CN107303509A - 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
- Publication number
- CN107303509A CN107303509A CN201610252529.1A CN201610252529A CN107303509A CN 107303509 A CN107303509 A CN 107303509A CN 201610252529 A CN201610252529 A CN 201610252529A CN 107303509 A CN107303509 A CN 107303509A
- Authority
- CN
- China
- Prior art keywords
- acid
- alumina support
- polyalcohol
- aqueous solution
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007598 dipping method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 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
- 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 10
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 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
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- 238000005360 mashing Methods 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910017604 nitric acid 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
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 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
- 235000006408 oxalic acid 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
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 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-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
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 210000000476 body water Anatomy 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 241000219782 Sesbania Species 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007812 deficiency Effects 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
- 230000002779 inactivation Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- -1 sorbierite Chemical compound 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis 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
- 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
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 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
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 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
- 238000005516 engineering process 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
- 150000002431 hydrogen Chemical class 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
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004537 pulping 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
- 238000005245 sintering Methods 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
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- B01J35/695—
Abstract
The invention discloses a kind of preparation method of carbon containing macropore alumina supporter, including following content：（1）Boehmite is mixed into mashing with deionized water, the mixed acid solution of appropriate organic acid and inorganic acid is added into above-mentioned slurries, processing is heated to reflux；（2）Add appropriate urea and carry out hydro-thermal process, then scrubbed, dry, the boehmite after processing obtains alumina support through shaping, dry and roasting；（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 obtained alumina support；（4）By step（3）Alumina support after dipping carries out hydro-thermal charing process, then dries, obtains carbon containing macropore alumina supporter.Alumina support prepared by this method has larger pore volume and aperture, 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, relate in particular to a kind of with larger pore volume, aperture
Carbon containing alumina support preparation method.
Background technology
At present, in the production process of mink cell focus HDM, because feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Deng impurity, deposition is easily formed, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, in addition inactivation, influence
Commercial Application.Catalyst with larger pore volume and larger bore dia holds metal and holds coke formation by force, can slow down catalyst
The service cycle for inactivating, making catalyst extends.The pore structure of catalyst is determined by the carrier for constituting catalyst, therefore, prepares tool
The carrier for having larger pore volume and larger bore dia is to prepare residual oil, especially prepare the decompression residuum higher for tenor and add
The key of hydrogen catalyst for demetalation.In addition, after load active component in roasting process, active metal component is easily and aluminum oxide
Carrier has an effect to form very strong M-O-Al keys, causes active component formation Spinel and loses activity, or makes activity
Component can not complete cure so as 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 boehmite dry glue powder to be mixed with water or the aqueous solution,
Plastic is kneaded into, obtained plastic is extruded into bar on banded extruder, dries and is calcined and obtain product, is characterized in,
Carbon powder is additionally added in above process as physics expanding agent and can occur chemical action with boehmite or aluminum oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.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, to
It is 4.3% aqueous solution of nitric acid kneading 30 minutes that mass fraction is added in said mixture, and it is 2.1% then to add mass fraction
Ammonia spirit kneading 25 minutes, extruded moulding after kneading is uniform, the fired obtained final alumina support of carrier after shaping.Its
The addition of middle 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 such as
Under：（1）Boehmite dry glue powder and extrusion aid are well mixed, then add and have dissolved physics expanding agent and chemical enlargement agent
The aqueous solution；（2）By step（1）Resulting material is well mixed, the extruded moulding on banded extruder；（3）By step（2）Resulting material is done
Final alumina support is made in dry, roasting.
In summary, prior art prepares usually used physics expanding agent and chemical enlargement during macropore alumina supporter
Agent improves the aperture of carrier, and the addition of expanding agent can make the increase of alumina support macropore content really.But add physics reaming
Intensity during agent often to carrier is impacted.In addition, between alumina support and active component prepared by prior art mutually
Effect 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 carbon containing macropore alumina supporter, this method
The alumina support of preparation has larger pore volume and aperture, 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.
The preparation method of the carbon containing macropore alumina supporter of the present invention, including following content：
（1）Boehmite is mixed into mashing with deionized water, the mixed of appropriate organic acid and inorganic acid is added into above-mentioned slurries
Acid solution is closed, the pH value for controlling slurries is 2-5, progress is heated to reflux processing；（2）Appropriate urea is added into above-mentioned slurries to carry out
Slurries after hydro-thermal process, hydro-thermal process are scrubbed, dry, and the boehmite after processing is obtained through shaping, dry and roasting
Alumina support；（3）Prepare the polyalcohol and/or the monose aqueous solution of at least two various concentrations, according to concentration from high to low
Order is sprayed in step（2）On obtained alumina support so that the concentration of polyalcohol and/or monose is formed by outer on carrier
Inwardly in gradient distribution from low to high；（4）By step（3）Alumina support after dipping carries out hydro-thermal charcoal in sealing container
Change is handled, and is then dried, is obtained carbon containing macropore alumina supporter.
In the inventive method, step（1）Described mixing pulping process is carried out using this area conventional method, intends thin water aluminium
Stone and the mass ratio of deionized water are preferably 1:3-1:10.Described organic acid be acetic acid, oxalic acid or citric acid in one kind or
Several mixing, described inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；Organic acid in mixed acid solution
Amount ratio with the material of inorganic acid is 1:3-1:6, 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, is heated to reflux the time for 1-5 hours.
In the inventive method, step（2）Described amount of urea and the mass ratio of boehmite are 1:5-1:10.Adding
Preferably while adding borate, described borate can be metaborate, ortho-borate and multi-borate while entering urea
In one or more of mixing, the addition of borate counts the mass ratio with boehmite as 0.5 using boron oxide:100-1.5:
100。
In the inventive method, step（2）Described hydro-thermal process is the heat treatment under the self-generated pressure of autoclave,
Treatment temperature is 120-160 DEG C, and processing time is 4-8 hours.
In the inventive method, step（2）Described drying temperature is 100-120 DEG C, and drying time is 6-10 hours.
In the inventive method, step（2）Described being molded, dry and be calcined can be carried out using this area conventional method.
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., and described extrusion aid refers to be conducive to squeezing
One or more in molded material, such as sesbania powder, carbon black, graphite powder, citric acid, the consumption of extrusion aid accounts for total material
1wt%~10wt% of butt.Described drying condition is：60-130 DEG C of drying temperature, drying time is 1-10 hours.Described
500-750 DEG C of sintering temperature is calcined, is calcined 2-10 hours.
In the inventive method, step（3）Described polyalcohol includes xylitol, sorbierite, mannitol or arabite etc.
In one or more；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, adjacent polyalcohol twice
And/or the concentration difference of the monose aqueous solution is 5%-30%, preferably 10%-20%；It is preferred that prepare 2-4 kind various concentrations polyalcohol and/
Or the monose aqueous solution.
In the inventive method, step（3）The described maceration extract consumption sprayed every time is alumina support saturated water adsorptive value
10%-60%, preferably 20%-30%, the total consumption of maceration extract repeatedly sprayed for alumina support saturated water adsorptive value to ensure oxygen
Change alumina supporter saturation dipping.
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
Leaching, detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, polyalcohol and/
Or the 20%-30% that the consumption of the monose aqueous solution is alumina support water absorption；Spray for the second time, polyalcohol and/or monose are water-soluble
The mass concentration of liquid is 10%-30%, and 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%, polyalcohol and/or the monose aqueous solution use
Measure as 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
Shape, trilobal, quatrefoil etc.）Or piece shape, preferably bar shaped or spherical, more preferably bar shaped.Also may be used in described alumina support
To add the one or more in the auxiliary elements such as Si, Ti, Zr, B or F as needed.
In the inventive method, step（4）Described hydro-thermal charing process temperature 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 ensure that polyalcohol and/or monose are carbonized completely.Wherein, self-generated pressure is relevant 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 inventive method, step（4）Described drying condition is：Drying temperature is 80-120 DEG C, and drying time is 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 relatively low, can influence final alumina support pore volume and macropore content.
The inventive method is first handled boehmite with mixed acid solution, due to mixed acid and boehmite work
With more moderate, the halfway deficiency of amorphous phase hydrated alumina is dissolved when can both overcome exclusive use organic acid, again can be with
Avoid damaging boehmite duct when inorganic acid is used alone, by nothing while boehmite pore structure is ensured
The hydrated alumina dissolving of setting phase is removed.Aluminium salt after dissolving is retained in slurries, then is added urea into slurries and sealed water
During heat treatment, urea is decomposed into NH in high temperature environments3And CO2, NH3And CO2NH is generated in the presence of water vapour4 +With
HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, makes boehmite crystal grain regrow and crystallization, makes plan thin
Diaspore crystal grain is grown up, and is changed the accumulation mode of crystal grain, is improved the content of macropore, while the Al of dissolving3+Occurs following reaction：
NH4Al(OH)2CO3Gas is produced during roasting can play good reaming effect.Borate and aluminium salt when adding borate
Occur double hydrolysis, form boron-aluminium-oxygen composite oxide, compared with infusion process and kneading method introduce boron, more effective modulation
The pore structure and surface nature of carrier.
When polyalcohol and/or the monose aqueous solution spray dipping of shaping carrier various concentrations, polyalcohol and/or monose
Concentration, in incremental distribution, is carbonized by carrier surface to center by hydro-thermal, and gradient point is formed on carrier surface and duct inwall
The relatively thin internal carbon-coating of carbon-coating is thicker outside the carbon-coating of cloth, i.e. carrier.Because the presence of carbon-coating effectively prevents metal component and load
Strong interaction between body, the gradient distribution of carbon layers having thicknesses, acts between active metal and carrier and gradually weakening from outside to inside,
I.e. catalyst activity is gradually stepped up from outside to inside, during HDM, promotes the reaction inside catalyst duct, has
Effect is avoided makes demetalization reaction acutely cause catalyst duct to block and make to urge because active component activity in outer surface is higher
The phenomenon of agent inactivation, extends the service life of catalyst while catalyst activity is improved.
Embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following implementation
Example.
Using N2Physics suction-desorption characterizes embodiment and comparative example carrier pore structure, and concrete operations are as follows：Using ASAP-
2420 type N2Physics is inhaled-is desorbed instrument and catalyst sample pore structure is characterized.Take a small amount of sample at 300 DEG C application of vacuum 3 ~
4 hours, product is finally placed in liquid nitrogen cryogenics（-200℃）Under the conditions of carry out nitrogen suction-desorption test.Wherein surface area according to
BET equations are obtained, 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：Using JEOL's JXA-8230 electronics
Probe is measured, and the accelerating potential selected during measure is 15KV, and probe current is 8 × 10-8A, beam spot size is 3 μm.Respectively
Measure 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 are the distance of line segment between any point in alumina support cross-section center and cross section outer most edge（Essence
On be cross section radius）, then by division calculation, obtain the ratio between each content.
Embodiment 1
Weigh 200g boehmite dry glue powders（The production of Wenzhou essence crystal alumina Co., Ltd）It is placed in round-bottomed flask, to flask
It is middle to add 600 grams of deionized water mashing, appropriate nitric acid molar concentration is added into above-mentioned slurries for 3mol/L, acetic acid molar concentration
For 1mol/L mixed acid solution, the pH value for controlling slurries is 3 and is heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are transferred to height
Press in kettle, 20 grams of urea are added into mixed material and are heat-treated autoclave sealing 6 hours after 140 DEG C.It is cooled to room temperature
Mixed serum is filtered afterwards, washed, 120 DEG C of dryings, 8 hours obtained boehmites.Boehmite and 8g sesbanias after processing
Powder is sufficiently mixed, and the appropriate aqueous solution kneading dissolved with 4g acetic acid is added into above-mentioned material uniformly, cylindrical bars are extruded into.After shaping
Wet stock is dried 8 hours in 110 DEG C, 600 DEG C of roastings, 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, to be atomized
Carrier of the mode into rolling pot sprays the xylose alcohol solution 25ml that impregnating effect concentration is 40%；Then it is 20% with mass concentration
Xylose alcohol solution 40ml continue spray oxide impregnation alumina supporter；Finally with the xylose alcohol solution that mass concentration is 10%
40ml continues to spray oxide impregnation alumina supporter.Dipping terminates alumina support being transferred in autoclave and autoclave is placed in into baking oven
In in charing process 9 hours under 180 DEG C, self-generated pressure, naturally cool to room temperature.Alumina support after hydro-thermal process is in 120
Dried 3 hours at DEG C, oxidation carrier S1 is made, support is shown in Table 1.
Embodiment 2
Be the same as Example 1, simply the addition of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol sulfuric acid and 1mol oxalic acid
Mixed 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 addition of urea is 30 grams, water
Heat treatment temperature is 120 DEG C, hydro-thermal process 8 hours.Alumina support is clover bar shaped, uses 30ml during spray dipping for the first time
Mass concentration is the aqueous solution of 30% sorbierite, is sprayed for the second time when impregnating with water of the 50ml mass concentrations for 10% sorbierite
Solution, with the aqueous solution of the 20ml mass concentrations for 5% sorbierite during third time spray dipping, temperature is 200 during charing process
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
Be the same as Example 1, simply the addition of deionized water is 2000 grams.Mixed acid is dissolved with 6mol/L sulfuric acid and 1mol/L lemons
The mixed acid of acid, the pH value for controlling slurries is 5, and it is 60 DEG C, return time 1 hour to be heated to reflux temperature.Urea addition is 40
Gram, 160 DEG C of hydro-thermal process temperature, hydrothermal conditions are 4 hours.The mass ratio for being 30% with mass concentration is 1:1 glucose
Boehmite is impregnated with the mixed aqueous solution of ribose 5 hours.Charing process temperature is 120 DEG C, and the charing process time is 16 small
When.Impregnated using four sprays, for the first time with the aqueous solution of the 20ml mass concentrations for 50% mannitol, second during spray dipping
It is dense with 20ml mass during third time spray dipping with the aqueous solution of the 40ml mass concentrations for 30% sorbierite during secondary spray dipping
The aqueous solution of the sorbierite for 20% is spent, 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, and alumina support S3 is made, and the property of carrier is shown in Table 1.
Embodiment 4
Be the same as Example 1,3.0 grams of sodium tetraborates are added into mixed material while simply adding urea.Using spray leaching twice
Stain, is used during spray dipping with the aqueous solution of the 50ml mass concentrations for 40% arabite during second of spray dipping for the first time
55ml mass concentrations are the aqueous solution of 20% arabite, and carbonization temperature is 250 DEG C, and carbonization time is 6 hours, and oxygen is made
Change alumina supporter S4, the property of carrier is shown in Table 1.
Embodiment 5
Be the same as Example 1, alumina support is bunge bedstraw herb bar shaped, and it is 1 that xylitol, which changes mass ratio into,:1:1:1 xylitol, Arab
The mixing alcohol solution dipping of sugar alcohol, sorbierite and mannitol, temperature is 220 DEG C during charing process, and processing time is 10 hours,
Alumina support S5 is made, the property of carrier is shown in Table 1.
Comparative example 1
Be the same as Example 1, simply the unmixed acid treatment of boehmite and urea liquid sealing hydro-thermal process, are made carrying alumina
Body S6, the property of carrier is shown in Table 1.
Comparative example 2
Be the same as Example 1, simply xylitol is not that multiple spray is impregnated into alumina support, but by same amount of xylitol with
The mode for once spraying dipping is impregnated into alumina support, and alumina support S7 is made, and the property of carrier is shown in Table 1.
Comparative example 3
Alumina support S8 is made in be the same as Example 1, the simply unmixed acid treatment of boehmite, 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 carbon containing macropore alumina supporter prepared using the inventive method, with the same of larger aperture
When there is larger pore volume, the pore size distribution of concentration, carbon content is in radially uneven distribution in alumina support.Prepared by this method
Alumina support 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 added3
Solution（Containing MoO312.0wt%, NiO3.0 wt%）Dipping 2 hours, filters off redundant solution, and 120 DEG C dry, then in 550 DEG C of temperature
It is calcined 5 hours in lower nitrogen atmosphere, obtains Hydrodemetalation catalyst C1-C7.
Embodiment 7
The following examples illustrate to take carrier and comparative example aluminum oxide as HDM prepared by carrier of aluminum oxide of the present invention
The catalytic performance of catalyst.
Using feedstock oil listed by table 2 as raw material, catalyst C1-C7 catalysis is evaluated on 200 milliliters of hydrogenation reaction device
Performance, catalyst is long 2 ~ 3 millimeters bar, and catalyst loading amount is 100 milliliters, and reaction temperature is 380 DEG C, and hydrogen dividing potential drop is 14MPa,
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, meter after 300 hours
Removal efficiency is calculated, 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 tool prepared by carrier of aluminum oxide of the present invention
There is higher HDM activity.
Claims (12)
1. a kind of preparation method of carbon containing macropore alumina supporter, it is characterised in that including following content：（1）By boehmite
Mashing is mixed with deionized water, the mixed acid solution of organic acid and inorganic acid is added into above-mentioned slurries, the pH value of slurries is controlled
For 2-5, progress is heated to reflux processing；（2）Urea is added into above-mentioned slurries and carries out the slurries warp after hydro-thermal process, hydro-thermal process
Washing, dry, the boehmite after being handled, the boehmite after processing are aoxidized through shaping, dry and roasting
Alumina supporter；（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, according to the order of concentration from high to low
Spray in step（2）On obtained alumina support so that the concentration of polyalcohol and/or monose forms ecto-entad on carrier
In gradient distribution from low to high；（4）By step（3）Alumina support after dipping is carried out at hydro-thermal charing in sealing container
Reason, then dries, obtains carbon containing macropore alumina supporter.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described organic acid is acetic acid, oxalic acid or lemon
One or more of mixing in acid, described inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；Mixed acid is molten
The amount ratio of the material of organic acid and inorganic acid in liquid is 1:3-1:6, the concentration of the mixed acid solution is calculated as 3- with inorganic acid
6mol/L。
3. in accordance with the method for claim 1, it is characterised in that：Step（1）The treatment temperature that is heated to reflux is 30-60
DEG C, the time is heated to reflux for 1-5 hours.
4. in accordance with the method for claim 1, it is characterised in that：Step（2）Described amount of urea and boehmite
Mass ratio is 1:5-1:10.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）Boric acid is added while urea is added simultaneously
Salt, described borate is one or more of mixing in metaborate, ortho-borate and multi-borate, the addition of borate
Mass ratio with boehmite is counted as 0.5 using boron oxide:100-1.5:100.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）Described hydro-thermal process is in autoclave
Self-generated pressure under heat treatment, treatment temperature be 120-160 DEG C, processing time be 4-8 hours.
7. in accordance with the method for claim 1, it is characterised in that：Step（3）Described polyalcohol be xylitol, sorbierite,
One or more in mannitol or arabite；Described monose is the one or more in glucose, ribose or fructose；Institute
The polyalcohol and/or the mass concentration of the monose aqueous solution stated are 5%-50%.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Described the spraying from high to low according to concentration
Sequentially, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5%-30%.
9. 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, the total consumption of maceration extract repeatedly sprayed is the saturated water adsorptive value of alumina support
To ensure that alumina support saturation impregnates.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Prepare 3 kinds of various concentrations polyalcohol and/or
The monose aqueous solution is sprayed, and detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is
The consumption of 30%-50%, polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption；Spray for the second time, it is many
The mass concentration of first alcohol and/or monose aqueous solution is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is carrying alumina
The 40%-60% of body water absorption；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, polyalcohol
And/or the 10%-40% that the consumption of the monose aqueous solution is alumina support water absorption.
11. in accordance with the method for claim 1, it is characterised in that：Step（3）Described alumina support is graininess；Institute
The one or more added in the alumina support stated in Si, Ti, Zr, B or F auxiliary element.
12. 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, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252529.1A CN107303509B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of carbon containing macropore alumina supporter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252529.1A CN107303509B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of carbon containing macropore alumina supporter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107303509A true CN107303509A (en) | 2017-10-31 |
| CN107303509B CN107303509B (en) | 2019-09-10 |
Family
ID=60152882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610252529.1A Active CN107303509B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of carbon containing macropore alumina supporter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107303509B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190123155A (en) * | 2018-04-23 | 2019-10-31 | 효성화학 주식회사 | Preparation method of alumina support |
| CN114653354A (en) * | 2020-12-23 | 2022-06-24 | 中国石油化工股份有限公司 | Preparation method of carbon-containing alumina carrier |
Family Cites Families (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 |
| CN103785400B (en) * | 2012-11-01 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst |
-
2016
- 2016-04-21 CN CN201610252529.1A patent/CN107303509B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190123155A (en) * | 2018-04-23 | 2019-10-31 | 효성화학 주식회사 | Preparation method of alumina support |
| KR102090234B1 (en) * | 2018-04-23 | 2020-03-18 | 효성화학 주식회사 | Preparation method of alumina support |
| CN114653354A (en) * | 2020-12-23 | 2022-06-24 | 中国石油化工股份有限公司 | Preparation method of carbon-containing alumina carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107303509B (en) | 2019-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107303490B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN107303485B (en) | A kind of preparation method of modified aluminium oxide supports | |
| CN103785400B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
| CN106140182B (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
| CN107303484B (en) | A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter | |
| CN108745392B (en) | Hydrodemetallization catalyst and preparation method thereof | |
| CN105709711B (en) | A kind of preparation method of alumina support | |
| CN106000476B (en) | The preparation method of boron modification aluminium oxide | |
| CN103785401A (en) | Preparation method of hydrodemetalization catalyst for residuum | |
| CN102861615B (en) | Preparation method of macroporous alumina carrier | |
| CN1123392C (en) | Alumina carrier containing Ni and its preparing process | |
| CN107303509A (en) | A kind of preparation method of carbon containing macropore alumina supporter | |
| CN107304062B (en) | A kind of preparation method of alumina support | |
| CN107303492A (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN107303491B (en) | The preparation method of Hydrodemetalation catalyst | |
| CN102861588B (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN105618072B (en) | The preparation method of Hydrodemetalation catalyst | |
| CN111375438A (en) | Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| JP3264813B2 (en) | Hydrodemetallation catalyst and its preparation | |
| CN111821990B (en) | Residual oil hydrogenation protective agent carrier, catalyst and preparation method thereof | |
| CN107303510B (en) | A kind of preparation method of carbon containing alumina support | |
| CN109722280A (en) | A kind of carrier for hydrotreating, catalyst and its preparation method and application | |
| CN105582947B (en) | A kind of preparation method of carbon containing residuum hydrogenating and metal-eliminating catalyst | |
| CN107297215B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN105582949B (en) | A kind of high-activity hydrodemetallizationcatalyst catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |