described in claim 28 in 26, wherein, the radial direction of formed body
Crushing strength is 10-55N/mm, is preferably 12-50N/mm.
30. a kind of production forming method of hydrated alumina containing halogen, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and separation of solid and liquid,
The first hydrated alumina wet gel is obtained, the condition of the separation of solid and liquid causes the i values of the first hydrated alumina wet gel
For not less than 60%, be preferably not lower than 62%, more preferably not above 82%, more preferably not higher than 80%, more into
One step is preferably not higher than 78.5%；
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(2) use the method in claim 11-21 described in any one by the first hydrated alumina wet gel with having
The compound mixing at least two proton acceptor sites, obtains hydrated alumina composition；
(3) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(4) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(5) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixing halogen contained compound is carried out in step (1) and/or step (2), so that
The hydrated alumina composition contains halogen contained compound.
31. a kind of production forming method of hydrated alumina containing halogen, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the first water
Close aluminium oxide wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), it is wet obtains the second hydrated alumina
Gel,
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid point
From obtaining the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are not low
It is further excellent more preferably not higher than 80% in 60%, preferably not lower than 62%, more preferably not above 82%
Elect as not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(3) use the method in claim 11-21 described in any one by the second hydrated alumina wet gel with having at least
The compound mixing in two proton acceptor sites, obtains hydrated alumina composition；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixing halogen contained compound is carried out in step (1) and/or step (2), so that
The hydrated alumina composition contains halogen contained compound.
32. the method according to claim 30 or 31, wherein, the separation of solid and liquid carries out one or more times, at least most
A separation of solid and liquid is pressure filtration and/or vacuum filter afterwards.
33. according to the method described in any one in claim 30-32, wherein, the alumina hydrate gel solution is warp
Cross aging or without aging by more than the precipitation method, Hydrolyze method, kind one or both of point-score and rapid dehydration method
Method is prepared.
34. formed body prepared by a kind of method in claim 30-33 described in any one.
35. formed body according to claim 34, wherein, the radial direction crushing strength of the formed body is 10-55N/mm, preferably
For 12-50N/mm.
36. it is a kind of with hydrogenation catalyst effect catalyst, the catalyst contain carrier and load on the carrier plus
Hydrogen activity component, wherein, the carrier be hydrated alumina containing halogen in claim 23,24 and 29 described in any one into
It is any in the formed body of aluminium oxide containing halogen, claim 28 and 29 in type body, claim 25,26 and 29 described in any one
Formed body in formed body or claim 34 and 35 described in one described in any one.
37. catalyst according to claim 36, wherein, the hydrogenation active component is selected from least one group VIII gold
Belong to element and at least one vib metals element；
Preferably, on the basis of the total amount of the catalyst, the content for the group VIII metallic element counted using oxide is 0.5-10
Weight %, the content for the vib metals element counted using oxide is 5-35 weight %.
38. a kind of preparation method of the catalyst with hydrogenation catalyst effect, this method are included in supported on carriers hydrogenation activity
Component, wherein, the carrier be the formed body of hydrated alumina containing halogen in claim 23,24 and 29 described in any one,
Any one in the formed body of aluminium oxide containing halogen, claim 28 and 29 in claim 25,26 and 29 described in any one
Formed body in the formed body or claim 34 and 35 described in any one.
39. according to the method for claim 38, wherein, the hydrogenation active component is selected from least one group VIII metal
Element and at least one vib metals element；
Preferably, on the basis of the total amount of the catalyst, the content for the group VIII metallic element counted using oxide is 0.5-10
Weight %, the content for the vib metals element counted using oxide is 5-35 weight %.
40. a kind of hydrotreating method, this method is included under hydroprocessing conditions, by hydrocarbon ils with having hydrogenation catalyst effect
Catalyst contacts, wherein, the catalyst with hydrogenation catalyst effect is urging described in any one in claim 36-37
Agent or the catalyst prepared as the method described in any one in claim 38-39.
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| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
| CN103864123A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Water column forming method of spherical aluminum oxide |
| CN104086201A (en) * | 2014-07-22 | 2014-10-08 | 南京理工宇龙新材料科技有限公司 | High-purity alumina fiber and preparation method thereof |
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| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
| CN103864123A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Water column forming method of spherical aluminum oxide |
| CN104086201A (en) * | 2014-07-22 | 2014-10-08 | 南京理工宇龙新材料科技有限公司 | High-purity alumina fiber and preparation method thereof |
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