CN107303485A - A kind of preparation method of modified aluminium oxide supports - Google Patents
A kind of preparation method of modified aluminium oxide supports Download PDFInfo
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- CN107303485A CN107303485A CN201610252528.7A CN201610252528A CN107303485A CN 107303485 A CN107303485 A CN 107303485A CN 201610252528 A CN201610252528 A CN 201610252528A CN 107303485 A CN107303485 A CN 107303485A
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- alumina support
- polyalcohol
- aqueous solution
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 29
- 238000007598 dipping method Methods 0.000 claims abstract description 21
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000007921 spray Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000000811 xylitol Substances 0.000 claims description 6
- 235000010447 xylitol Nutrition 0.000 claims description 6
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 6
- 229960002675 xylitol Drugs 0.000 claims description 6
- 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 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 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 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- 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
- 238000002803 maceration Methods 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 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 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 sorbierite Chemical compound 0.000 claims description 3
- 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 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 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 2
- 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 2
- 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 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005245 sintering 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
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 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
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 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
- 238000004364 calculation method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of modified aluminium oxide supports, including following content：（1）By the clay after high-temperature process and boehmite kneading and compacting, article shaped is through drying, low-temperature bake；（2）Use aqueous slkali soaking step（1）Obtained material simultaneously seals heat treatment, then scrubbed, dry and be calcined, and alumina support is made；（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed on the alumina support according to the order of concentration from high to low；（4）By step（3）Alumina support after dipping carries out hydro-thermal charing process in sealing container, and modified aluminium oxide supports are made in drying process.Alumina support prepared by this method has suitable pore structure simultaneously, and alumina support channel surfaces are carried out with carbon modification, and carbon content is in radially uneven distribution in carrier, and the carrier is applied to prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, a kind of preparation method of carbon modified aluminium oxide supports is related in particular to.
Background technology
At present, in the production process of mink cell focus HDM, because feedstock oil contains the impurity such as a certain amount of vanadium, sulphur, arsenic, nickel, deposition is easily formed, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, or even inactivation, influence commercial Application.Catalyst with larger pore volume and larger bore dia holds metal and holds that coke formation is strong, and the inactivation that can slow down catalyst, the service cycle for making catalyst extend.The pore structure of catalyst is determined that therefore, it is to prepare residual oil, especially prepare the key of the decompression residuum Hydrodemetalation catalyst higher for tenor to prepare the carrier with larger pore volume and larger bore dia by the carrier for constituting catalyst.In addition, after load active component in roasting process, active metal component easily has an effect to form very strong M-O-Al keys with alumina support, causes active component formation Spinel and loses activity, or make active component can not complete cure so as to reducing catalyst activity.
CN1160602A discloses a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and preparation method thereof.The preparation method of the macropore alumina supporter includes boehmite dry glue powder to be mixed with water or the aqueous solution, it is kneaded into plastic, obtained plastic is extruded into bar on banded extruder, dry and be calcined and obtain product, it is characterized in, carbon powder is additionally added in above process as physics expanding agent and can occur the chemical enlargement agent of the phosphorous of chemical action, silicon or boron compound with boehmite or aluminum oxide.Wherein carbon powder consumption is 3-10 weights %（On the basis of the weight of aluminum oxide）.Obtained alumina support can be used for preparing mink cell focus particularly residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 proposes to be used as expanding agent using carbon black.Expanding agent is well mixed with boehmite dry glue powder, it is 4.3% aqueous solution of nitric acid kneading 30 minutes that mass fraction is added into said mixture, then it is 2.1% ammonia spirit kneading 25 minutes to add mass fraction, extruded moulding after kneading is uniform, the fired obtained final alumina support of carrier after shaping.The addition of wherein carbon powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.The step of this method prepares alumina support is as follows：（1）Boehmite dry glue powder and extrusion aid are well mixed, then add the aqueous solution for having dissolved physics expanding agent and chemical enlargement agent；（2）By step（1）Resulting material is well mixed, the extruded moulding on banded extruder；（3）By step（2）Resulting material is dried, final alumina support is made in roasting.
In summary, prior art improves the aperture of carrier usually using physics expanding agent and chemical enlargement agent during preparing macropore alumina supporter, and the addition of expanding agent can make the increase of alumina support macropore content really.But because the addition of physics expanding agent can be impacted to the mechanical strength of carrier, in addition, the interaction of active component and carrier is remained to be further improved.
The content of the invention
For existing technical deficiency, the present invention provides a kind of preparation method of modified aluminium oxide supports, alumina support prepared by this method has suitable pore structure simultaneously, carbon modification is carried out to alumina support channel surfaces, and carbon content is in radially uneven distribution in carrier, the carrier is applied to prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
The preparation method of the modified aluminium oxide supports of the present invention, including following content：
（1）By the clay after high-temperature process and appropriate boehmite kneading and compacting, article shaped is through drying, low-temperature bake；
（2）Use aqueous slkali soaking step（1）Obtained material simultaneously seals that material after heat treatment, processing is scrubbed, dries and is calcined, and alumina support is made.
（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed according to the order of concentration from high to low in step（2）On alumina support so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on carrier；
（4）By step（3）Alumina support after dipping carries out hydro-thermal charing process in sealing container, and modified aluminium oxide supports are made in drying process.
In the inventive method, step（1）Described clay is one or more of mixing in kaolin, montmorillonite, diatomite or concavo-convex rod soil, clay（Without high-temperature process）The mass ratio of boehmite after being carbonized with hydro-thermal is 5:100-15:100.
In the inventive method, step（1）Described high-temperature process temperature is 950-1100 DEG C, and processing time is 5-10 hours.
In the inventive method, step（1）Described drying, shaping can be carried out using this area conventional method.Described drying condition is：60-130 DEG C of drying temperature, drying time is 1-10 hours.In forming process, the one or more that can be added as needed in conventional shaping assistant, such as peptizing agent, extrusion aid etc..Described peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., described extrusion aid refers to the material for being conducive to extrusion forming, one or more in such as sesbania powder, carbon black, graphite powder, citric acid, the consumption of extrusion aid accounts for 1wt%~10wt% of total material butt.
In the inventive method, step（1）Described low-temperature bake temperature is 250-350 DEG C, and preferably 280-320 DEG C, roasting time is 3-6 hours.
In the inventive method, step（2）Described 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 consumption of aqueous slkali and the mass ratio of clay are 40:1-60:1
In the inventive method, step（2）Described sealing is heat-treated to be carried out in autoclave, and heat treatment temperature is 70-100 DEG C, and processing time is 3-5 hours.The sintering temperature is 550-700 DEG C, and roasting time is 6-10 hours.
In the inventive method, step（3）Described polyalcohol includes the one or more in xylitol, sorbierite, mannitol or arabite etc.；Described monose includes the one or more in glucose, ribose or fructose etc..
In the inventive method, step（3）Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5%-50%.
In the inventive method, step（3）It is described according to concentration from high to low spray order, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5%-30%, preferably 10%-20%；It is preferred that preparing the polyalcohol and/or the monose aqueous solution of 2-4 kind various concentrations.
In the inventive method, step（3）The described maceration extract consumption sprayed every time is 10%-60%, the preferably 20%-30% of alumina support saturated water adsorptive value, and the total consumption of maceration extract repeatedly sprayed is the saturated water adsorptive value of alumina support to ensure that alumina support saturation impregnates.
In the inventive method, step（3）It is preferred that the polyalcohol and/or the monose aqueous solution of preparing 3 kinds of various concentrations are sprayed, detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of alumina support water absorption.
In the inventive method, step（3）Described alumina support is graininess, can be spherical, bar shaped（Including cylinder, trilobal, quatrefoil etc.）Or piece shape, preferably bar shaped or spherical, more preferably bar shaped.The one or more that can also be added as needed in the auxiliary elements such as Si, Ti, Zr, B or F in described alumina support.
In the inventive method, step（4）Described hydro-thermal charing process temperature is 180-250 DEG C, and preferably 200-230 DEG C, hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, ensure that polyalcohol and/or monose are carbonized completely under this hydro-thermal carbonization condition.Wherein, self-generated pressure is relevant with treatment temperature, when temperature is 100 DEG C, pressure 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.
Clay and the molding of boehmite of the invention by high-temperature roasting, again pass by low-temperature bake, boehmite is also not converted into aluminum oxide, in alkaline solution during hydro-thermal process, the silica being substantially carried out in alkali desilication reaction, clay particle is largely dissolved and removed, improve macropore content in carrier in the duct of formation, remaining aluminum oxide is more in clay particles exists with σ, θ, alpha-phase aluminum oxide, and the alumina grain of these forms is larger, improves the aperture of carrier；Under boehmite alkalescence simultaneously after low-temperature bake, hydrothermal condition, crystal grain secondary crystallization improves crystal particle scale, improves carrier hole structurally and mechanically intensity.
When spraying dipping with the polyalcohol and/or the monose aqueous solution of various concentrations, the concentration of polyalcohol and/or monose is by carrier surface to center in incremental distribution, carbonized by hydro-thermal, the relatively thin internal carbon-coating of carbon-coating outside the carbon-coating of gradient distribution, i.e. carrier is formed on carrier surface and duct inwall thicker.The strong interaction between metal component and carrier is effectively prevented due to the presence of carbon-coating, the gradient distribution of carbon layers having thicknesses, act on and gradually weakening from outside to inside between active metal and carrier, i.e. catalyst activity is gradually stepped up from outside to inside, during HDM, promote the reaction inside catalyst duct, it effectively prevent due to the higher service life for making demetalization reaction acutely cause catalyst duct to block and make the phenomenon of catalyst inactivation, catalyst being extended while catalyst activity is improved of outer surface active component activity.
Embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following examples.
Using N2Physics suction-desorption characterizes embodiment and comparative example carrier pore structure, and concrete operations are as follows：Using ASAP-2420 types N2Physics is inhaled-is desorbed instrument and sample pore structure is characterized.A small amount of sample application of vacuum 3 ~ 4 hours at 300 DEG C are taken, product is finally placed in liquid nitrogen cryogenics（-200℃）Under the conditions of carry out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equations, and pore-size distribution and pore volume are obtained according to BJH models.
Carbon content in alumina support is determined using EPMA, concrete operations are as follows：It is measured using JEOL's JXA-8230 electron probes, the accelerating potential selected during measure is 15KV, probe current is 8 × 10-8A, beam spot size is 3 μm.It is respectively the carbon content at 1/4R, 1/2R, 3/4R and R at measurement alumina support cross-section center and with distance at alumina support kernel of section, wherein R is the distance of line segment between any point in alumina support cross-section center and cross section outer most edge（The substantially radius of cross section）, then by division calculation, obtain the ratio between each content.
Embodiment 1
10 grams of montmorillonite is weighed, is calcined 5 hours in 950 DEG C, the montmorillonite after roasting and 200g boehmite dry glue powders（Shandong Aluminum Co., Ltd. Co., Ltd produces）, 6 grams of sesbania powder is well mixed, and the appropriate aqueous solution dissolved with 5 grams of acetic acid is added into mixed material, extruded moulding, article shaped is dried 5 hours in 120 DEG C, and dried object is calcined 5 hours in 300 DEG C.Boehmite after roasting is placed in autoclave polytetrafluoroethyllining lining, while it is 4 to add 400 grams of concentration
Mol/L sodium hydroxide solution, autoclave after sealing is heat-treated 4 hours in 90 DEG C, and the material after processing is through filtering, deionized water washing, 110 DEG C of drying 6 hours, and 600 DEG C are calcined 8 hours obtained alumina supports.
Weigh above-mentioned 100 grams of γ phases cylinder bar shaped alumina support to be put into spray rolling pot, under rotary state, impregnating effect concentration is sprayed as 40% xylose alcohol solution 25ml using carrier of the atomizing type into rolling pot；Then continue to spray oxide impregnation alumina supporter for 20% xylose alcohol solution 40ml with mass concentration；Finally continue to spray oxide impregnation alumina supporter for 10% xylose alcohol solution 40ml with mass concentration.Dipping terminates alumina support being transferred in autoclave and autoclave is placed in baking oven in charing process 9 hours under 180 DEG C, self-generated pressure, naturally cools to room temperature.In being dried 3 hours at 120 DEG C carbon containing oxidation carrier S1 is made, support is shown in Table 1 in alumina support after hydro-thermal process.
Embodiment 2
Be the same as Example 1, diatomaceous addition is 30 grams.Low-temperature bake temperature is 250 DEG C, and roasting time is 10 hours.Aqueous slkali is the potassium hydroxide solution that concentration is 3 mol/L, and solution usage is 1500 grams.Mixture heat treatment temperature is 100 DEG C, and processing time is 3 hours.Alumina support is clover bar shaped, for the first time with the aqueous solution of the 30ml mass concentrations for 30% sorbierite during spray dipping, with the aqueous solution of the 50ml mass concentrations for 10% sorbierite during second of spray dipping, with the aqueous solution of the 20ml mass concentrations for 5% sorbierite during third time spray dipping, temperature is 200 DEG C during charing process, carbonization time is 8 hours, and carbon containing alumina support S2 is made, and the property of carrier is shown in Table 1.
Embodiment 3
The montmorillonite of be the same as Example 1 is changed to kaolin, and sintering temperature is 1000 DEG C, and kaolinic addition is 20 grams.Low-temperature bake temperature is 350 DEG C, and roasting time is 7 hours.Aqueous slkali is that concentration is 5mol/L, and solution usage is 1200 grams.Mixture heat treatment temperature is 70 DEG C, and processing time is 4 hours.Impregnated using four sprays, for the first time with the aqueous solution of the 20ml mass concentrations for 50% mannitol during spray dipping, with the aqueous solution of the 40ml mass concentrations for 30% sorbierite during second of spray dipping, with the aqueous solution of the 20ml mass concentrations for 20% sorbierite during third time spray dipping, with the aqueous solution of the 20ml mass concentrations for 10% sorbierite during the 4th spray dipping.Temperature is 240 DEG C during charing process, and carbonization time is 12 hours.Carbon containing alumina support S3 is made, the property of carrier is shown in Table 1.
Embodiment 4
Be the same as Example 1, simply using spray dipping twice, for the first time with the aqueous solution of the 50ml mass concentrations for 40% arabite during spray dipping, with the aqueous solution of the 55ml mass concentrations for 20% arabite during second of spray dipping, carbonization temperature is 250 DEG C, and carbonization time is 6 hours.Carbon containing alumina support S4 is made, the property of carrier is shown in Table 1.
Embodiment 5
Be the same as Example 1, simply alumina support is bunge bedstraw herb bar shaped, and it is 1 that xylitol, which changes mass ratio into,:1:1:1 xylitol, arabite, the mixing alcohol solution dipping of sorbierite and mannitol, temperature is 220 DEG C during charing process, and processing time is 10 hours.Carbon containing alumina support S5 is made, the property of carrier is shown in Table 1.
Comparative example 1
Be the same as Example 1, does not simply add clay in carrier, and comparative example alumina support S6 is made, and the property of carrier is shown in Table 1.
Comparative example 2
Be the same as Example 1, simply xylitol solution is not using multiple spray dipping but uses once to spray and be impregnated on alumina support by the way of dipping, comparative example alumina support S7 is made, the property of carrier is shown in Table 1.
Comparative example 3
Be the same as Example 1, does not spray dipping xylitol solution simply, but by same amount of deionized water dipping to alumina support, comparative example alumina support S8 is made, and the property of carrier is shown in Table 1.
The carrying alumina volume property of table 1
The pore volume that pore size distribution refers to the diameter range endoporus of certain in carrier accounts for the percentage of total pore volume.
The result of table 1 shows, the alumina support prepared using the inventive method, and carbon is contained on surface while with suitable pore structure, and carbon content is in radially uneven distribution in carrier.Alumina support prepared by this method is applied to weight, residuum hydrogenating and metal-eliminating field.
Embodiment 6
Aluminum oxide prepares Hydrodemetalation catalyst as carrier obtained by the present embodiment using above-described embodiment and comparative example.
Each 100 grams of alumina support prepared by embodiment 1-5 and comparative example 1-3 is weighed, 150mlMo-Ni-NH is added3Solution（Containing MoO312.0wt%,
NiO3.0 wt%）Dipping 2 hours, filters off redundant solution, 120 DEG C of drying, then is calcined 5 hours under 550 DEG C of nitrogen atmospheres, obtains Hydrodemetalation catalyst C1-C8.
Embodiment 7
The following examples illustrate be by carrier and comparative example aluminum oxide of aluminum oxide of the present invention Hydrodemetalation catalyst prepared by carrier catalytic performance.
Using feedstock oil listed by table 2 as raw material, C1-C8 catalytic performance is evaluated on 200 milliliters of hydrogenation reaction device, catalyst is long 2 ~ 3 millimeters bar, and catalyst loading amount is 100 milliliters, and reaction temperature is 375 DEG C, and hydrogen dividing potential drop is 13MPa, and liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio is 1000, and reaction determines the content of each impurity in generation oil after 200 hours, calculates metal phase to removal efficiency, evaluation result is shown in Table 3.
The raw material oil nature of table 2
The catalyst hydrogenation performance comparison of table 3
It can be seen from the data of table 3 compared with contrasting alumina support, the catalyst prepared by carrier of aluminum oxide of the present invention has higher HDM activity.
Claims (14)
1. a kind of preparation method of modified aluminium oxide supports, including following content：（1）By the clay after high-temperature process and boehmite kneading and compacting, article shaped is through drying, low-temperature bake；（2）Use aqueous slkali soaking step（1）Obtained material simultaneously seals that material after heat treatment, processing is scrubbed, dries and is calcined, and alumina support is made；（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed according to the order of concentration from high to low in step（2）On alumina support so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on carrier；（4）By step（3）Alumina support after dipping carries out hydro-thermal charing process in sealing container, and modified aluminium oxide supports are made in drying process.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described clay is one or more of mixing in kaolin, montmorillonite, diatomite or concavo-convex rod soil.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）The mass ratio of described clay and the boehmite after hydro-thermal charing is 5:100-15:100.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Described high-temperature process temperature is 950-1100 DEG C, and processing time is 5-10 hours.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described low-temperature bake temperature is 250-350 DEG C, and roasting time is 3-6 hours.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）Described aqueous slkali is sodium hydroxide and/or potassium hydroxide solution, and the molar concentration of aqueous slkali is with OH-It is calculated as 3-5mol/L.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）The consumption of described aqueous slkali and the mass ratio of clay are 40:1-60:1.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）Described sealing is heat-treated to be carried out in autoclave, and heat treatment temperature is 70-100 DEG C, and processing time is 3-5 hours.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described polyalcohol is the one or more in xylitol, sorbierite, mannitol or arabite；Described monose is the one or more in glucose, ribose or fructose etc..
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5%-50%.
11. in accordance with the method for claim 1, it is characterised in that：Step（3）It is described according to concentration from high to low spray order, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5%-30%.
12. in accordance with the method for claim 1, it is characterised in that：Step（3）The described maceration extract consumption sprayed every time is the 10%-60% of alumina support saturated water adsorptive value, and the total consumption of maceration extract repeatedly sprayed is the saturated water adsorptive value of alumina support to ensure that alumina support saturation impregnates.
13. in accordance with the method for claim 1, it is characterised in that：Step（3）The polyalcohol and/or the monose aqueous solution for preparing 3 kinds of various concentrations are sprayed, and detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of alumina support water absorption.
14. in accordance with the method for claim 1, it is characterised in that：Step（4）Described hydro-thermal charing process temperature is 180-250 DEG C, and hydrothermal conditions are 6-12 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019080921A1 (en) * | 2017-10-27 | 2019-05-02 | 中国石油化工股份有限公司 | Aluminum oxide carrier material and preparation method therefor, hydrogenation catalyst and method for residual oil hydrogenation |
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| CN111889065A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Modified macroporous material and preparation method thereof |
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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 |
-
2016
- 2016-04-21 CN CN201610252528.7A patent/CN107303485B/en active Active
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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019080921A1 (en) * | 2017-10-27 | 2019-05-02 | 中国石油化工股份有限公司 | Aluminum oxide carrier material and preparation method therefor, hydrogenation catalyst and method for residual oil hydrogenation |
| US11207669B2 (en) | 2017-10-27 | 2021-12-28 | China Petroleum & Chemical Corporation | Alumina supporter material and preparation method thereof, hydrogenation catalyst and residual oil hydrogenation processing |
| CN111821968A (en) * | 2019-04-19 | 2020-10-27 | 中国石油化工股份有限公司 | Silicon-aluminum composite oxide and preparation method thereof |
| CN111822056A (en) * | 2019-04-19 | 2020-10-27 | 中国石油化工股份有限公司 | High-acid-content silicon-aluminum material and preparation method thereof |
| CN111821968B (en) * | 2019-04-19 | 2023-01-10 | 中国石油化工股份有限公司 | Silicon-aluminum composite oxide and preparation method thereof |
| CN111889065A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Modified macroporous material and preparation method thereof |
| CN111889065B (en) * | 2019-05-06 | 2023-04-18 | 中国石油化工股份有限公司 | Modified macroporous material and preparation method thereof |
| CN112742406A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN114713229A (en) * | 2022-04-24 | 2022-07-08 | 北京化工大学 | Ni-based alloy catalyst induced by carrier coordination structure and preparation method and application thereof |
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