CN107303510B - A kind of preparation method of carbon containing alumina support - Google Patents
A kind of preparation method of carbon containing alumina support Download PDFInfo
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- CN107303510B CN107303510B CN201610252530.4A CN201610252530A CN107303510B CN 107303510 B CN107303510 B CN 107303510B CN 201610252530 A CN201610252530 A CN 201610252530A CN 107303510 B CN107303510 B CN 107303510B
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- alumina support
- polyalcohol
- aqueous solution
- monosaccharide
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 38
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 37
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 32
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 32
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 30
- 238000007598 dipping method Methods 0.000 claims abstract description 23
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 239000007921 spray Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000010447 xylitol Nutrition 0.000 claims description 9
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000000811 xylitol Substances 0.000 claims description 8
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 8
- 229960002675 xylitol Drugs 0.000 claims description 8
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 7
- 229930195725 Mannitol Natural products 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000594 mannitol Substances 0.000 claims description 7
- 235000010355 mannitol Nutrition 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 5
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- -1 sorbierite Chemical compound 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910001648 diaspore Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 210000000476 body water Anatomy 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- 239000003795 chemical substances by application Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black 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
- 239000003921 oil Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 5
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910018551 Ni—NH Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of carbon containing alumina support, including following content: (1) impregnating boehmite dry glue powder with the aqueous solution containing polyalcohol and/or glucide, material after dipping carries out hydro-thermal charing process, treated, and boehmite through molding, drying and roasts, and obtains alumina support；(2) polyalcohol and/or monosaccharide aqueous solution of at least two various concentrations are prepared, it is sprayed on step (1) alumina support according to the sequence of concentration from high to low, so that the concentration of polyalcohol and/or monosaccharide forms ecto-entad in gradient distribution from low to high on carrier；(3) alumina support after step (2) dipping is subjected in sealing container hydro-thermal charing process, is dried and the carbon containing alumina support of the present invention is made.The alumina support of this method preparation has large hole appearance and aperture, and for carbon content in carrier radial direction distribution gradient, which is suitable for the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The present invention relates to a kind of preparation methods of alumina support, relate in particular to a kind of system of carbon containing alumina support
Preparation Method.
Background technique
Currently, in the production process of mink cell focus hydrodemetallization, since feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Equal impurity, easily form deposition, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, or even inactivation, influence
Industrial application.Hold with large hole and the catalyst of larger bore dia holds metal and appearance coke formation is strong, catalyst can be slowed down
The operation cycle for inactivating, making catalyst extends.The pore structure of catalyst is determined that therefore, preparation has by the carrier for constituting catalyst
Large hole is held and the carrier of larger bore dia is to prepare residual oil, especially prepare and add for the higher decompression residuum of tenor
The key of hydrogen catalyst for demetalation.In addition, active metal component is easy and aluminium oxide after load active component in roasting process
Carrier has an effect to form very strong M-O-Al key, causes active component to form Spinel and lose activity, or make activity
Component can not complete cure to reducing catalyst activity.
CN1160602A disclose a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and its
Preparation method.The preparation method of the macropore alumina supporter includes that boehmite dry glue powder is mixed with water or aqueous solution,
It is kneaded into plastic, obtained plastic is extruded into bar on banded extruder, drying simultaneously roasts to obtain product, its main feature is that,
It is additionally added carbon black powder in above process as physics expanding agent and chemical action can occur with boehmite or aluminium oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon black powder dosage is 3-10 weight %(on the basis of the weight of aluminium oxide).
Alumina support obtained can be used for preparing mink cell focus especially residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 is proposed using carbon black as expanding agent.Expanding agent is uniformly mixed with boehmite dry glue powder, to
Aqueous solution of nitric acid kneading 30 minutes that mass fraction is 4.3% are added in said mixture, it is 2.1% that mass fraction, which is then added,
Ammonia spirit kneading 25 minutes, kneading uniformly after extruded moulding, carrier after molding, which is fired, is made final alumina support.Its
The additional amount of middle carbon black powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.This method prepares the step of alumina support such as
Under: (1) boehmite dry glue powder and extrusion aid be uniformly mixed, and is then added and has dissolved physics expanding agent and chemical enlargement agent
Aqueous solution；(2) step (1) resulting material is uniformly mixed, the extruded moulding on banded extruder；(3) step (2) resulting material is dry
Final alumina support is made in dry, roasting.
In conclusion usually using physics expanding agent and chemical enlargement during prior art preparation macropore alumina supporter
Agent improves the aperture of carrier, and the addition of expanding agent can be such that alumina support macropore content increases really.But in alumina support
Forming process, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents at plastic, then extruded moulding, due to squeezing
The presence of the larger pressure of process can make the macropore of alumina powder itself that part occur to collapse, to make the Kong Rong of final carrier
And macropore content substantially reduces.In addition, interaction needs into one between the alumina support and active component of prior art preparation
Step improves.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of preparation method of carbon containing alumina support, this method preparation
Alumina support there is large hole to hold and aperture, carbon content in carrier radial direction distribution gradient, the carrier be suitable for preparation weight,
The fields such as residuum hydrogenating and metal-eliminating catalyst.
The preparation method of carbon containing alumina support of the invention, including following content:
(1) impregnate boehmite dry glue powder with the aqueous solution containing polyalcohol and/or glucide, the material after dipping into
Row hydro-thermal charing process, treated, and boehmite through molding, drying and roasts, and obtains alumina support；
(2) polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, according to the sequence of concentration from high to low
It sprays on step (1) alumina support, so that it is in by low that the concentration of polyalcohol and/or monosaccharide forms ecto-entad on carrier
To high gradient distribution；
(3) alumina support after step (2) dipping is subjected in sealing container hydro-thermal charing process, is dried system
Obtain carbon containing alumina support of the invention.
In the method for the present invention, polyalcohol described in step (1) is in xylitol, sorbierite, mannitol or arabite
It is one or more of；The carbohydrate is the mixing of one or more of glucose, ribose or fructose etc.；Containing polyalcohol and/or sugar
The mass concentration of the aqueous solution of substance is 20%-40%.The dosage of aqueous solution containing polyalcohol and/or glucide is thin for that will intend
Diaspore dry glue powder is totally submerged, and dip time is 3-5 hours.
In the method for the present invention, hydro-thermal charing process described in step (1) is the heat treatment carried out in sealing device, preferably
Autoclave can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；The hydro-thermal charing process temperature
It is 120-160 DEG C, the processing time is 8-16 hours.
In the method for the present invention, molding, drying and roasting described in step (1) can be carried out using conventional method in that art.
In forming process, it can according to need and one of conventional shaping assistant, such as peptizing agent, extrusion aid etc. or a variety of is added.
The peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., and the extrusion aid, which refers to, to be conducive to squeeze
One or more of molded substance, such as sesbania powder, carbon black, graphite powder, citric acid, the total material of dosage Zhan of extrusion aid
1wt%~10wt% of butt.The drying condition are as follows: drying temperature is 60-130 DEG C, and drying time is 1-10 hours.It is described
Maturing temperature be 500-750 DEG C, calcining time be 2-10 hours.
In the method for the present invention, the boehmite described in step (1) after hydro-thermal charing process is preferably according to such as lower section
Alumina support is made in formula: by after high-temperature process clay and treated boehmite kneading and compacting, molding through drying,
Then low-temperature bake with aqueous slkali soaking and seals heat treatment, treated, and material is washed, dried and roasted, and obtains oxygen
Change alumina supporter；Wherein the clay is the mixing of one or more of kaolin, montmorillonite, diatomite or concavo-convex rod soil, is glued
The mass ratio of boehmite after native (without high-temperature process) and hydro-thermal charing is 5:100-15:100；The high-temperature process
Temperature is 950-1100 DEG C, and the processing time is 5-10 hours；The drying, molding can using conventional method in that art into
Row；The drying condition are as follows: 60-130 DEG C of drying temperature, drying time is 1-10 hours；It, can be according to need in forming process
One of conventional shaping assistant, such as peptizing agent, extrusion aid etc. or a variety of is added.The peptizing agent is hydrochloric acid, nitre
One or more of in acid, sulfuric acid, acetic acid, oxalic acid etc., the extrusion aid refers to the substance for being conducive to extrusion forming, such as sesbania
One or more of powder, carbon black, graphite powder, citric acid etc., 1wt%~10wt% of the total material butt of the dosage Zhan of extrusion aid；
The low-temperature bake temperature is 250-350 DEG C, and preferably 280-320 DEG C, calcining time is 3-6 hours；At the sealing heat
Reason carries out in autoclave, and heat treatment temperature is 70-100 DEG C, and the processing time is 3-5 hours；The aqueous slkali is hydroxide
Sodium and/or potassium hydroxide solution, the molar concentration of aqueous slkali is with OH-It is calculated as 3-5mol/L, the dosage of aqueous slkali and the matter of clay
Amount is than being 40:1-60:1
In the method for the present invention, polyalcohol described in step (2) includes xylitol, sorbierite, mannitol or arabite etc.
One or more of；The monosaccharide includes one or more of glucose, ribose or fructose etc..
In the method for the present invention, the mass concentration of polyalcohol described in step (2) and/or monosaccharide aqueous solution is 5%-50%.
In the method for the present invention, described in step (2) according to concentration from high to low spray sequence, adjacent polyalcohol twice
And/or the concentration difference of monosaccharide aqueous solution is 5%-30%, preferably 10%-20%；It is preferred that prepare 2-4 kind various concentration polyalcohol and/
Or monosaccharide aqueous solution.
In the method for the present invention, the maceration extract dosage sprayed every time described in step (2) is alumina support saturated water adsorptive value
10%-60%, preferably 20%-30%, the total dosage of the maceration extract repeatedly sprayed be alumina support saturated water adsorptive value to ensure oxygen
Change alumina supporter saturation dipping.
In the method for the present invention, the preferred polyalcohol for preparing 3 kinds of various concentrations of step (2) and/or monosaccharide aqueous solution are sprayed
Leaching, detailed process is as follows: spray for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 30%-50%, polyalcohol and/
Or the dosage of monosaccharide aqueous solution is the 20%-30% of alumina support water absorption；It sprays for the second time, polyalcohol and/or monosaccharide are water-soluble
The mass concentration of liquid is 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is the 40%-60% of alumina support water absorption；
Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%, the use of polyalcohol and/or monosaccharide aqueous solution
Amount is the 10%-40% of alumina support water absorption.
In the method for the present invention, alumina support described in step (2) is graininess, can be spherical, bar shaped (including cylinder
Shape, trilobal, quatrefoil etc.) or piece shape, preferably bar shaped or spherical shape, more preferably bar shaped.It can also in the alumina support
One or more of auxiliary elements such as Si, Ti, Zr, B or F to be added as needed.
In the method for the present invention, hydro-thermal charing process temperature described in step (3) be 180-250 DEG C, preferably 200-230 DEG C,
Hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, under this hydro-thermal carbonization condition
It can guarantee that polyalcohol and/or monosaccharide carbonize completely.Wherein, self-generated pressure is related with treatment temperature, when temperature is 100 DEG C, pressure
Force value (gauge pressure) general 0.1MPa, at 150 DEG C, pressure value is generally 0.43MPa, and at 250 DEG C, pressure value is generally 1.95MPa.
For boehmite dry glue powder through hydro-thermal charing process, it is intercrystalline that the carbons substance of formation is filled in boehmite
In duct, when extruded moulding, due to the presence of carbon particle, good supporting role can be played, effectively prevents and intends thin water
The collapsing of aluminium stone macropore, the hole for improving carrier holds and macropore content.
Desilication reaction, the titanium dioxide in clay particle occur when being heat-treated in alkaline solution for boehmite after molding
Silicon is largely dissolved and removes, and macropore content in carrier is improved in the duct of formation.And in clay particles remaining aluminium oxide mostly with
σ, θ, alpha-phase aluminum oxide exist, and the alumina grain of these forms is larger, improves the aperture of carrier.Intending after low-temperature bake is thin
Diaspore is heat-treated in alkaline solution, due to alkalinity, the presence of hydrothermal condition, is made boehmite crystal grain secondary crystallization, is mentioned
High crystal particle scale improves carrier pore structure.
When the polyalcohol and/or monosaccharide aqueous solution of shaping carrier various concentration spray dipping, polyalcohol and/or monosaccharide
Concentration, in distribution is incremented by, is carbonized by carrier surface to center by hydro-thermal, and gradient point is formed on carrier surface and duct inner wall
The relatively thin internal carbon-coating of carbon-coating is thicker outside the carbon-coating of cloth, i.e. carrier.Since the presence of carbon-coating effectively prevents metal component and carries
Strong interaction between body, the gradient distribution of carbon layers having thicknesses act between active metal and carrier and gradually weakening from outside to inside,
I.e. catalyst activity is gradually increased from outside to inside, during hydrodemetallization, promotes the reaction inside catalyst duct, has
Effect is avoided makes demetalization reaction acutely catalyst duct be caused to block and make to urge since outer surface active component activity is higher
The phenomenon that agent inactivates, extends the service life of catalyst while improving catalyst activity.
Specific embodiment
The effect and effect of the method for the present invention are further illustrated below with reference to embodiment, but are not limited to following implementation
Example.
Using N2Physics suction-desorption characterization embodiment and comparative example carrier pore structure, concrete operations are as follows: using ASAP-
2420 type N2Physics is inhaled-is desorbed instrument and characterizes to catalyst sample pore structure.Take a small amount of sample be vacuum-treated 3 at 300 DEG C ~
Product is finally placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test by 4 h.Wherein surface area is according to BET
Equation obtains, and pore-size distribution and pore volume are obtained according to BJH model.
Using carbon content in EPMA measurement alumina support, concrete operations are as follows: using Japan Electronics JXA-8230 electronics
Probe is measured, and the acceleration voltage that when measurement selects is 15KV, and probe current is 8 × 10-8A, beam spot size are 3 μm.Respectively
It measures at alumina support cross-section center and with distance at alumina support kernel of section as at 1/4R, 1/2R, 3/4R and R
Carbon content, wherein R is that alumina support cross-section center is (substantive at a distance from line segment between any point in the outer most edge of cross section
On be cross section radius), then by division calculation, obtain the ratio between each content.
Embodiment 1
It weighs boehmite (production of Shandong Aluminum Co., Ltd. Co., Ltd) 200g to be placed in a beaker, 400mL is added into beaker
The xylose alcohol solution that mass concentration is 25% impregnates 4 hours.Through filtering, filter cake is transferred in autoclave material after dipping
Charing process is carried out, treatment temperature is 140 DEG C, and the processing time is 10 hours.Treated, and boehmite is filled with 4g sesbania powder
Point mixing, is added in Xiang Shangshu material uniform dissolved with the aqueous solution kneading of 2g acetic acid in right amount, is extruded into cylindrical bars.Wet object after molding
Expect, 600 DEG C roasting 8 hour obtained alumina support 8 hours dry in 110 DEG C.
It weighs 100 grams of alumina support of above-mentioned γ phase cylinder bar shaped to be put into spray rolling pot, under rotary state, with atomization
The xylose alcohol solution 25ml that carrier spray impregnating effect concentration of the mode into rolling pot is 40%；It then is 20% with mass concentration
Xylose alcohol solution 40ml continue spray oxide impregnation alumina supporter；The xylose alcohol solution for being finally 10% with mass concentration
40ml continues to spray oxide impregnation alumina supporter.Dipping terminates for alumina support to be transferred in autoclave and autoclave is placed in baking oven
In under 180 DEG C, self-generated pressure charing process 9 hours, cooled to room temperature.Alumina support after hydro-thermal process is in 120
Oxidation carrier S1 of the present invention is made within dry 3 hours at DEG C, support is shown in Table 1.
Embodiment 2
With embodiment 1, the mixing of the sorbierite and mannitol that are only 1:1 with the mass ratio that mass concentration is 40% is water-soluble
Liquid impregnates boehmite 3 hours.Charing process temperature is 130 DEG C, is handled the time 14 hours.Alumina support is clover item
Shape, the aqueous solution for the sorbierite for being for the first time 30% with 30ml mass concentration when spray dipping use 50ml when spray dipping for the second time
The aqueous solution for the sorbierite that mass concentration is 10%, the water for the sorbierite that third time spray is 5% with 20ml mass concentration when impregnating
Solution, temperature is 200 DEG C when charing process, and carbonization time is 8 hours.Alumina support S2 of the present invention, the property of carrier is made
It is shown in Table 1.
Embodiment 3
With embodiment 1, the mixed aqueous solution of the glucose and ribose that are only 1:1 with the mass ratio that mass concentration is 30%
Dipping boehmite 5 hours.Charing process temperature is 120 DEG C, and the charing process time is 16 hours.It is soaked using four sprays
Stain, the aqueous solution for the mannitol for being for the first time 50% with 20ml mass concentration when spray dipping use 40ml when spray dipping for the second time
The aqueous solution for the sorbierite that mass concentration is 30%, the water for the sorbierite that third time spray is 20% with 20ml mass concentration when impregnating
Solution, the 4th time spray dipping when with 20ml mass concentration be 10% sorbierite aqueous solution.Temperature is 240 when charing process
DEG C, carbonization time is 12 hours.Alumina support S3 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 4
With embodiment 1, the mixing water of the arabite and fructose that are only 1:1 with the mass ratio that mass concentration is 20%
Solution impregnates boehmite 4 hours.Charing process temperature is 150 DEG C, and the charing process time is 12 hours.Weigh montmorillonite 10
Gram, it is roasted 5 hours in 950 DEG C, 200 grams of boehmite after montmorillonite and above-mentioned charing after roasting, 6 grams of sesbania powder mixing
Uniformly, it being added into mixed material in right amount dissolved with the aqueous solution of 5 grams of acetic acid, extruded moulding, molding is 5 hours dry in 120 DEG C,
Dried object roasts 5 hours in 300 DEG C.Boehmite after roasting is placed in autoclave polytetrafluoroethyllining lining, is added simultaneously
Enter the sodium hydroxide solution that 400 grams of concentration are 4 mol/L, autoclave after sealing is heat-treated 4 hours in 90 DEG C, treated object
Material filtered, deionized water washing, 110 DEG C drying 6 hours, 600 DEG C roasting 8 hours.Using spray dipping twice, spray for the first time
The aqueous solution for the arabite for being 40% with 50ml mass concentration when leaching dipping is dense with 55ml mass when spray dipping for the second time
The aqueous solution for the arabite that degree is 20%, carbonization temperature are 250 DEG C, and carbonization time is 6 hours.Aluminium oxide of the present invention is made
The property of carrier S 4, carrier is shown in Table 1.
Embodiment 5
With embodiment 1, only impregnated boehmite 5 hours with the sorbitol aqueous solution that mass concentration is 35%.At charing
Managing temperature is 160 DEG C, and the charing process time is 8 hours.30 grams of diatomite are weighed, is roasted 5 hours in 950 DEG C, the silicon after roasting
200 grams of boehmite after diatomaceous earth and above-mentioned charing, 6 grams of sesbania powder are uniformly mixed, and are added into mixed material in right amount dissolved with 5
The aqueous solution of gram acetic acid, extruded moulding, molding is 5 hours dry in 120 DEG C, and dried object roasts 5 hours in 320 DEG C.It will roasting
Boehmite afterwards is placed in autoclave polytetrafluoroethyllining lining, while the hydroxide that 1500 grams of concentration are 4 mol/L is added
Potassium solution, autoclave after sealing are heat-treated 4 hours in 90 DEG C, and treated material is through filtering, deionized water washing, and 110 DEG C
6 hours dry, 600 DEG C roast 8 hours.Alumina support is bunge bedstraw herb bar shaped, and xylitol changes the wood that mass ratio is 1:1:1:1 into
Sugar alcohol, arabite, sorbierite and mannitol mixing alcohol solution dipping, temperature is 220 DEG C when charing process, when processing
Between be 10 hours.Alumina support S5 of the present invention is made, the property of carrier is shown in Table 1.
Comparative example 1
With embodiment 1, only not instead of repeatedly spray is not impregnated into alumina support xylitol, by same amount of xylose
Alcohol is impregnated into alumina support in such a way that primary spray impregnates, and comparative example alumina support S6 is made, and the property of carrier is shown in
Table 1.
Comparative example 2
With embodiment 1, only xylitol is not added in boehmite with impregnation method, by 15 grams of xylitols
It is added in the form of kneading in carrier molding, comparative example alumina support S7 is made, the property of carrier is shown in Table 1.
Comparative example 3
With embodiment 1, only shaping carrier does not spray dipping xylitol solution and comparison alumina support S8 is made.
1 carrying alumina volume property of table
Pore size distribution refers to that the Kong Rong of certain diameter range inner hole in carrier accounts for the percentage of total pore volume.
Table 1 the result shows that, using the method for the present invention prepare carbon containing alumina support, have larger aperture while have
There is biggish Kong Rong, the pore size distribution of concentration, carbon content is in alumina support radial direction distribution gradient.The aluminium oxide of this method preparation
Carrier is suitable for weight, residuum hydrogenating and metal-eliminating field.
Embodiment 6
The present embodiment prepares Hydrodemetalation catalyst using aluminium oxide obtained by above-mentioned embodiment and comparative example as carrier.
Each 100 grams of alumina support prepared by embodiment 1-5 and comparative example 1-3 are weighed, 150mlMo-Ni-NH is added3
Solution (contains MoO312.0wt%, NiO3.0 wt%) dipping 2 hours, redundant solution is filtered off, 120 DEG C dry, then in 550 DEG C of temperature
It is roasted 5 hours in lower nitrogen atmosphere, obtains Hydrodemetalation catalyst C1-C7.
Embodiment 7
The following examples illustrate by carrier of aluminium oxide of the present invention and comparative example aluminium oxide is prepared by carrier plus hydrogen is de-
The catalytic performance of metallic catalyst.
Using feedstock oil listed by table 2 as raw material, the catalytic performance of C1-C7 is evaluated on 200 milliliters of hydrogenation reaction device, is urged
Agent is long 2 ~ 3 millimeters of item, and catalyst loading is 100 milliliters, and reaction temperature is 380 DEG C, hydrogen partial pressure 13MPa, liquid space-time
Speed is 1.0 hours-1, hydrogen to oil volume ratio 1000, measurement generates the content of each impurity in oil after reaction 200 hours, calculates metal
Opposite removal efficiency, evaluation result are shown in Table 3.
2 raw material oil nature of table
3 catalyst hydrogenation performance comparison of table
It can be seen from 3 data of table compared with comparing alumina support, the catalysis that is prepared using aluminium oxide of the present invention as carrier
Agent hydrodemetallization activity with higher.
Claims (4)
1. a kind of preparation method of carbon containing alumina support, it is characterised in that including following content: (1) with containing polyalcohol and/or
The aqueous solution of glucide impregnates boehmite dry glue powder, and the material after dipping carries out hydro-thermal charing process, and it is quasi- that treated
Boehmite obtains alumina support through molding, drying and roasting；(2) prepare at least two various concentrations polyalcohol and/
Or monosaccharide aqueous solution, sprayed on step (1) alumina support according to the sequence of concentration from high to low so that polyalcohol and/or
The concentration of monosaccharide forms ecto-entad in gradient distribution from low to high on carrier；(3) by the aluminium oxide after step (2) dipping
Carrier carries out hydro-thermal charing process in sealing container, is dried, carbon containing alumina support is made；It is more described in step (1)
First alcohol is one or more of xylitol, sorbierite, mannitol or arabite；The carbohydrate be glucose, ribose or
The mixing of one or more of fructose；The mass concentration of aqueous solution containing polyalcohol and/or glucide is 20%-40%；Containing more
The dosage of the aqueous solution of first alcohol and/or glucide is to be totally submerged boehmite dry glue powder, and dip time is that 3-5 is small
When；Hydro-thermal charing process described in step (1) is the heat treatment carried out in sealing device, the hydro-thermal charing process temperature
It is 120-160 DEG C, the processing time is 8-16 hours；Polyalcohol described in step (2) be xylitol, sorbierite, mannitol or Ah
One or more of laubi alcohol；The monosaccharide is one or more of glucose, ribose or fructose；The polyalcohol
And/or the mass concentration of monosaccharide aqueous solution is 5%-50%；Described in step (2) according to concentration from high to low spray sequence, phase
The adjacent concentration difference of polyalcohol and/or monosaccharide aqueous solution twice is 5%-30%；Hydro-thermal charing process temperature described in step (3) is
180-250 DEG C, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
2. according to the method for claim 1, it is characterised in that: described in step (1) after hydro-thermal charing process intend it is thin
Alumina support is made in diaspore as follows: by clay and treated the boehmite kneading after high-temperature process at
Then type, molding with aqueous slkali soaking and seal heat treatment, treated, and material is washed, done through drying, low-temperature bake
Dry and roasting, obtains alumina support；Wherein the clay is one in kaolin, montmorillonite, diatomite or concavo-convex rod soil
The mass ratio of boehmite after kind or several mixing, clay and hydro-thermal charing is 5:100-15:100；At the high temperature
Managing temperature is 950-1100 DEG C, and the processing time is 5-10 hours；The low-temperature bake temperature is 250-350 DEG C, calcining time
It is 3-6 hours；The sealing heat treatment carries out in autoclave, and heat treatment temperature is 70-100 DEG C, and the processing time is that 3-5 is small
When；The aqueous slkali is sodium hydroxide and/or potassium hydroxide solution, and the molar concentration of aqueous slkali is with OH-3-5mol/L is calculated as,
The dosage of aqueous slkali and the mass ratio of clay are 40:1-60:1.
3. according to the method for claim 1, it is characterised in that: the maceration extract dosage sprayed every time described in step (2) is
The 10%-60% of alumina support saturated water adsorptive value, the total dosage of the maceration extract repeatedly sprayed are the saturated water adsorptive value of alumina support
To ensure alumina support saturation dipping.
4. according to the method for claim 1, it is characterised in that: step (2) prepare 3 kinds of various concentrations polyalcohol and/or
Monosaccharide aqueous solution is sprayed, and detailed process is as follows: being sprayed for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is
The dosage of 30%-50%, polyalcohol and/or monosaccharide aqueous solution is the 20%-30% of alumina support water absorption；It sprays for the second time, it is more
The mass concentration of first alcohol and/or monosaccharide aqueous solution is 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is carrying alumina
The 40%-60% of body water absorption；Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%, polyalcohol
And/or the dosage of monosaccharide aqueous solution is the 10%-40% of alumina support water absorption.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006062889A (en) * | 2004-08-24 | 2006-03-09 | Rikogaku Shinkokai | Carbonaceous material and method for producing the same |
| CN102310000A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN103785400A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetalization catalyst for residuum |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
| CN105080563A (en) * | 2014-05-05 | 2015-11-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006062889A (en) * | 2004-08-24 | 2006-03-09 | Rikogaku Shinkokai | Carbonaceous material and method for producing the same |
| CN102310000A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN103785400A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetalization catalyst for residuum |
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
| CN105080563A (en) * | 2014-05-05 | 2015-11-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor |
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