CN106311263A - Highly-supported modified boron hydrofining catalyst and the preparation method thereof - Google Patents
Highly-supported modified boron hydrofining catalyst and the preparation method thereof Download PDFInfo
- Publication number
- CN106311263A CN106311263A CN201610614764.9A CN201610614764A CN106311263A CN 106311263 A CN106311263 A CN 106311263A CN 201610614764 A CN201610614764 A CN 201610614764A CN 106311263 A CN106311263 A CN 106311263A
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- CN
- China
- Prior art keywords
- catalyst
- alumina
- boron
- high capacity
- boron modification
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001638 boron Chemical class 0.000 title abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 229910052796 boron Inorganic materials 0.000 claims abstract description 67
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims description 41
- 230000004048 modification Effects 0.000 claims description 41
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 34
- 239000004327 boric acid Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000001125 extrusion Methods 0.000 claims description 21
- 238000005470 impregnation Methods 0.000 claims description 18
- 229910001593 boehmite Inorganic materials 0.000 claims description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Chemical group 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000000470 constituent Substances 0.000 abstract 3
- 239000013078 crystal Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012752 auxiliary agent Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 229910003296 Ni-Mo Inorganic materials 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 7
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/615—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Abstract
The invention discloses a highly-supported modified boron hydrofining catalyst and the preparation method thereof. The catalyst is composed of an active metal constituent and a supporter. The active metal constituent is loaded on the supporter. The active metal constituent is composed of the oxide containing two metals, namely, VIB metal group and VIII metal group, wherein VIB metal group is MO and/or W, and VIII metal group is Ni and/or Co; the supporter is modified alumina supporter of boron. In the modified boron hydrofining catalyst prepared using the method hereof, B2O3 distributes evenly and focuses on the surface of the alumina supporter, and can prevent the active component from entering the crystal lattice of alumina, thereby improving the dispersion degree and utilization ratio of the metal component, and further improving the hydrogenation activity of the catalyst. Highly-supported boron-loaded hydrofining catalyst can be obtained from the modified boron hydrofining catalyst, and the boron-loaded hydrofining catalyst has higher activity in denitrification.
Description
Technical field
The present invention relates to catalyst and preparation method thereof, in particular to a kind of high capacity amount boron modification Hydrobon catalyst
And preparation method thereof.
Background technology
Typical Hydrobon catalyst is typically made up of alumina support and hydrogenation active metals.Hydrogenation active metals is
Vib and/or group VIII metal, conventional vib metals is Mo and/or W, and group VIII metal is Co and/or Ni.
Aluminium oxide, as a kind of carrier material, has purposes widely in hydrogenation catalyst field.But owing to alumina acidic is the most weak, and
Easy and active metal component generation strong interaction generates inactive species, thus affects activity and the stability of catalyst.For
Improve the acidity of aluminium oxide and regulate the active force of itself and metal component, often through introducing the auxiliary agents pair such as Si, P, Ti, B, F
Aluminium oxide is modified processing.
Boron is mainly reflected in raising and the raising of metal dispersity of denitrification activity to the impact of Hydrobon catalyst, from
And improve the hydrogenation activity of catalyst for refining.Document (Lewandowski M, Fuel, 2000,79,487) have studied auxiliary agent boron pair
The impact of Hydrobon catalyst hydrodenitrogenationactivity activity, it was found that along with the increase of boron load capacity, the hydrodenitrogeneration of catalyst
Activity gradually steps up, and the deactivation rate of catalyst slows down.Auxiliary agent boron has deepened hydrogenation reaction degree, and this is owing to boron is at aluminium oxide
Surface forms B2O3, promote the sulfuration of catalyst, decrease the carbon deposition quantity in hydrogenation process, improve active metal component
Dispersion.
Boron is as alumina modified auxiliary agent, and common adding method is divided into two kinds: a kind of is the process in carrier molding
Middle introducing boron, including coprecipitation and physical mixed method；Another kind is to be introduced by pre-preg after carrier molding.Boron typically with
H3BO3Form add on carrier, and H3BO3Dissolubility at room temperature be only 6g/100ml water, limit to a certain extent
The load capacity of boron.
The Chinese invention patent of Publication No. CN00122919.2 discloses a kind of hydrodenitrogenation catalyst and preparation side thereof
Method, catalyst is with aluminium oxide or silicon-containing alumina as carrier, with Mo-Ni as active component, adds boron additive.Steady by making
Fixed alkaline Mo-Ni-B solution, uses co-impregnation technology so that the hydrodenitrogenationactivity activity of catalyst is improved.This catalyst
Use step impregnation, introduce ammonia, pollute environment.
The Chinese invention patent of Publication No. CN00110018.1 discloses a kind of hydrogenation catalyst and preparation method thereof, should
Catalyst, with vib and group VIII metal as hydrogenation active component, supports the auxiliary agent such as boron, silicon, uses coprecipitation to prepare, and one
A little active metals cover possibly into body phase or oxidized alumina particles during co-precipitation and extrusion, the utilization of active metal
Rate reduces, and hydrogenation activity is relatively low.
The Chinese invention patent of Publication No. CN101491767A discloses the preparation method of a kind of hydrogenation catalyst, and this is urged
Auxiliary agent fluorine in agent carrier, silicon, phosphorus etc. are by two sections of additions during the plastic of dry glue powder and in carrier forming process
, active metal dispersion from the teeth outwards can be effectively improved, improve the utilization rate of active metal, and then improve making of catalyst
Use performance.In this catalyst, the content of auxiliary agent boron is only about 1%.
In patent disclosed above, all refer to the modification to Hydrobon catalyst of the auxiliary agent boron.Prior art exists
Problem has two aspects: one is to use conventional method to introduce auxiliary agent boron not produce useful to active metal component dispersion on carrier
Impact；Two is that the load capacity of auxiliary agent boron is relatively low, and the activity of catalyst hydrogenation denitrogenation is restricted.
Summary of the invention
The present invention is directed to deficiency of the prior art, it is provided that a kind of high capacity amount boron modification Hydrobon catalyst and system thereof
Preparation Method.Can not only make auxiliary agent boron that surface at alumina support is better distributed by this method, improve active component
Dispersion, additionally it is possible to be effectively improved boron load capacity in the catalyst, improves the hydrodenitrogenationactivity activity of catalyst.Prepared by the present invention
Hydrobon catalyst be particularly well-suited to the hydrofinishing of high-nitrogen raw oil.
For achieving the above object, a kind of high capacity amount boron modification Hydrobon catalyst that the present invention provides, described catalysis
Agent is made up of active metal component and carrier, and described active metal component is supported on carrier, and described active metal group is by containing
The oxide composition of vib and two kinds of metals of VIII, wherein, vib metals is Mo and/or W, and group VIII metal is
Ni and/or Co, described carrier is the alumina support of boron modification.
Further, in described catalyst, the oxide content containing vib metals is 8.9～30.1%, containing
The oxide content of group VIII metal is 1.9～10.1%, and in the alumina support of described boron modification, boron accounts for the quality of catalyst
Mark is 1.0～11.5%.
Yet further, the described oxide content containing vib metals is 15.0～26.0%, described group VIII
Metal is preferably Ni, and the oxide content containing Ni is 2.2～6.5%, and it is 2.0～4.0% that boron accounts for the mass fraction of catalyst.
Yet further, in described catalyst, the specific surface area of catalyst is 130～320m2/ g, total hole pore volume are 0.15
～0.50cm3/g。
Yet further, the specific surface area of described catalyst is 190～250m2/ g, total hole pore volume are 0.33～0.40cm3/
g。
Yet further, the preparation method of the alumina support of described boron modification, comprise the following steps:
1) weigh alumina precursor, extrusion aid and peptizer, roll through mixing, extrusion obtains alumina extrudate, then warp
Cross dry, roasting, obtain alumina support；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5～5.6%；
3) weigh step 1) alumina support that obtains is placed in hydrothermal treatment consists stove, pressure be 0～0.5mpa, temperature be
0.5～9h is reacted, then by step 2 under the conditions of 350～700 DEG C) boric acid aqueous solution prepared is passed through in stove, obtains boron modification
Alumina support.
Yet further, described step 1) in, described alumina precursor be amorphous hydroted alumina, false boehmite,
Any one or a few in boehmite, gibbsite, surge aluminum stone, promise diaspore, or fired after can be converted into γ-
Al2O3Aluminum oxide；Extrusion aid is citric acid and/or sesbania powder, and the quality of extrusion aid accounts for the 1.0 of carrying alumina weight
～5.0%；Peptizer is organic acid or inorganic aqueous acid, and organic acid is formic acid and/or acetic acid, and mineral acid is nitric acid, phosphorus
Acid, in hydrochloric acid any one or a few；In peptizer, the content of acid accounts for the 1.0～7.0% of carrying alumina weight.
Yet further, the quality of described extrusion aid accounts for the 2.0～3.5% of carrying alumina weight；Acid in peptizer
Content accounts for the 1.8～4.0% of carrying alumina weight.
Yet further, described step 1) in, baking temperature is 60～190 DEG C, and drying time is 0.1～22h；Roasting temperature
Degree is 300～650 DEG C, and roasting time is 3～6h.
Yet further, described step 1) in, baking temperature is 90～130 DEG C, and drying time is 1.5～8h；Roasting temperature
Degree is 420～540 DEG C, and roasting time is 3～6h.
Yet further, described step 1) in, alumina support is shaped as cylinder, Herba Trifolii Pratentis, Herba Galii Bungei or gear shape,
Wherein, the alumina support particle diameter of cylinder strip is 1.2～1.6mm, a length of 5～10mm；Herba Trifolii Pratentis or two leaves of Herba Galii Bungei
Spacing is 1.1～1.8mm, a length of 5～10mm.
Yet further, described step 3) in, when boric acid aqueous solution is passed through stove, the mass space velocity of boric acid aqueous solution is 0.1
～5.5h-1。
Yet further, the mass space velocity of described boric acid aqueous solution is 1.2～4.0h-1。
The invention provides the preparation method of a kind of high capacity amount boron modification Hydrobon catalyst, it is characterised in that bag
Include following steps:
1) weigh alumina precursor, extrusion aid and peptizer, roll through mixing, extrusion obtains alumina extrudate, then warp
Cross dry, roasting, obtain alumina support；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5～5.6%；
3) weigh step 1) alumina support that obtains is placed in hydrothermal treatment consists stove, pressure be 0-0.5mpa, temperature be
0.5～9h is reacted, then by step 2 under the conditions of 350～700 DEG C) boric acid aqueous solution prepared is passed through in stove, obtains boron modification
Alumina support；
4) weigh containing vib and the slaine of two kinds of metals of VIII, be configured to corresponding metal salt solution；
5) according to the difference of metal oxide supported amount, step 3 is weighed) alumina support of boron modification that obtains immerses step
Rapid 4) metal salt solution obtained impregnates；Dipping method can select incipient impregnation, excess dipping, it is also possible to selects
Two kinds of metal component co-impregnation or step impregnation, preferably equal-volume co-impregnation.
6) by step 5) in dipping after carrier be dried, roasting, obtain Hydrobon catalyst.
Preferably, described step 4) in, metallic cobalt is selected from cobalt nitrate, cobaltous chloride, carbonyl cobalt and cobalt carbonate；Metal
Molybdenum is selected from ammonium molybdate, molybdenum oxide and ammonium paramolybdate；Tungsten is selected from ammonium metatungstate and ammonium paratungstate；Metallic nickel selected from nickel nitrate,
Basic nickel carbonate and nickelous carbonate.
Preferably, described step 6) in, baking temperature is 70～200 DEG C, preferably 95～125 DEG C, when being dried
Between be 1.0～24h, preferably 3～6h, sintering temperature is 250～600 DEG C, preferably 400～510 DEG C, roasting time be 1～
15h, preferably 3～5h.
Preferably, described step 6) in, baking temperature is 95～125 DEG C, and drying time is 3～6h, roasting temperature
Degree is 400～510 DEG C, and roasting time is 3～5h.
The beneficial effects of the present invention is:
1) the boron modification Hydrobon catalyst that prepared by the inventive method, B2O3It is evenly distributed and concentrates on alumina support
Surface, can stop active component to enter in aluminium oxide lattice, be conducive to improving the dispersion of metal component, improve metal component
Utilization rate, and then improve catalyst hydrogenation activity；
2) the boron modification Hydrobon catalyst that prepared by the present invention, can obtain the hydrofinishing catalysis of high capacity amount boracic
Agent, catalyst has higher denitrification activity.
Detailed description of the invention
In order to preferably explain the present invention, it is further elucidated with the main contents of the present invention below in conjunction with specific embodiment, but
Present disclosure is not limited solely to following example.
The preparation of raw material:
The compound method of Ni-W metal salt solution:
With Nickelous nitrate hexahydrate and ammonium metatungstate as raw material, according to NiO and WO in impregnation liquid3Aimed concn, weigh suitable
The slaine of amount is in deionized water, and stirring and dissolving is to blackish green settled solution, standby.NiO in Ni-W metal salt solution contains
Amount is 10～15g/100ml, WO3Content is 40～44g/100ml.
The compound method of Ni-Mo metal salt solution:
With basic nickel carbonate, molybdenum trioxide and phosphoric acid as raw material, according to NiO and MoO in impregnation liquid3Aimed concn, claim
Take appropriate slaine and phosphoric acid solution, be heated to reflux, obtain the blackish green solution of clarification, standby.Wherein, Ni-Mo slaine
NiO content in solution is 6～8g/100ml, MoO3Content is 38～42g/100ml.
Select according to above-mentioned preparation method, slaine and oxide and determine according to practical situation, such as:
Metal molybdenum is selected from ammonium molybdate, molybdenum oxide and ammonium paramolybdate；
Tungsten is selected from ammonium metatungstate and ammonium paratungstate；
Metallic nickel is selected from nickel nitrate, basic nickel carbonate and nickelous carbonate.
The raw material that following embodiment uses all is purchased from market.
Embodiment 1
1) weighing the boehmite of 150g, (butt of boehmite is 80%, specific surface to be false boehmite
For 380m2/ g, total hole pore volume is 0.86cm3/ g), the sesbania powder of 5g, measure the dust technology that 120ml mass concentration is 4% water-soluble
Liquid, is rolled into extrudable mixture cake in edge runner mill, and by banded extruder extrusion molding, extrudate is the cylinder of diameter 1.5mm；To squeeze
Go out thing in 90 DEG C of dry 16h, then at 530 DEG C of roasting 6h, obtain alumina support Z1；
2) weighing the boric acid solid of 58g, be dissolved in 1000ml deionized water under room temperature, stirring, to being completely dissolved, obtains matter
Amount concentration is the boric acid aqueous solution A1 of 5.5%；
3) weighing the Z1 of 80g in hydrothermal treatment consists stove, control reaction pressure is 0.1mpa, and reaction temperature is 500 DEG C, reaction
Time is 3.5h, and boric acid aqueous solution A1 is 1.2h to the mass space velocity of alumina support Z1-1, obtain the alumina support of boron modification
BZ1；
4) with metal salt solution incipient impregnation carrier B Z1 containing Ni-Mo, 100 DEG C of dry 5h, 500 DEG C of roasting 3h, obtain
Catalyst C1.
Embodiment 2
1) (butt of amorphous hydroted alumina is 70%, and specific surface is 370m to weigh the amorphous hydroted alumina of 200g2/
G, total hole pore volume is 0.89cm3/ g), the sesbania powder of 5g, measure the acetic acid aqueous solution that 120ml mass concentration is 5%, at edge runner mill
In be rolled into extrudable mixture cake, by banded extruder extrusion molding, extrudate is the Herba Trifolii Pratentis of two blade gap distance 1.6mm；By extrudate in
100 DEG C of dry 12h, then at 510 DEG C of roasting 6h, obtain alumina support Z2；
2) weighing the boric acid solid of 60g, be dissolved in 1200ml deionized water under room temperature, stirring, to being completely dissolved, obtains matter
Amount concentration is the boric acid aqueous solution A2 of 4.8%；
3) weighing the Z2 of 80g in hydrothermal treatment consists stove, control reaction pressure is 0.2mpa, and reaction temperature is 550 DEG C, reaction
Time is 4.0h, and boric acid aqueous solution A2 is 1.5h to the mass space velocity of alumina support Z2-1；Obtain the alumina support of boron modification
BZ2；
4) with metal salt solution incipient impregnation carrier B Z2 containing Ni-Mo, 110 DEG C of dry 5h, 480 DEG C of roasting 4h, obtain
Catalyst C2.
Embodiment 3
1) (butt of surge aluminum stone is 75%, and specific surface is 350m to weigh the surge aluminum stone of 200g2/ g, total hole pore volume is
0.92cm3/ g), 6g sesbania powder, measure the acetic acid aqueous solution that 150ml mass concentration is 4%, edge runner mill is rolled into extrudable mixture
Cake, by banded extruder extrusion molding, extrudate is the Herba Trifolii Pratentis of two blade gap distance 1.6mm.By extrudate in 110 DEG C of dry 8h, then
In 530 DEG C of roasting 6h, obtain alumina support Z3；
2) weighing the boric acid solid of 50g, be dissolved in 1500ml deionized water under room temperature, stirring, to being completely dissolved, obtains matter
Amount concentration is the boric acid aqueous solution A3 of 3.2%；
3) weighing the Z3 of 80g in hydrothermal treatment consists stove, control reaction pressure is 0.15mpa, and reaction temperature is 600 DEG C, instead
Between Ying Shi be 6.0h, boric acid aqueous solution A3 be 2.0h to the mass space velocity of alumina support Z3-1, obtain the carrying alumina of boron modification
Body BZ3；
4) with metal salt solution incipient impregnation carrier B Z3 containing Ni-Mo, 110 DEG C of dry 5h, 500 DEG C of roasting 4h, obtain
Catalyst C3.
Embodiment 4
1) (butt of boehmite is 80%, and specific surface is 380m to weigh the boehmite of 200g2/ g, hole, total hole
Hold for 0.86cm3/ g), the sesbania powder of 8g, measure the aqueous solution of nitric acid that 150ml mass concentration is 4%, be rolled in edge runner mill
Extrudable mixture cake, by banded extruder extrusion molding, extrudate is the cylinder of diameter 1.6mm, by extrudate in 110 DEG C of dry 8h,
Then at 530 DEG C of roasting 6h, obtain alumina support Z4.
2) weighing the boric acid solid of 40g, be dissolved in 1500ml deionized water under room temperature, stirring, to being completely dissolved, obtains matter
Amount concentration is the boric acid aqueous solution A4 of 2.6%；
3) weighing 80gZ4 in hydrothermal treatment consists stove, control reaction pressure is 0.15mpa, and reaction temperature is 600 DEG C, reaction
Time is 5.0h, and boric acid aqueous solution A4 is 3.0h to the mass space velocity of alumina support Z4-1.Obtain the alumina support of boron modification
BZ4；
4) with metal salt solution incipient impregnation carrier B Z4 containing Ni-W, 120 DEG C of dry 5h, 520 DEG C of roasting 4h, obtain
Catalyst C4.
Comparative example 1
1) (butt of boehmite is 80%, and specific surface is 380m to weigh the boehmite of 150g2/ g, hole, total hole
Hold for 0.86cm3/ g), 5g sesbania powder, measure the diluted nitric acid aqueous solution that 120ml mass concentration is 4%, be rolled in edge runner mill
Extrudable mixture cake, by banded extruder extrusion molding, extrudate is the cylinder of diameter 1.5mm.By extrudate in 90 DEG C of dry 16h,
Then at 530 DEG C of roasting 6h, obtain alumina support Z5.
2) weighing the boric acid solid of 55g, be dissolved in 1000ml deionized water under room temperature, stirring, to being completely dissolved, obtains matter
Amount concentration is the boric acid aqueous solution A5 of 5.2%.
3) weighing the Z5 of 80g in hydrothermal treatment consists stove, control reaction pressure is 0.1mpa, and reaction temperature is 500 DEG C, reaction
Time is 2.0h, and boric acid aqueous solution A5 is 0.8h to the mass space velocity of alumina support Z5-1.Obtain the alumina support of boron modification
BZ5。
4) with metal salt solution incipient impregnation carrier B Z5 containing Ni-Mo, 100 DEG C of dry 5h, 500 DEG C of roasting 3h, obtain
Catalyst C5.
Comparative example 2
1) (butt of boehmite is 80%, and specific surface is 380m to weigh the boehmite of 200g2/ g, hole, total hole
Hold for 0.86cm3/ g), add 6g sesbania powder, add the dust technology that 150ml mass concentration is 4% of the boric acid being dissolved with 9g
Solution, is rolled into material cake in Wet wheel roller, puts into extrusion molding in banded extruder, and extrudate is that diameter 1.5mm is cylindrical.Will
Extrudate, in 90 DEG C of dry 16h, then at 530 DEG C of roasting 6h, obtains alumina support Z6.
2) with the metal salt solution incipient impregnation carrier 80g carrier Z6 containing Ni-Mo, 100 DEG C of dry 5h, 500 DEG C of roastings
3h, obtains catalyst C6.
The physico-chemical property of each catalyst is shown in Table 1.Metal dispersity uses photoelectron spectroscopy to be measured, and the value of dispersion is more
Greatly, the best of metal dispersion is represented.I is the areal intensity of certain element Photoelectron peak, INi/IAlRepresent Ni element on alumina
Dispersion, IMo/IAlRepresent Mo element dispersion on alumina, IW/IAlRepresent W element dispersion on alumina.
Table 1 catalyst physico-chemical property collects
Catalyst performance evaluation of the present invention is carried out in 30ml fixed bed reactors, needs to enter catalyst before reaction
Row presulfurization.The performance evaluation condition of catalyst is, reaction pressure 10.5mpa, hydrogen to oil volume ratio 1200, and feedstock volume is empty
Speed 1.5h-1, reaction temperature 385 DEG C.Raw oil character refers to table 2, and activity rating of catalyst the results are shown in Table 3.
As can be seen from Table 1, using the inventive method to prepare the Hydrobon catalyst of boracic, active component is at aluminium oxide
Dispersion on carrier is preferable, and the utilization rate of metal component is improved, it is possible to significantly improve the hydrogenation activity of catalyst.Table 3
Data show, use the content of B in the inventive method boracic Hydrobon catalyst C1～C5, C1～the C4 that prepare be 2.0～
4.0%, there is higher hydrogenation activity, aromatic hydrocarbons in raw oil and sulfur nitrogen content have and significantly reduce, and C4 shows excellence
Hydrogenation activity.In catalyst C5, the content of B is only 0.98%, and denitrification activity is the poorest.Use boracic hydrogenation essence prepared by kneading method
Catalyst C6 processed, due to auxiliary agent boron skewness in the carrier, hydrogenation activity and denitrification activity are minimum.
Table 2 raw oil character
| Project | Result |
| Density (20 DEG C), g/ml | 0.9310 |
| Boiling range, DEG C | |
| IBP/EBP | 312/547 |
| Arene content, m% | 18.26 |
| S, m% | 1.20 |
| N, m% | 0.16 |
Table 3 product oil character
Other unspecified part is prior art.Although above-described embodiment is made that detailed retouching to the present invention
State, but its a part of embodiment that is only the present invention rather than all embodiment, people can also according to the present embodiment without
Obtaining other embodiments under creative premise, these embodiments broadly fall into scope.
Claims (17)
1. a high capacity amount boron modification Hydrobon catalyst, described catalyst is made up of active metal component and carrier, institute
State active metal component to be supported on carrier, it is characterised in that: described active metal group is by containing vib and VIII two kinds
The oxide composition of metal, wherein, vib metals is Mo and/or W, and group VIII metal is Ni and/or Co, described carrier
Alumina support for boron modification.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 1, it is characterised in that: in described catalyst,
Oxide content containing vib metals is 8.9～30.1%, the oxide content containing group VIII metal be 1.9～
10.1%, in the alumina support of described boron modification, boron accounts for the mass fraction of catalyst is 1.0～11.5%.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 2, it is characterised in that: described contain VIB
The oxide content of race's metal is 15.0～26.0%, and described group VIII metal is Ni, and the oxide content containing Ni is 2.2
～6.5%, it is 2.0～4.0% that boron accounts for the mass fraction of catalyst.
4. according to high capacity amount boron modification Hydrobon catalyst described in claim 1 or 2 or 3, it is characterised in that: described catalysis
In agent, the specific surface area of catalyst is 130～320m2/ g, total hole pore volume are 0.15～0.50cm3/g。
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 4, it is characterised in that:
The specific surface area of described catalyst is 190～250m2/ g, total hole pore volume are 0.33～0.40cm3/g。
6. according to high capacity amount boron modification Hydrobon catalyst described in claim 1 or 2 or 3, it is characterised in that: described boron changes
The preparation method of the alumina support of property, comprises the following steps:
1) weigh alumina precursor, extrusion aid and peptizer, roll through mixing, extrusion obtains alumina extrudate, then through overdrying
Dry, roasting, obtains alumina support；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5～5.6%；
3) weigh step 1) alumina support that obtains is placed in hydrothermal treatment consists stove, pressure be 0～0.5mpa, temperature be 350
～react 0.5～9h under the conditions of 700 DEG C, then by step 2) boric acid aqueous solution prepared is passed through in stove, obtains the oxygen of boron modification
Change alumina supporter.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 6, it is characterised in that: described step 1) in,
Described alumina precursor is amorphous hydroted alumina, false boehmite, boehmite, gibbsite, surge aluminum stone, promise diaspore
In any one or a few, or fired after can be converted into γ-Al2O3Aluminum oxide；Extrusion aid is citric acid
And/or sesbania powder, the quality of extrusion aid accounts for the 1.0～5.0% of carrying alumina weight；Peptizer is organic acid or mineral acid
Aqueous solution, organic acid is formic acid and/or acetic acid, mineral acid be in nitric acid, phosphoric acid, hydrochloric acid any one or a few；In peptizer
The content of acid accounts for the 1.0～7.0% of carrying alumina weight.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 7, it is characterised in that: the matter of described extrusion aid
Amount accounts for the 2.0～3.5% of carrying alumina weight；In peptizer, the content of acid accounts for the 1.8～4.0% of carrying alumina weight.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 6, it is characterised in that: described step 1) in,
Baking temperature is 60～190 DEG C, and drying time is 0.1～22h；Sintering temperature is 300～650 DEG C, and roasting time is 3～6h.
The boron modification Hydrobon catalyst of high capacity amount the most according to claim 9, it is characterised in that: described step 1) in,
Baking temperature is 90～130 DEG C, and drying time is 1.5～8h；Sintering temperature is 420～540 DEG C, and roasting time is 3～6h.
11. according to high capacity amount boron modification Hydrobon catalyst described in claim 7 or 9, it is characterised in that: described step 1)
In, alumina support is shaped as cylinder, Herba Trifolii Pratentis, Herba Galii Bungei or gear shape, wherein, the alumina support particle diameter of cylinder strip
It is 1.2～1.6mm, a length of 5～10mm；Two blade gap distances of Herba Trifolii Pratentis or Herba Galii Bungei are 1.1～1.8mm, a length of 5～
10mm。
12. according to high capacity amount boron modification Hydrobon catalyst described in claim 7 or 9, it is characterised in that: described step 3)
In, when boric acid aqueous solution is passed through stove, the mass space velocity of boric acid aqueous solution is 0.1～5.5h-1。
13. according to high capacity amount boron modification Hydrobon catalyst described in claim 7 or 9, it is characterised in that: described boric acid water
The mass space velocity of solution is 1.2～4.0h-1。
The preparation method of high capacity amount boron modification Hydrobon catalyst described in 14. 1 kinds of claim 1, it is characterised in that bag
Include following steps:
1) weigh alumina precursor, extrusion aid and peptizer, roll through mixing, extrusion obtains alumina extrudate, then through overdrying
Dry, roasting, obtains alumina support；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5～5.6%；
3) weigh step 1) alumina support that obtains is placed in hydrothermal treatment consists stove, pressure be 0-0.5mpa, temperature be 350～
0.5～9h is reacted, then by step 2 under the conditions of 700 DEG C) boric acid aqueous solution prepared is passed through in stove, obtains the oxidation of boron modification
Alumina supporter；
4) weigh containing vib and the slaine of two kinds of metals of VIII, be configured to corresponding metal salt solution；
5) according to the difference of metal oxide supported amount, step 3 is weighed) alumina support of boron modification that obtains immerses step 4)
The metal salt solution obtained impregnates；Dipping method can select incipient impregnation, excess dipping, it is also possible to selects two kinds
Metal component co-impregnation or step impregnation, preferably equal-volume co-impregnation.
6) by step 5) in dipping after carrier be dried, roasting, obtain Hydrobon catalyst.
15. according to the preparation method of high capacity amount boron modification Hydrobon catalyst described in claim 14, it is characterised in that: institute
State step 4) in, metallic cobalt is selected from cobalt nitrate, cobaltous chloride, carbonyl cobalt and cobalt carbonate；Metal molybdenum is selected from ammonium molybdate, molybdenum oxide and secondary
Ammonium molybdate；Tungsten is selected from ammonium metatungstate and ammonium paratungstate；Metallic nickel is selected from nickel nitrate, basic nickel carbonate and nickelous carbonate.
16. according to the preparation method of high capacity amount boron modification Hydrobon catalyst described in claim 14, it is characterised in that: institute
State step 6) in, baking temperature is 70～200 DEG C, preferably 95～125 DEG C, and drying time is 1.0～24h, preferably 3～
6h, sintering temperature is 250～600 DEG C, preferably 400～510 DEG C, and roasting time is 1～15h, preferably 3～5h.
17. according to the preparation method of high capacity amount boron modification Hydrobon catalyst described in claim 14, it is characterised in that: institute
State step 6) in, baking temperature is 95～125 DEG C, and drying time is 3～6h, and sintering temperature is 400～510 DEG C, roasting time
It is 3～5h.
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| WO2018019203A1 (en) | 2018-02-01 |
| CN106311263B (en) | 2018-10-23 |
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