CN107303509B - A kind of preparation method of carbon containing macropore alumina supporter - Google Patents
A kind of preparation method of carbon containing macropore alumina supporter Download PDFInfo
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- CN107303509B CN107303509B CN201610252529.1A CN201610252529A CN107303509B CN 107303509 B CN107303509 B CN 107303509B CN 201610252529 A CN201610252529 A CN 201610252529A CN 107303509 B CN107303509 B CN 107303509B
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- alumina support
- polyalcohol
- acid
- aqueous solution
- alumina
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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 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 29
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 26
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000007921 spray Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000010009 beating Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000811 xylitol Substances 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 5
- 229960002675 xylitol Drugs 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
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 229910052796 boron Inorganic materials 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
- 238000007789 sealing Methods 0.000 claims description 4
- 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 3
- 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 3
- 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 3
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- -1 sorbierite Chemical compound 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 210000000476 body water Anatomy 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000003795 desorption Methods 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
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005507 spraying 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
- 244000025254 Cannabis sativa Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 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
- 241000219782 Sesbania Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 238000009825 accumulation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- FYSNRPHRLRVCSW-UHFFFAOYSA-N dodecasodium;tetraborate Chemical class [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] FYSNRPHRLRVCSW-UHFFFAOYSA-N 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
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005360 mashing 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
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 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
- 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
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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/695—Pore distribution polymodal
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 macropore alumina supporter, including following content: (1) being mixed with beating boehmite and deionized water, the mixed acid solution of appropriate organic acid and inorganic acid is added in Xiang Shangshu slurries, be heated to reflux processing；(2) appropriate urea is added and carries out hydro-thermal process, then washed, dry, treated boehmite obtains alumina support through molding, drying and roasting；(3) polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, spray on the alumina support that step (2) obtains according to the sequence of concentration from high to low；(4) alumina support after step (3) dipping is subjected to hydro-thermal charing process, then dries, obtains carbon containing macropore alumina supporter.The alumina support of this method preparation has large hole appearance and aperture, carbon content are radially in uneven distribution in carrier, 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 with large hole appearance, aperture
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 physics reaming is added
Often the intensity of carrier is impacted when agent.In addition, between the alumina support and active component of prior art preparation mutually
Effect remains to be further improved.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of preparation method of carbon containing macropore alumina supporter, this method
The alumina support of preparation has large hole appearance and aperture, carbon content are radially in uneven distribution in carrier, which is suitable for
Prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
The preparation method of carbon containing macropore alumina supporter of the invention, including following content:
(1) boehmite and deionized water are mixed with beating, appropriate organic acid and inorganic acid is added in Xiang Shangshu slurries
Mixed acid solution, control slurries pH value be 2-5, carry out being heated to reflux processing；(2) appropriate urea is added in Xiang Shangshu slurries
Carry out hydro-thermal process, the slurries after hydro-thermal process are washed, dry, treated boehmite through molding, drying and roasting,
Obtain alumina support；(3) prepare at least two various concentrations polyalcohol and/or monosaccharide aqueous solution, according to concentration by height to
Low sequence sprays on the alumina support that step (2) obtains, so that the concentration of polyalcohol and/or monosaccharide is formed on carrier
Ecto-entad is in gradient distribution from low to high；(4) alumina support after step (3) dipping is subjected to water in sealing container
Hot charing process, is then dried, and obtains carbon containing macropore alumina supporter.
In the method for the present invention, it is mixed with beating process described in step (1) and is carried out using conventional method in that art, intends thin water aluminium
Stone and the mass ratio of deionized water are preferably 1:3-1:10.The organic acid be one of acetic acid, oxalic acid or citric acid or
Several mixing, the inorganic acid are the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid；Organic acid in mixed acid solution
The mass ratio of the material with inorganic acid is 1:3-1:6, and the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid.It is described to add
Hot reflow treatment temperature is 30-60 DEG C, and being heated to reflux the time is 1-5 hours.
In the method for the present invention, the mass ratio of amount of urea described in step (2) and boehmite is 1:5-1:10.Adding
Preferably while borate is added while entering urea, the borate can be metaborate, ortho-borate and multi-borate
One or more of mixing, the additional amount of borate is 0.5:100-1.5 with the mass ratio of boehmite in terms of boron oxide:
100。
In the method for the present invention, hydro-thermal process described in step (2) is the heat treatment under the self-generated pressure of autoclave,
Treatment temperature is 120-160 DEG C, and the processing time is 4-8 hours.
In the method for the present invention, drying temperature described in step (2) is 100-120 DEG C, and drying time is 6-10 hours.
In the method for the present invention, molding, drying and roasting described in step (2) 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: 60-130 DEG C of drying temperature, drying time is 1-10 hours.Described
500-750 DEG C of maturing temperature of roasting roasts 2-10 hours.
In the method for the present invention, polyalcohol described in step (3) 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 (3) and/or monosaccharide aqueous solution is 5%-50%.
In the method for the present invention, described in step (3) 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 (3) 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 (3) 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 (3) 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 (4) 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.
In the method for the present invention, drying condition described in step (4) are as follows: drying temperature is 80-120 DEG C, drying time 2-
10 hours.
Can there are the unformed phase hydrated alumina in part, this partially hydrated alumina pore in boehmite preparation process
Appearance, aperture are lower, will affect final carrying alumina body opening appearance and macropore content.
The method of the present invention is first handled boehmite with mixed acid solution, since mixed acid and boehmite are made
With more moderate, it can not only overcome and dissolve amorphous phase hydrated alumina halfway deficiency when organic acid is used alone, but also can be with
It avoids damaging boehmite duct when inorganic acid is used alone, by nothing while guaranteeing boehmite pore structure
Setting phase hydrated alumina dissolution is removed.Dissolved aluminium salt is retained in slurries, then urea and sealing water are added into slurries
When heat treatment, urea is decomposed into NH under high temperature environment3And CO2, NH3And CO2NH is generated in the presence of water vapour4 +With
HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, regrows boehmite crystal grain and crystallization, makes to intend thin
Diaspore crystal grain is grown up, and the accumulation mode of crystal grain is changed, and improves the content of macropore, while the Al dissolved3+Following reaction occurs:
NH4Al(OH)2CO3Gas is generated when roasting can play good reaming effect.Be added borate when borate with
Double hydrolysis occur for aluminium salt, form boron-aluminium-oxygen composite oxide, compared with infusion process and kneading method introduce boron, more effectively
The modulation pore structure and surface nature of carrier.
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 ~
4 hours, finally product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test.Wherein surface area 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
Weigh 200g boehmite dry glue powder (production of Wenzhou essence crystal alumina Co., Ltd) set in a round bottom flask, to
600 grams of deionized water mashing are added in flask, it is 3mol/L, acetic acid mole that appropriate nitric acid molar concentration, which is added, in Xiang Shangshu slurries
Concentration is the mixed acid solution of 1mol/L, and the pH value for controlling slurries is 3 and is heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are turned
Enter in autoclave, 20 grams of urea are added into mixed material and are heat-treated 6 hours after sealing autoclave in 140 DEG C.It is cooled to
Mixed serum is filtered after room temperature, is washed, 120 DEG C of dryings, 8 hours obtained boehmites.Treated boehmite and 8g
Sesbania powder is sufficiently mixed, and is added uniform dissolved with the aqueous solution kneading of 4g acetic acid in right amount in Xiang Shangshu material, is extruded into cylindrical bars.Molding
Wet stock afterwards is 8 hours dry in 110 DEG C, 600 DEG C of roastings, 8 hours obtained alumina supports.
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
It is 3 hours dry at DEG C, oxidation carrier S1 is made, support is shown in Table 1.
Embodiment 2
With embodiment 1, only the additional amount of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol sulfuric acid and 1mol grass
The mixed acid of acid, the pH value for controlling slurries is 2, and the temperature being heated to reflux is 30 DEG C, is flowed back 5 hours.The additional amount of urea is 30
Gram, hydro-thermal process temperature is 120 DEG C, hydro-thermal process 8 hours.Alumina support is clover bar shaped, for the first time when spray dipping
With the aqueous solution for the sorbierite that 30ml mass concentration is 30%, the sorb that second of spray is 10% with 50ml mass concentration when impregnating
The aqueous solution of alcohol, the aqueous solution for the sorbierite that when third time spray dipping is 5% with 20ml mass concentration, temperature when charing process
It is 200 DEG C, carbonization time is 8 hours, and alumina support S2 is made, and the property of carrier is shown in Table 1.
Embodiment 3
With embodiment 1, only the additional amount of deionized water is 2000 grams.Mixed acid is dissolved with 6mol/L sulfuric acid and 1mol/L
The mixed acid of citric acid, the pH value for controlling slurries is 5, and being heated to reflux temperature is 60 DEG C, return time 1 hour.Urea additional amount
It is 40 grams, 160 DEG C of hydro-thermal process temperature, hydrothermal conditions are 4 hours.The Portugal for being 1:1 with the mass ratio that mass concentration is 30%
The mixed aqueous solution of grape sugar and ribose impregnates boehmite 5 hours.Charing process temperature is 120 DEG C, and the charing process time is
16 hours.It is impregnated using four sprays, the aqueous solution for the mannitol for being for the first time 50% with 20ml mass concentration when spray dipping,
The aqueous solution for the sorbierite for being 30% with 40ml mass concentration when spraying dipping for the second time, third time spray when impregnating with 20ml matter
Measure concentration be 20% sorbierite aqueous solution, the 4th time spray dipping when with 20ml mass concentration be 10% sorbierite it is water-soluble
Liquid.Temperature is 240 DEG C when charing process, and carbonization time is 12 hours, and alumina support S3 is made, and the property of carrier is shown in Table 1.
Embodiment 4
With embodiment 1,3.0 grams of sodium tetraborates are added into mixed material while urea is only added.Using spraying twice
Leaching dipping, the aqueous solution for the arabite for being for the first time 40% with 50ml mass concentration when spray dipping, second of spray dipping
When with 55ml mass concentration be 20% arabite aqueous solution, carbonization temperature be 250 DEG C, carbonization time be 6 hours, system
Alumina support S4 is obtained, the property of carrier is shown in Table 1.
Embodiment 5
With embodiment 1, alumina support is bunge bedstraw herb bar shaped, xylitol change into the xylitol that mass ratio is 1:1:1:1, Ah
Draw the mixing alcohol solution dipping of primary sugar alcohol, sorbierite and mannitol, temperature is 220 DEG C when charing process, and the processing time is 10
Hour, alumina support S5 is made, the property of carrier is shown in Table 1.
Comparative example 1
With embodiment 1, only the unmixed acid processing of boehmite and urea liquid seal hydro-thermal process, and oxidation is made
The property of alumina supporter S6, carrier are shown in Table 1.
Comparative example 2
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 alumina support S7 is made, and the property of carrier is shown in Table 1.
Comparative example 3
With embodiment 1, only the unmixed acid processing of boehmite, is made alumina support S8, the property of carrier is shown in
Table 1.
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, the carbon containing macropore alumina supporter prepared using the method for the present invention is same with larger aperture
When have biggish Kong Rong, the pore size distribution of concentration, carbon content is radially in uneven distribution in alumina support.This method preparation
Alumina support 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 catalysis of catalyst C1-C7 is evaluated on 200 milliliters of hydrogenation reaction device
Performance, catalyst are long 2 ~ 3 millimeters of item, and catalyst loading is 100 milliliters, and reaction temperature is 380 DEG C, hydrogen partial pressure 14MPa,
Liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio 1000, measurement generates the content of each impurity in oil, meter after reaction 300 hours
Removal efficiency is calculated, evaluation result is 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 (6)
1. a kind of preparation method of carbon containing macropore alumina supporter, it is characterised in that including following content: (1) by boehmite
It is mixed with beating with deionized water, the mixed acid solution of organic acid and inorganic acid is added in Xiang Shangshu slurries, controls the pH value of slurries
For 2-5, carry out being heated to reflux processing；(2) urea is added in Xiang Shangshu slurries and carries out hydro-thermal process, the slurries warp after hydro-thermal process
Washing, dry, the boehmite that obtains that treated, treated boehmite is aoxidized through molding, drying and roasting
Alumina supporter；(3) 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 the alumina support that step (2) obtains, so that the concentration of polyalcohol and/or monosaccharide forms ecto-entad on carrier
In gradient distribution from low to high；(4) alumina support after step (3) dipping is carried out at hydro-thermal charing in sealing container
Reason, then dries, obtains carbon containing macropore alumina supporter；Organic acid described in step (1) is in acetic acid, oxalic acid or citric acid
One or more mixing, the inorganic acid are the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid；In mixed acid solution
The mass ratio of the material of organic acid and inorganic acid is 1:3-1:6, and the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid；
Step (1) treatment temperature that is heated to reflux is 30-60 DEG C, and being heated to reflux the time is 1-5 hours；Hydro-thermal described in step (2)
Processing is the heat treatment under the self-generated pressure of autoclave, and treatment temperature is 120-160 DEG C, and the processing time is 4-8 hours；
Polyalcohol described in step (3) is one or more of xylitol, sorbierite, mannitol or arabite；The monosaccharide
For one or more of glucose, ribose or fructose；The mass concentration of the polyalcohol and/or monosaccharide aqueous solution is 5%-
50%；Described in step (3) according to concentration from high to low spray sequence, adjacent polyalcohol twice and/or monosaccharide aqueous solution it is dense
Degree difference is 5%-30%；Hydro-thermal charing process temperature described in step (4) is 180-250 DEG C, and hydrothermal conditions are 6-12 hours,
Hydro-thermal process pressure is self-generated pressure.
2. according to the method for claim 1, it is characterised in that: amount of urea described in step (2) and boehmite
Mass ratio is 1:5-1:10.
3. according to the method for claim 1, it is characterised in that: borate is added while urea is added in step (2), institute
The borate stated is the mixing of one or more of metaborate, ortho-borate and multi-borate, and the additional amount of borate is with oxygen
The mass ratio for changing boron meter and boehmite is 0.5:100-1.5:100.
4. according to the method for claim 1, it is characterised in that: the maceration extract dosage sprayed every time described in step (3) 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.
5. according to the method for claim 1, it is characterised in that: step (3) 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.
6. according to the method for claim 1, it is characterised in that: alumina support described in step (3) is graininess；It is described
Alumina support in one or more of Si, Ti, Zr, B or F auxiliary element is added.
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|---|---|---|---|---|
| US6027706A (en) * | 1998-05-05 | 2000-02-22 | Board Of Trustees Operating Michigan State University | Porous aluminum oxide materials prepared by non-ionic surfactant assembly route |
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| CN102861590A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6027706A (en) * | 1998-05-05 | 2000-02-22 | Board Of Trustees Operating Michigan State University | Porous aluminum oxide materials prepared by non-ionic surfactant assembly route |
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| CN102861590A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| 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 |
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