CN106311263B - High load amount boron modification Hydrobon catalyst and preparation method thereof - Google Patents
High load amount boron modification Hydrobon catalyst and preparation method thereof Download PDFInfo
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- CN106311263B CN106311263B CN201610614764.9A CN201610614764A CN106311263B CN 106311263 B CN106311263 B CN 106311263B CN 201610614764 A CN201610614764 A CN 201610614764A CN 106311263 B CN106311263 B CN 106311263B
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- boron modification
- high load
- alumina
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 68
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000012986 modification Methods 0.000 title claims abstract description 46
- 230000004048 modification Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 99
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 150000002739 metals Chemical class 0.000 claims abstract description 14
- 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 29
- 238000001125 extrusion Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 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
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 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
- 239000000243 solution Substances 0.000 claims description 7
- 238000005303 weighing Methods 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
- 241000219793 Trifolium Species 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
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 241001101998 Galium Species 0.000 claims description 4
- 235000014820 Galium aparine Nutrition 0.000 claims description 4
- 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
- 241000612118 Samolus valerandi Species 0.000 claims description 4
- 239000004411 aluminium Substances 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
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 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
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000002253 acid Substances 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
- 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 17
- 239000006185 dispersion Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000012141 concentrate Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012752 auxiliary agent Substances 0.000 description 12
- 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
- 239000003921 oil Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002803 maceration Methods 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 239000002245 particle Substances 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of high load amount boron modification Hydrobon catalysts and preparation method thereof, the catalyst is made of active metal component and carrier, the active metal component is supported on carrier, the active metal group is made of the oxide containing two kinds of metals of group VIB and VIII group, wherein, vib metals are Mo and/or W, and group VIII metal is Ni and/or Co, and the carrier is the alumina support of boron modification.Boron modification Hydrobon catalyst prepared by the method for the present invention, B2O3It is evenly distributed and concentrates on alumina carrier surface, active component can be prevented to enter in aluminium oxide lattice, be conducive to the dispersion degree for improving metal component, improve the utilization rate of metal component, and then improve the hydrogenation activity of catalyst；Boron modification Hydrobon catalyst prepared by the present invention, can obtain the Hydrobon catalyst of high load amount boracic, and catalyst has higher denitrification activity.
Description
Technical field
The present invention relates to catalyst and preparation method thereof, in particular to a kind of high load amount boron modification Hydrobon catalyst
And preparation method thereof.
Background technology
Typical Hydrobon catalyst is generally made of alumina support and hydrogenation active metals.Hydrogenation active metals are
Group VIB and/or group VIII metal, common vib metals are Mo and/or W, and group VIII metal is Co and/or Ni.
Aluminium oxide has extensive purposes as a kind of carrier material, in hydrogenation catalyst field.But since alumina acidic is very weak, and
Strong interaction easily occurs with active metal component and generates inactive species, to influence the activity and stability of catalyst.For
Improve the acidity of aluminium oxide and adjust its active force with metal component, often through introducing the auxiliary agents pair such as Si, P, Ti, B, F
Aluminium oxide is modified processing.
Influence of the boron to Hydrobon catalyst is mainly reflected in the raising of denitrification activity and the raising of metal dispersity, from
And improve the hydrogenation activity of catalyst for refining.Document (Lewandowski M, Fuel, 2000,79,487) has studied auxiliary agent boron pair
The influence of Hydrobon catalyst hydrodenitrogenationactivity activity, as a result, it has been found that, with the increase of boron load capacity, the hydrodenitrogeneration of catalyst
Activity is gradually increased, and the deactivation rate of catalyst slows down.Auxiliary agent boron has deepened hydrogenation reaction degree, this is because boron is in aluminium oxide
Surface forms B2O3, the vulcanization of catalyst is promoted, reduces the carbon deposition quantity in hydrogenation process, improves active metal component
Dispersion degree.
Boron is divided into two kinds as alumina modified auxiliary agent, common adding method：One is in the molding process of carrier
Middle introducing boron, including coprecipitation and physical mixed method；Another kind is introduced by pre-preg after carrier molding.Boron generally with
H3BO3Form be added on carrier, and H3BO3Solubility 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 its preparation side
Method, catalyst is using aluminium oxide or silicon-containing alumina as carrier, using Mo-Ni as active component, adds boron additive.It is steady by making
Fixed alkaline Mo-Ni-B solution, using co-impregnation technology so that the hydrodenitrogenationactivity activity of catalyst is improved.The catalyst
Using step impregnation, ammonium hydroxide is introduced, pollutes environment.
The Chinese invention patent of Publication No. CN00110018.1 discloses a kind of hydrogenation catalyst and preparation method thereof, should
Catalyst is supported the auxiliary agents such as boron, silicon, is prepared using coprecipitation using group VIB and group VIII metal as hydrogenation active component, and one
A little active metals are covered possibly into body phase during co-precipitation and extrusion or by alumina particle, the utilization of active metal
Rate reduces, and hydrogenation activity is relatively low.
The Chinese invention patent of Publication No. CN101491767A discloses a kind of preparation method of hydrogenation catalyst, this is urged
Auxiliary agent fluorine, silicon, phosphorus in agent carrier etc. are by two sections of additions during the plastic of dry glue powder and in carrier forming process
, the dispersion degree of active metal on the surface can be effectively improved, improves the utilization rate of active metal, and then improve making for catalyst
Use performance.The content of auxiliary agent boron is only 1% or so in the catalyst.
In patent disclosed above, modification of the auxiliary agent boron to Hydrobon catalyst has been all referred to.It is of the existing technology
Problem has two aspects：First, it is beneficial to introduce dispersion generation of the auxiliary agent boron not to active metal component on carrier using conventional method
Influence；Second is that the load capacity of auxiliary agent boron is relatively low, the activity of catalyst hydrogenation denitrogenation is restricted.
Invention content
The present invention is directed to deficiency in the prior art, provides a kind of high load amount boron modification Hydrobon catalyst and its system
Preparation Method.Auxiliary agent boron can not only be made to be better distributed on the surface of alumina support by this method, improve active component
Dispersion degree, additionally it is possible to effectively improve the load capacity of boron in the catalyst, improve the hydrodenitrogenationactivity activity of catalyst.It is prepared by the present invention
Hydrofinishing of the Hydrobon catalyst especially suitable for high-nitrogen raw oil.
To achieve the above object, a kind of high load amount boron modification Hydrobon catalyst provided by the invention, the catalysis
Agent is made of active metal component and carrier, and the active metal component is supported on carrier, and the active metal group is by containing
The oxide of two kinds of metals of group VIB and VIII group forms, wherein vib metals are Mo and/or W, and group VIII metal is
Ni and/or Co, the carrier are the alumina support of boron modification.
Further, in the catalyst, the oxide content containing vib metals is 8.9~30.1%, contains the
The oxide content of group VIII metal is 1.9~10.1%, and boron accounts for the quality of catalyst in the alumina support of the boron modification
Score is 1.0~11.5%.
Still further, the oxide content containing vib metals is 15.0~26.0%, the group VIII
Metal is preferably Ni, and the oxide content containing Ni is 2.2~6.5%, and the mass fraction that boron accounts for catalyst is 2.0~4.0%.
Still further, in the catalyst, the specific surface area of catalyst is 130~320m2/ g, total Kong Kongrong are 0.15
~0.50cm3/g。
Still further, the specific surface area of the catalyst is 190~250m2/ g, total Kong Kongrong are 0.33~0.40cm3/
g。
Still further, the preparation method of the alumina support of the boron modification, includes the following steps：
1) alumina precursor, extrusion aid and peptizing agent are weighed, is rolled through mixing, extrusion obtains alumina extrudate, then is passed through
Dry, roasting is crossed, alumina support is obtained；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5~5.6%；
3) it weighs the alumina support that step 1) obtains to be placed in hydro-thermal process stove, pressure is 0~0.5mpa, temperature is
0.5~9h is reacted under the conditions of 350~700 DEG C, and then the boric acid aqueous solution that step 2) is prepared is passed through in stove, obtains boron modification
Alumina support.
Still further, in the step 1), the alumina precursor be amorphous hydroted alumina, false boehmite,
In boehmite, gibbsite, surge aluminium stone, promise diaspore any one or a few or it is 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%；Peptizing agent is the aqueous solution of organic acid or inorganic acid, and organic acid is formic acid and/or acetic acid, and inorganic acid is nitric acid, phosphorus
Any one or a few in acid, hydrochloric acid；Sour content accounts for the 1.0~7.0% of carrying alumina weight in peptizing agent.
Still further, the quality of the extrusion aid accounts for the 2.0~3.5% of carrying alumina weight；It is sour in peptizing agent
Content accounts for the 1.8~4.0% of carrying alumina weight.
Still further, in the step 1), drying 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.
Still further, in the step 1), drying 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.
Still further, in the step 1), carrying alumina shape is cylinder, clover, bunge bedstraw herb or gear shape,
Wherein, the alumina support grain size of cylinder strip is 1.2~1.6mm, and length is 5~10mm；Two leaves of clover or bunge bedstraw herb
Spacing is 1.1~1.8mm, and length is 5~10mm.
Still further, in the step 3), when boric acid aqueous solution is passed through stove, the mass space velocity of boric acid aqueous solution is 0.1
~5.5h-1。
Still further, the mass space velocity of the boric acid aqueous solution is 1.2~4.0h-1。
The present invention provides a kind of preparation methods of high load amount boron modification Hydrobon catalyst, which is characterized in that packet
Include following steps：
1) alumina precursor, extrusion aid and peptizing agent are weighed, is rolled through mixing, extrusion obtains alumina extrudate, then is passed through
Dry, roasting is crossed, alumina support is obtained；
2) boric acid solid is configured to the boric acid aqueous solution that mass fraction is 0.5~5.6%；
3) it weighs the alumina support that step 1) obtains to be placed in hydro-thermal process stove, pressure is 0-0.5mpa, temperature is
0.5~9h is reacted under the conditions of 350~700 DEG C, and then the boric acid aqueous solution that step 2) is prepared is passed through in stove, obtains boron modification
Alumina support；
4) metal salt containing two kinds of metals of group VIB and VIII group is weighed, corresponding metal salt solution is configured to；
5) according to the difference of metal oxide supported amount, the alumina support for weighing the boron modification that step 3) obtains immerses step
It is impregnated in the rapid metal salt solution 4) obtained；Dipping method can select incipient impregnation, excessive dipping, can also select
Two kinds of metal component co-impregnations or step impregnation, preferably isometric co-impregnation.
6) carrier after dipping in step 5) is dried, roasted, obtain Hydrobon catalyst.
Preferably, in the step 4), metallic cobalt is selected from cobalt nitrate, cobalt 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 be selected from nickel nitrate,
Basic nickel carbonate and nickelous carbonate.
Preferably, in the step 6), drying temperature is 70~200 DEG C, preferably 95~125 DEG C, when dry
Between for 1.0~for 24 hours, preferably 3~6h, calcination temperature is 250~600 DEG C, preferably 400~510 DEG C, roasting time is 1~
15h, preferably 3~5h.
Preferably, in the step 6), drying 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 are：
1) boron modification Hydrobon catalyst prepared by the method for the present invention, B2O3It is evenly distributed and concentrates on alumina support
Surface can prevent active component from entering in aluminium oxide lattice, be conducive to the dispersion degree for improving metal component, improve metal component
Utilization rate, and then improve catalyst hydrogenation activity；
2) boron modification Hydrobon catalyst prepared by the present invention can obtain the hydrofinishing catalysis of high load amount boracic
Agent, catalyst have higher denitrification activity.
Specific implementation mode
In order to preferably explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
Present disclosure is not limited solely to following embodiment.
The preparation of raw material：
The preparation method of Ni-W metal salt solutions：
Using Nickelous nitrate hexahydrate and ammonium metatungstate as raw material, according to NiO in maceration extract and WO3Aimed concn, weigh suitable
For the metal salt of amount in deionized water, stirring and dissolving is spare to blackish green clear solution.NiO in Ni-W metal salt solutions contains
Amount is 10~15g/100ml, WO3Content is 40~44g/100ml.
The preparation method of Ni-Mo metal salt solutions：
Using basic nickel carbonate, molybdenum trioxide and phosphoric acid as raw material, according to NiO in maceration extract and MoO3Aimed concn, claim
Suitable metal salt and phosphoric acid solution are taken, is heated to reflux, clear blackish green solution is obtained, it is spare.Wherein, Ni-Mo metal salts
NiO contents in solution are 6~8g/100ml, MoO3Content is 38~42g/100ml.
According to above-mentioned preparation method, metal salt and oxide are selected determines according to actual conditions, 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 embodiments use is purchased from market.
Embodiment 1
1) boehmite of 150g is weighed, (butt of boehmite is 80% to as false boehmite, specific surface
For 380m2/ g, total Kong Kongrong are 0.86cm3/ g), it is water-soluble to measure the dust technology that 120ml mass concentrations are 4% for the sesbania powder of 5g
Liquid is rolled into extrudable mixture cake in edge runner, and by banded extruder extrusion molding, extrudate is the cylinder of diameter 1.5mm；It will squeeze
Go out object and obtains alumina support Z1 then at 530 DEG C of roasting 6h in 90 DEG C of dry 16h；
2) the boric acid solid for weighing 58g, is dissolved at room temperature in 1000ml deionized waters, stirs to being completely dissolved, obtains matter
Measure a concentration of 5.5% boric acid aqueous solution A1；
3) Z1 of 80g is weighed in hydro-thermal process stove, and 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 Z1,100 DEG C of dry 5h containing Ni-Mo, 500 DEG C roast 3h, obtain
Catalyst C1.
Embodiment 2
1) weigh 200g amorphous hydroted alumina (butt of amorphous hydroted alumina be 70%, specific surface 370m2/
G, total Kong Kongrong are 0.89cm3/ g), the sesbania powder of 5g measures the acetic acid aqueous solution that 120ml mass concentrations are 5%, in edge runner
In be rolled into extrudable mixture cake, by banded extruder extrusion molding, extrudate is the clover of two leaf spacing 1.6mm；By extrudate in
100 DEG C of dry 12h obtain alumina support Z2 then at 510 DEG C of roasting 6h；
2) the boric acid solid for weighing 60g, is dissolved at room temperature in 1200ml deionized waters, stirs to being completely dissolved, obtains matter
Measure a concentration of 4.8% boric acid aqueous solution A2；
3) Z2 of 80g is weighed in hydro-thermal process stove, and 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 Z2,110 DEG C of dry 5h containing Ni-Mo, 480 DEG C roast 4h, obtain
Catalyst C2.
Embodiment 3
1) weigh 200g surge aluminium stone (butt of surge aluminium stone be 75%, specific surface 350m2/ g, total Kong Kongrong are
0.92cm3/ g), 6g sesbania powders measure the acetic acid aqueous solution that 150ml mass concentrations are 4%, extrudable mixture are rolled into edge runner
Cake, by banded extruder extrusion molding, extrudate is the clover of two leaf spacing 1.6mm.By extrudate in 110 DEG C of dry 8h, then
6h is roasted in 530 DEG C, obtains alumina support Z3；
2) the boric acid solid for weighing 50g, is dissolved at room temperature in 1500ml deionized waters, stirs to being completely dissolved, obtains matter
Measure a concentration of 3.2% boric acid aqueous solution A3；
3) Z3 of 80g is weighed in hydro-thermal process stove, and control reaction pressure is 0.15mpa, and reaction temperature is 600 DEG C, instead
It is 6.0h between seasonable, boric acid aqueous solution A3 is 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 Z3,110 DEG C of dry 5h containing Ni-Mo, 500 DEG C roast 4h, obtain
Catalyst C3.
Embodiment 4
1) weigh 200g boehmite (butt of boehmite be 80%, specific surface 380m2/ g, total hole hole
It is 0.86cm to hold3/ g), the sesbania powder of 8g measures the aqueous solution of nitric acid that 150ml mass concentrations are 4%, is rolled into edge runner
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, alumina support Z4 is obtained.
2) the boric acid solid for weighing 40g, is dissolved at room temperature in 1500ml deionized waters, stirs to being completely dissolved, obtains matter
Measure a concentration of 2.6% boric acid aqueous solution A4；
3) 80gZ4 is weighed in hydro-thermal process stove, and 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 Z4,120 DEG C of dry 5h containing Ni-W, 520 DEG C roast 4h, obtain
Catalyst C4.
Comparative example 1
1) weigh 150g boehmite (butt of boehmite be 80%, specific surface 380m2/ g, total hole hole
It is 0.86cm to hold3/ g), 5g sesbania powders measure the diluted nitric acid aqueous solution that 120ml mass concentrations are 4%, are rolled into edge runner
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, alumina support Z5 is obtained.
2) the boric acid solid for weighing 55g, is dissolved at room temperature in 1000ml deionized waters, stirs to being completely dissolved, obtains matter
Measure a concentration of 5.2% boric acid aqueous solution A5.
3) Z5 of 80g is weighed in hydro-thermal process stove, and 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 Z5,100 DEG C of dry 5h containing Ni-Mo, 500 DEG C roast 3h, obtain
Catalyst C5.
Comparative example 2
1) weigh 200g boehmite (butt of boehmite be 80%, specific surface 380m2/ g, total hole hole
It is 0.86cm to hold3/ g), 6g sesbania powders are added, add the dust technology that the 150ml mass concentrations of the boric acid dissolved with 9g are 4%
Solution is rolled into material cake in Wet wheel roller, is put into extrusion molding in banded extruder, and extrudate is diameter 1.5mm cylindrical.It will
Extrudate obtains alumina support Z6 in 90 DEG C of dry 16h then at 530 DEG C of roasting 6h.
2) with metal salt solution incipient impregnation carrier 80g carriers Z6,100 DEG C of dry 5h containing Ni-Mo, 500 DEG C of roastings
3h obtains catalyst C6.
The physico-chemical property of each catalyst is shown in Table 1.Metal dispersity is measured using photoelectron spectroscopy, and the value of dispersion degree is got over
Greatly, the better of metal dispersion is indicated.I is the areal intensity of certain element Photoelectron peak, INi/IAlIndicate Ni elements on alumina
Dispersion degree, IMo/IAlIndicate the dispersion degree of Mo elements on alumina, IW/IAlIndicate the dispersion degree of W elements on alumina.
1 catalyst physico-chemical property of table summarizes
Catalyst performance evaluation of the present invention carries out in 30ml fixed bed reactors, needed before reaction to catalyst into
Row presulfurization.The performance evaluation condition of catalyst is reaction pressure 10.5mpa, hydrogen to oil volume ratio 1200, and feedstock volume is empty
Fast 1.5h-1, 385 DEG C of reaction temperature.Raw material oil nature refers to table 2, and the Activity evaluation of catalyst is shown in Table 3.
As can be seen from Table 1, the Hydrobon catalyst of boracic is prepared using the method for the present invention, active component is in aluminium oxide
Dispersion degree on carrier is preferable, and the utilization rate of metal component is improved, and can significantly improve the hydrogenation activity of catalyst.Table 3
Data show, in the boracic the Hydrobon catalyst C1~C5, C1~C4 that are prepared using the method for the present invention the content of B be 2.0~
4.0%, there is higher hydrogenation activity, the aromatic hydrocarbons and sulphur nitrogen content in feedstock oil have and significantly reduces, and C4 shows excellent
Hydrogenation activity.The content of B is only 0.98% in catalyst C5, and denitrification activity is slightly poor.The boracic prepared using kneading method adds hydrogen smart
Catalyst C6 processed, since auxiliary agent boron is unevenly distributed in the carrier, hydrogenation activity and denitrification activity are minimum.
2 raw material oil nature of table
| Project | As a 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 |
3 product oil nature of table
Other unspecified parts are the prior art.Although above-described embodiment is made that the present invention and retouches in detail
State, but it is only a part of the embodiment of the present invention, rather than whole embodiments, people can also according to the present embodiment without
Other embodiment is obtained under the premise of creativeness, these embodiments belong to the scope of the present invention.
Claims (16)
1. a kind of high load amount boron modification Hydrobon catalyst, the catalyst are made of active metal component and carrier, institute
Active metal component is stated to be supported on carrier, it is characterised in that：The active metal group is by containing two kinds of group VIB and VIII group
The oxide of metal forms, wherein vib metals are Mo and/or W, and group VIII metal is Ni and/or Co, the carrier
For the alumina support of boron modification；Wherein, the preparation method of the alumina support of the boron modification, includes the following steps：
1) alumina precursor, extrusion aid and peptizing agent are weighed, is rolled through mixing, extrusion obtains alumina extrudate, using dry
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) alumina support that step 1) obtains is weighed to be placed in hydro-thermal process stove, pressure be 0~0.5mpa, temperature 350
0.5~9h is reacted under the conditions of~700 DEG C, and then the boric acid aqueous solution that step 2) is prepared is passed through in stove, obtains the oxygen of boron modification
Change alumina supporter.
2. high load amount boron modification Hydrobon catalyst according to claim 1, it is characterised in that：In the catalyst,
Oxide content containing vib metals be 8.9~30.1%, the oxide content containing group VIII metal be 1.9~
10.1%, the mass fraction that boron accounts for catalyst in the alumina support of the boron modification is 1.0~11.5%.
3. high load amount boron modification Hydrobon catalyst according to claim 2, it is characterised in that：It is described to contain Section VI B
The oxide content of race's metal is 15.0~26.0%, and the group VIII metal is Ni, and the oxide content containing Ni is 2.2
~6.5%, the mass fraction that boron accounts for catalyst is 2.0~4.0%.
4. according to claims 1 or 2 or the 3 high load amount boron modification Hydrobon catalysts, it is characterised in that：The catalysis
In agent, the specific surface area of catalyst is 130~320m2/ g, total Kong Kongrong are 0.15~0.50cm3/g。
5. high load amount boron modification Hydrobon catalyst according to claim 4, it is characterised in that：The ratio of the catalyst
Surface area is 190~250m2/ g, total Kong Kongrong are 0.33~0.40cm3/g。
6. high load amount boron modification Hydrobon catalyst according to claim 1, it is characterised in that：In the step 1),
The alumina precursor is amorphous hydroted alumina, false boehmite, boehmite, gibbsite, surge aluminium stone, promise diaspore
In any one or a few or it is fired after can be converted into γ-Al2O3Aluminum oxide；Extrusion aid is citric acid
And/or sesbania powder, the quality of extrusion aid account for the 1.0~5.0% of carrying alumina weight；Peptizing agent is organic acid or inorganic acid
Aqueous solution, organic acid are formic acid and/or acetic acid, and inorganic acid is any one or a few in nitric acid, phosphoric acid, hydrochloric acid；In peptizing agent
The content of acid accounts for the 1.0~7.0% of carrying alumina weight.
7. high load amount boron modification Hydrobon catalyst according to claim 6, it is characterised in that：The matter of the extrusion aid
Amount accounts for the 2.0~3.5% of carrying alumina weight；Sour content accounts for the 1.8~4.0% of carrying alumina weight in peptizing agent.
8. high load amount boron modification Hydrobon catalyst according to claim 1, it is characterised in that：In the step 1),
Drying temperature is 60~190 DEG C, and drying time is 0.1~22h；Calcination temperature is 300~650 DEG C, and roasting time is 3~6h.
9. high load amount boron modification Hydrobon catalyst according to claim 8, it is characterised in that：In the step 1),
Drying temperature is 90~130 DEG C, and drying time is 1.5~8h；Calcination temperature is 420~540 DEG C, and roasting time is 3~6h.
10. according to the high load amount boron modification Hydrobon catalyst of claim 6 or 8, it is characterised in that：The step 1)
In, carrying alumina shape is cylinder, clover, bunge bedstraw herb or gear shape, wherein the alumina support grain size of cylinder strip
For 1.2~1.6mm, length is 5~10mm；Two leaf spacing of clover or bunge bedstraw herb be 1.1~1.8mm, length be 5~
10mm。
11. according to the high load amount boron modification Hydrobon catalyst of claim 6 or 8, it is characterised in that：The 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。
12. according to the high load amount boron modification Hydrobon catalyst of claim 6 or 8, it is characterised in that：The boric acid water
The mass space velocity of solution is 1.2~4.0h-1。
13. the preparation method of high load amount boron modification Hydrobon catalyst described in a kind of claim 1, which is characterized in that packet
Include following steps：
1) alumina precursor, extrusion aid and peptizing agent are weighed, is rolled through mixing, extrusion obtains alumina extrudate, using dry
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) alumina support that step 1) obtains is weighed to be placed in hydro-thermal process stove, pressure be 0-0.5mpa, temperature be 350~
0.5~9h is reacted under the conditions of 700 DEG C, and then the boric acid aqueous solution that step 2) is prepared is passed through in stove, obtains the oxidation of boron modification
Alumina supporter；
4) metal salt containing two kinds of metals of group VIB and VIII group is weighed, corresponding metal salt solution is configured to；
5) according to the difference of metal oxide supported amount, the alumina support for weighing the boron modification that step 3) obtains immerses step 4)
It is impregnated in obtained metal salt solution；Dipping method can select incipient impregnation, excessive dipping, can also select two kinds
Metal component co-impregnation or step impregnation；
6) carrier after dipping in step 5) is dried, roasted, obtain Hydrobon catalyst.
14. according to the preparation method of high load amount boron modification Hydrobon catalyst described in claim 13, it is characterised in that：Institute
It states in step 4), metallic cobalt is selected from cobalt nitrate, cobalt 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.
15. according to the preparation method of high load amount boron modification Hydrobon catalyst described in claim 13, it is characterised in that：Institute
It states in step 6), drying temperature is 70~200 DEG C, drying time is 1.0~for 24 hours, calcination temperature is 250~600 DEG C, when roasting
Between be 1~15h.
16. according to the preparation method of high load amount boron modification Hydrobon catalyst described in claim 13, it is characterised in that：Institute
It states in step 6), drying temperature is 95~125 DEG C, and drying time is 3~6h, and calcination temperature is 400~510 DEG C, roasting time
For 3~5h.
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| WO2018019203A1 (en) | 2018-02-01 |
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