CN116037218A - Boron modified alumina carrier, hydrogenation carbon residue removal catalyst and preparation method thereof - Google Patents
Boron modified alumina carrier, hydrogenation carbon residue removal catalyst and preparation method thereof Download PDFInfo
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- CN116037218A CN116037218A CN202111261176.9A CN202111261176A CN116037218A CN 116037218 A CN116037218 A CN 116037218A CN 202111261176 A CN202111261176 A CN 202111261176A CN 116037218 A CN116037218 A CN 116037218A
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- boron
- alumina
- boehmite
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 120
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 28
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000000295 fuel oil Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 22
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 22
- 239000004327 boric acid Substances 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001228 spectrum Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 28
- 239000003921 oil Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- -1 aluminum alkoxide Chemical class 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/638—Pore volume more than 1.0 ml/g
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- 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
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a boron modified alumina carrier, a hydrogenation carbon residue removal catalyst and a preparation method thereof. The boron modified alumina carrier is a composite carrier of boron modified flaky alumina and boron modified granular alumina, the total boron content is 3.5-8.5 wt% calculated by elements, the boron content on the boron modified flaky alumina is 3.5-10 wt%, and the boron content on the boron modified granular alumina is 1.0-2.5 wt%. The preparation method comprises the following steps: (1) preparing boron modified gamma-phase alumina powder; (2) preparing flaky boron modified flaky pseudo-boehmite P1; (3) Mixing and kneading the boron modified sheet pseudo-boehmite P1 and pseudo-boehmite P2 to form, drying, roasting, soaking the boron-containing solution again, drying and roasting to obtain the boron modified alumina carrier. The method obtains the hydrogenation carbon residue removal catalyst by carrying out stepwise boron modification treatment on the alumina carrier and further impregnating active components, and has higher hydrogenation desulfurization, denitrification and carbon residue removal activities in the heavy oil hydrogenation treatment process.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a heavy oil hydrodecarbonization catalyst and a preparation method thereof.
Background
In recent years, with the heavy crude oil resources, the consumption requirements of fuel oil are increased and environmental protection regulations are increasingly strict, and the hydrogenation technology is adopted to convert heavy oil including residual oil into high-quality fuel oil and chemical products, thereby being beneficial to improving the crude oil processing depth, reducing the environmental pollution, improving the light oil yield, improving the product quality and the like. Most of impurities such as metal, sulfur, nitrogen, carbon residue and the like in crude oil are mainly enriched in residual oil after atmospheric and vacuum distillation, and the impurities must be removed in advance to prevent poisoning of the hydrocracking catalyst. The residual oil hydrotreatment mainly removes most of metal, sulfur, nitrogen, carbon residue and other impurities in the feed oil, and mainly comprises hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, hydrodecarbon residue and other processes.
The heavy oil hydrogenation carbon residue removal reaction is an important reaction in the residual oil hydrogenation process, and the conversion rate of carbon residue is an important index of the residual oil hydrogenation process. The high carbon residue value raw material can greatly influence the operation stability and product distribution of the heavy oil catalytic cracking device. Reducing the carbon residue value of the oil produced by the residuum hydrogenation device will help to increase the economic benefit of the residuum hydrogenation and catalytic cracking combination device.
The carbon residue value is closely related to the content of polycyclic aromatic hydrocarbon with more than five rings in heavy oil. The carbon residue precursor is usually composed mainly of asphaltenes and larger polycyclic aromatic hydrocarbons in gums. The essence of the residual oil hydrodecarbonization is that the precursor of the residual carbon is treated, so that the precursor compound of the residual carbon is reduced, and the reaction is similar to the lightening reaction of the residual oil. Therefore, in addition to improving the hydrogenation capacity of the catalyst for carbon residue precursor, the acidity of the catalyst needs to be properly improved to promote the hydrocracking, ring opening and isomerization reactions of macromolecules.
CN106622264a discloses a hydrodecarbonization catalyst and a preparation method and application thereof, the catalyst comprises an active metal component and a modified hydrogenation catalyst carrier, the modified hydrogenation catalyst carrier comprises a carrier, and a metal auxiliary agent and an acid auxiliary agent which are loaded on the carrier, wherein the metal auxiliary agent and the acid auxiliary agent are distributed on the carrier in a layered manner, a shell layer is the metal auxiliary agent, a core layer is the acid auxiliary agent, the metal auxiliary agent is an IA metal component and/or an IIA metal component, and the acid auxiliary agent is at least one component selected from F, P and B. The method adjusts the structure and acidity of the catalyst by adding metal auxiliary agents and acid auxiliary agents, but the prepared catalyst has low matching degree between the acidity structure and the pore structure of the catalyst.
CN111821986a discloses a preparation method of a hydrodecarbonization catalyst, and the preparation process of the catalyst comprises the following steps: (1) Mixing a pore-expanding agent with pseudo-boehmite to obtain a mixture A; (2) Mixing metakaolin, ammonium bicarbonate and water, sealing for crystallization, drying, roasting, dealuminizing and drying the crystallized material to obtain a material B; (3) the mixture A is formed by rolling balls to obtain a precursor I; (4) Mixing the material B with the precursor I, performing rolling ball forming, drying, roasting, and loading active components to obtain the hydrodecarbonization catalyst. Although the catalyst prepared by the method has larger surface pore canal and higher acid content, the acid content in the catalyst is relatively lower, which is unfavorable for the carbon residue removal reaction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a boron modified alumina carrier, a hydrogenation carbon residue removal catalyst and a preparation method thereof. According to the method, the alumina carrier is subjected to stepwise boron modification treatment, the matching degree of the pore channel structure of the carrier with the L acid content and the B acid content on the surface is adjusted, and the hydrogenation carbon residue removal catalyst is obtained by further dipping active components, so that the catalyst has higher hydrogenation desulfurization, denitrification and carbon residue removal activities in the heavy oil hydrogenation treatment process.
The boron modified alumina carrier is a composite carrier of boron modified alumina flake alumina and boron modified granular alumina, the grain size of the boron modified flake alumina is 100-500 nm, and the grain size of the boron modified granular alumina is 20-100 nm; the total boron content is 3.5 to 8.5 weight percent based on the weight of the boron modified alumina carrier, the boron content on the boron modified flaky alumina is 3.5 to 10 weight percent based on the element, and the boron content on the boron modified granular alumina is 1.0 to 2.5 weight percent based on the element. The method for measuring the boron content comprises the following steps: the total boron content was obtained by measurement using an X-ray fluorescence spectrometer. The boron content on the boron modified flaky alumina and the boron modified granular alumina is measured by adopting a scanning electron microscope-energy spectrometer to select areas, 5 areas of two morphology particles are randomly selected for measurement, 10 points are selected for each measurement area, the distance between each point is more than 2 mu m, and the average value of the contents of different measurement positions of each area is taken as the micro-area content.
The preparation method of the boron modified alumina carrier comprises the following steps:
(1) Preparing boron modified gamma-phase alumina powder;
(2) Preparing flaky boron modified flaky pseudo-boehmite P1 by taking the boron modified gamma-phase alumina powder in the step (1) as a raw material;
(3) Mixing and kneading the boron modified sheet pseudo-boehmite P1 and pseudo-boehmite P2 to form, drying, roasting, soaking the boron-containing solution again, drying and roasting to obtain the boron modified alumina carrier.
In the method, the boron modified gamma-phase alumina powder in the step (1) is gamma-phase alumina powder containing boron, wherein the boron content in the powder is 5-8wt% calculated by the elements, and the balance is alumina. The preparation process includes impregnating gamma-phase alumina powder with boric acid solution with boron content of 3-100-10 g/100mL, soaking in equal volume or over volume, and drying at 100-160 deg.c for 4-10 hr. After the last impregnation, the impregnated material is preferably subjected to a calcination treatment, the calcination temperature being generally 450-550 ℃ and the calcination time being 4-8 hours. The gamma-phase alumina powder can be a commercial product or can be prepared according to the prior art, and is generally prepared by taking a pseudo-boehmite precursor which is sold in the market or prepared by the prior art as a raw material and roasting the pseudo-boehmite precursor to obtain the gamma-phase alumina powder; the roasting temperature is 450-550 ℃ and the roasting time is 4-8 hours.
In the method, the preparation process of the boron modified sheet pseudo-boehmite in the step (2) comprises the steps of mixing boron modified alumina powder with propylene oxide aqueous solution, performing hydrothermal treatment, and performing liquid-solid separation and drying on the treated material. Wherein the mass percentage concentration of the propylene oxide aqueous solution is 2.5-12%, preferably 4-8%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the boron modified gamma-phase alumina powder is 3:1-10:1, preferably 4:1-8:1, a step of; the hydrothermal treatment is carried out in a closed container, the sealed container is preferably an autoclave, the treatment temperature is 110-180 ℃, preferably 120-160 ℃, the treatment time is 4-8 hours, and the pressure in the sealed container is autogenous pressure during the hydrothermal treatment; the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
In the method of the invention, the boron modified sheet pseudo-boehmite P1 prepared in the step (2) has the following properties: 1.0<F 1 ≤1.5，1.5<F 2 ≤1.8，F 1 =D（120）/ D（031），F 2 =d (120)/D (020); the D (120) represents the crystal grain size of a crystal face corresponding to a (120) peak in an XRD spectrum of pseudo-boehmite crystal grain; d (031) represents the grain size of a crystal face corresponding to the (031) peak in the pseudo-boehmite crystal grain XRD spectrum; d (020) represents a crystal grain size of a crystal face corresponding to a (020) peak in the pseudo-boehmite crystal grain XRD spectrum; the 120 peak refers to 25.5-Characteristic peak of 29.9 degrees; the 031 peak is a characteristic peak with the 2 theta of 36.3-40.5 degrees in an XRD spectrum; the 020 peak is a characteristic peak with 2 theta of 12.0-16.2 degrees in an XRD spectrum, D=Kλ/(Bcosθ), K is Scherrer constant, λ is diffraction wavelength of a target material, B is half-peak width of the diffraction peak, and θ is diffraction angle.
In the method of the invention, the pseudo-boehmite P2 in the step (3) has the following properties: 0.6<F 1 <1.0，1.0<F 2 <Pseudo-boehmite with a pore size of 8-15nm is preferred in 1.5. The pseudo-boehmite P2 particles are granular and can be prepared by the prior methods, such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis and the like.
In the method, the mass ratio of the boron modified sheet pseudo-boehmite P1 to the pseudo-boehmite P2 in the step (3) is 1:3-1:1.
in the method of the invention, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and in the molding process, one or more conventional molding aids such as a peptizing agent, an extrusion aid and the like can be added according to requirements. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the mass percentage concentration of the peptizing agent is 0.5% -2%, and the dosage of the peptizing agent is determined according to the molding effect; the extrusion aid is sesbania powder, and the addition amount of the extrusion aid is 1-3% of the weight of the final alumina carrier.
In the method, the boron-containing solution in the step (3) is an aqueous solution of boric acid, wherein the boron content in the solution is 0.5g/100mL-5g/100mL calculated by elements, and the solution dosage is the saturated water absorption capacity of the alumina carrier.
In the method, the drying temperature in the step (3) is 100-160 ℃ and the drying time is 6-10 hours; the roasting temperature is 450-750 ℃, preferably 500-650 ℃ and the roasting time is 4-6 hours.
The invention also provides a hydrogenation carbon residue removal catalyst which comprises a hydrogenation active metal component and a boron modified alumina carrier. The content of the hydrogenation active metal component is 10 to 30 weight percent calculated by oxide, and the content of the boron modified alumina carrier is 70 to 90 weight percent; wherein the hydrogenation active metal component is a metal of a VIB group and a metal of a VIII group, the metal of the VIB group is selected from W and/or Mo, and the metal of the VIII group is selected from Co and/or Ni; preferably, the group VIB metal is present in an amount of 8.5wt% to 20.5wt% on an oxide basis and the group VIII metal is present in an amount of 2.5wt% to 10.5wt% on an oxide basis.
The specific surface area of the hydrodecarbonization catalyst of the invention is 240-330m 2 The pore volume per gram is 0.7-1.1mL/g, the pores with the diameter of 8-15nm account for 55% -80% of the total pore volume, the total acid content of the catalyst is 0.35-0.5 mmol/g, the acid content of B is 0.05-0.15 mmol/g, and the acid content of L is 0.3-0.4 mmol/g.
The preparation method of the hydrodecarbonization catalyst comprises the following steps: and loading the active metal component on the boron modified alumina carrier to obtain the hydrodecarbonization catalyst.
The loading process generally adopts an impregnation mode, and drying and roasting are carried out after impregnation. The impregnation may be selected from isovolumetric impregnation or over volumetric impregnation, preferably isovolumetric impregnation. The impregnating solution is a solution containing a group VIB metal and a group VIII metal. The VIB metal is Mo and/or W, preferably Mo, the VIII metal is Ni and/or Co, preferably Ni, the content of the VIB metal is 6.5-20.5g/100mL calculated by oxide, the content of the VIII metal is 1.5-10.0g/100mL calculated by oxide, and the active component impregnating solution can be ammonia solution, aqueous solution or phosphoric acid solution of the VIB metal and the VIII metal, preferably phosphoric acid solution containing the VIB metal and the VIII metal; the drying and roasting conditions are well known to those skilled in the art, such as drying temperature 100-160 ℃ and drying time 6-10 hours; roasting temperature is 450-550 ℃ and roasting time is 4-6 hours.
The application of the hydrodecarbonization catalyst in the heavy oil hydrotreating process has the following general reaction conditions: the reaction temperature is 350-430 ℃, the pressure is 10-15MPa, and the liquid hourly space velocity is 0.5-1.3 hours -1 The volume ratio of hydrogen oil is 500-1200.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, firstly, boric acid solution is used for impregnating gamma-phase alumina powder, and when the powder is roasted, boric acid acts on an alumina carrier and forms hydroxyl connected with boron oxide tetrahedron, so that the flake alumina formed by rehydration has higher B acid content. When the alumina carrier is prepared, two pseudo-boehmite with different properties are used as raw materials, wherein one pseudo-boehmite secondary particle form is a flaky particle stacking body, the particles are formed by stacking flaky particles relatively poorly, more open macroporous channels can be formed in the final alumina carrier, and meanwhile, the macroporous part has higher B acid content and proper L acid content; the other pseudo-boehmite secondary particle form is a spherical particle stacking body, and the pore channel structure of the alumina carrier can be adjusted when the two pseudo-boehmite with different forms are used as raw materials for preparing the alumina carrier, so that the content of macropores is improved.
(2) When the formed alumina carrier is subjected to boron modification again, on one hand, the hydroxyl structure on the surface of the alumina carrier can be totally improved due to the addition of boron, and the B acid content of the carrier is moderately improved; on the other hand, due to the regulation of the surface property of the alumina carrier by the boron, the action of active metal and the carrier in the final catalyst is improved, and the activity of the catalyst is improved.
(3) The catalyst prepared by the invention has two pore structures, one is a pore structure formed by stacking flaky alumina, wherein the pore structure is relatively large, and the other is a conventional pore formed by stacking granular alumina. In the hydrogenation reaction process, macromolecular reactants more easily enter holes formed by stacking of flaky alumina, the acid content of B at the hole channels is relatively high, and the reactants entering the hole channels are easy to undergo ring opening and cracking reactions, so that the sizes of the reactants are reduced. So that the formed unreacted and completely cracked products can easily enter the conventional pore canal formed by stacking the granular alumina, and further hydrogenation reaction is carried out to reduce the impurity content. The catalyst has high hydrogenation impurity removing activity due to the organic combination of two forms and surface acidic alumina.
Drawings
FIG. 1 is an SEM image of boron modified pseudo-boehmite P1-1 prepared in example 1.
FIG. 2 is an XRD spectrum of boron modified pseudo-boehmite P1-1 prepared in example 1.
FIG. 3 is a cross-sectional SEM image of the hydrodecarbonization catalyst prepared in example 5.
Detailed Description
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited thereto. Wherein, in the invention, wt% represents mass fraction.
The method for measuring the grain size of the flaky alumina comprises the following steps: and observing the morphology of the particles in the cross section of the sample by using a scanning electron microscope, randomly selecting a stacking area of the flaky alumina crystal grains for observation, measuring the lengths of 100 flaky alumina crystal grains, and obtaining an average value as the sizes of the flaky alumina crystal grains.
The grain size determination method of the granular alumina comprises the following steps: and observing the particle morphology of the cross section of the sample by using a scanning electron microscope, randomly selecting a stacking area of the granular alumina grains for observation, measuring the radial longest dimension of 100 granular alumina grains, and obtaining an average value as the grain size of the granular alumina grains.
BET method: application N 2 Physical adsorption-desorption characterization examples and comparative examples the pore structure of the carriers were as follows: using ASAP-2420 type N 2 The physical adsorption-desorption instrument characterizes the structure of the sample hole. And (3) taking a small amount of sample, vacuum-treating for 3-4 hours at 300 ℃, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the specific surface area is obtained according to BET equation, and the distribution ratio of pore volume and pore diameter below 30nm is obtained according to BJH model.
The microstructure of the alumina carrier is characterized by applying a scanning electron microscope, and the specific operation is as follows: the JSM-7500F scanning electron microscope is adopted to characterize the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 mu A, and the working distance is 8mm.
And (3) measuring the components of the catalyst micro-regions by using an EDAX spectrometer, wherein the resolution is 144eV, and detecting the element C-U.
X-ray diffraction (XRD) analysis was performed on a D/max-2500 type full-automatic rotary target X-ray diffractometer manufactured by Japanese Kabushiki Kaisha. The Cu target, the K alpha radiation source, the graphite monochromator and the tube voltage of 40kV and the tube current of 80mA are adopted.
L acid content determination: will bePlacing the sample into a vacuum system, and pumping the sample to 1×10 -2 Pa, heating to 500 ℃ and keeping the temperature for 1h, purifying the sample, removing adsorbate, water and the like which are covered on the surface of the sample, then continuously vacuumizing, cooling to room temperature, introducing pyridine for adsorption, then heating to 160 ℃ for measuring the L acid content, and measuring and calculating according to a method for measuring the acidity of the solid surface of the catalyst by a literature weight adsorption-infrared spectrometry (modern chemical industry, volume 39, 5).
XRF characterization: analyzing sample components by using a Japan-based ZSX100 e-type X-ray fluorescence spectrometer, and performing light path atmosphere on a target Rh: vacuum conditions.
Desulfurization percentage = (sulfur content of raw oil-sulfur content of product)/sulfur content of raw oil x 100%.
Denitrification rate% = (raw oil nitrogen content-product nitrogen content)/raw oil nitrogen content x 100%.
Percent carbon removal = (raw oil carbon residue value-product carbon residue value)/raw oil carbon residue value x 100%.
Relative impurity removal rate: the impurity removal rate of a certain catalyst was measured and defined as 100% relative impurity removal rate, and the impurity removal rate of other catalyst was defined as 100% relative impurity removal rate.
Preparation of boron modified sheet pseudo-boehmite:
example 1
500 g of pseudo-boehmite (prepared by an aluminum sulfate-sodium metaaluminate method, dry basis weight content of 75.5%) is weighed, and placed in a muffle furnace to be roasted for 6 hours at 500 ℃ to prepare gamma-phase alumina powder. And (3) immersing the gamma-phase alumina powder in a supersaturated immersing way for 2 hours by using a boric acid solution with the boron content of 5.5g/100mL, separating liquid from solid after immersing, drying the solid material at 120 ℃ for 6 hours, and roasting at 500 ℃ for 6 hours to obtain the boron-modified gamma-phase alumina powder, wherein the boron content of the powder is 5.8wt% calculated by elements.
Weighing 100 g of the boron modified gamma-phase alumina powder, adding 530 g of propylene oxide solution with the mass concentration of 6.3%, magnetically stirring for 30 minutes, transferring the mixed material into an autoclave, sealing, heating at 145 ℃ for 6.5 hours, cooling, filtering and washing the solid material, and drying at 110 ℃ for 6 hours to obtain boron modified flaky pseudo-boehmite P1-1, wherein the properties of the pseudo-boehmite are shown in table 1, the scanning electron microscope image of the pseudo-boehmite is shown in figure 1, and the XRD spectrogram is shown in figure 2.
Example 2
The same as in example 1 except that the boron content in the boric acid-containing solution was 4.8%, the firing temperature of the pseudo-boehmite and the gamma-phase alumina powder impregnated with the boric acid solution was 450 ℃, and the boron content in the prepared boron-modified gamma-phase alumina powder was 5.1% by weight in terms of the element. The propylene oxide solution was used in an amount of 640 g and the mass concentration of the solution was 5.1%. The heat treatment temperature is 145 ℃ and the treatment time is 5.5 hours, and the pseudo-boehmite P1-2 is prepared, and the properties of the pseudo-boehmite are shown in Table 1.
Example 3
The same as in example 1 except that the boron content in the boric acid-containing solution was 6.5%, the boron content in the prepared boron-modified gamma-phase alumina powder was 6.2% by weight in terms of element. The propylene oxide solution was used in an amount of 440 g and the mass concentration of the solution was 7.5%. The heat treatment temperature is 125 ℃ and the treatment time is 7.5 hours, and the pseudo-boehmite P1-3 is prepared, and the properties of the pseudo-boehmite are shown in Table 1.
Example 4
The same as in example 1 except that the boron content in the boric acid-containing solution was 6.9%, the boron content in the prepared boron-modified gamma-phase alumina powder was 7.1% by weight in terms of element. The propylene oxide solution was used in an amount of 760 g and the mass concentration of the solution was 4.3%. The heat treatment temperature is 155 ℃ and the treatment time is 4.5 hours, and the pseudo-boehmite P1-4 is prepared, and the properties of the pseudo-boehmite are shown in Table 1.
Comparative example 1
A comparative boehmite P5 was prepared as in example 1, except that propylene oxide was replaced with the same amount of ethylene oxide, and the properties of the pseudo-boehmite are shown in Table 1.
Comparative example 2
Comparative boehmite P6, the properties of which are shown in Table 1, were obtained by replacing propylene oxide with the same amount of distilled water as in example 1.
Comparative example 3
Comparative boehmite P7 was prepared as in example 1 except that boric acid solution was not impregnated on gamma-phase alumina powder but the same amount of boric acid solution was impregnated on pseudo-boehmite to prepare comparative pseudo-boehmite P7, and the properties of pseudo-boehmite are shown in Table 1.
Comparative example 4
Comparative boehmite P8, which does not contain boron and has properties shown in Table 1, was prepared as in example 1 except that the alumina powder was not subjected to boron modification treatment.
Preparing a hydrogenation carbon residue removal catalyst:
example 5
50 g (pore diameter 9.5 nm) of pseudo-boehmite P2 is weighed, 27 g of boron modified pseudo-boehmite P1-1 prepared in example 1 and 0.5g of sesbania powder are evenly mixed, a proper amount of acetic acid aqueous solution with mass concentration of 1% is added for mixing and kneading, extrusion molding is carried out, the molded product is dried for 6 hours at 140 ℃, and the dried product is baked for 5 hours in the air at 600 ℃ to prepare the alumina carrier.
50 g of the alumina carrier is weighed, the alumina carrier is impregnated with boric acid solution with the boron content of 2.0g/100mL calculated as elements in an equal volume impregnation mode, the impregnated carrier is roasted in air at 650 ℃ for 5 hours, the boron modified alumina carrier S1 is prepared, the properties of the carrier are shown in Table 2, and a scanning electron microscope image of the cross section of the carrier is shown in figure 3.
40 g of the boron modified alumina carrier is weighed, the alumina carrier is impregnated with Mo-Ni-P impregnating solution with the concentration of molybdenum oxide of 16.5g/100mL and the concentration of nickel oxide of 3.4g/100mL in a saturated impregnation mode, the impregnated material is dried at 120 ℃ for 6 hours, and the dried material is roasted in air at 500 ℃ for 5 hours, so that the hydrodecarbonization catalyst Cat-1 is prepared.
Example 6
As in example 5, except that boron modified pseudo-boehmite was prepared in example 2, the amount of added boron modified pseudo-boehmite was 33 g. When the alumina carrier is immersed in boric acid, the boron content in the boric acid solution is 1.5g/100mL in terms of element concentration, and the boron modified alumina carrier S2 is prepared, and the carrier properties are shown in Table 2. The carrier is impregnated with active components to prepare the hydrodecarbonization catalyst Cat-2.
Example 7
As in example 5, except that boron modified pseudo-boehmite was prepared in example 3, the amount of added boron modified pseudo-boehmite was 22 g. When the alumina carrier is immersed in boric acid, the boron content in the boric acid solution is 2.3g/100mL in terms of element concentration, and the boron modified alumina carrier S3 is prepared, and the carrier properties are shown in Table 2. The carrier is impregnated with active components to prepare the hydrodecarbonization catalyst Cat-3.
Example 8
As in example 5, except that boron modified pseudo-boehmite was prepared in example 4, the amount of added boron modified pseudo-boehmite was 40 g. When the alumina carrier is immersed in boric acid, the boron content in the boric acid solution is 1.2g/100mL in terms of element concentration, and the boron modified alumina carrier S4 is prepared, and the carrier properties are shown in Table 2. The carrier is impregnated with active components to prepare the hydrodecarbonization catalyst Cat-4.
Comparative example 5
Comparative alumina carrier S5 was prepared as in example 5 except that boron modified flaky pseudo-boehmite P1-1 was changed to pseudo-boehmite P5 prepared in comparative example 1 in the same amount, and the carrier properties are shown in Table 2. The catalyst Cat-5 for hydrodecarbonization of the comparative example is prepared after the carrier is impregnated with the active component.
Comparative example 6
Comparative alumina carrier S6 was prepared as in example 5 except that boron modified flaky pseudo-boehmite P1-1 was changed to pseudo-boehmite P6 prepared in comparative example 2 in the same amount, and the carrier properties are shown in Table 2. The catalyst Cat-6 for hydrodecarbonization of the comparative example is prepared after the carrier is impregnated with the active component.
Comparative example 7
Comparative alumina carrier S7 was prepared as in example 5 except that boron modified flaky pseudo-boehmite P1-1 was changed to pseudo-boehmite P7 prepared in comparative example 3 in the same amount, and the carrier properties are shown in Table 2. The catalyst Cat-7 for hydrodecarbonization of the comparative example is prepared after the carrier is impregnated with the active component.
Comparative example 8
Comparative alumina carrier S8 was prepared as in example 5 except that boron modified sheet pseudo-boehmite P1-1 was replaced with the same amount of pseudo-boehmite P8 prepared in comparative example 4, and the content of boron in boric acid were 4.6g/100mL when the alumina carrier was impregnated with boric acid, and the carrier properties were as shown in Table 2. The catalyst Cat-8 for hydrodecarbonization of the comparative example is prepared after the carrier is impregnated with the active component.
TABLE 1 pseudo-boehmite properties
TABLE 2 hydrodecarbonization catalyst Properties
Catalytic performance evaluation:
the hydrodecarbonization catalysts (Cat-1-Cat-8) prepared in the above examples and comparative examples were subjected to catalytic performance evaluation as follows:
the sulfur content in the raw oil was 5.1wt%, the nitrogen content was 0.4wt%, and the carbon residue value was 18.9wt%. The catalytic performance of the catalyst Cat-1-Cat-8 was evaluated on a fixed bed residuum hydrogenation reactor under the following reaction conditions: the reaction temperature is 380 ℃, the hydrogen partial pressure is 13.5MPa, and the liquid hourly space velocity is 0.85 hour -1 The hydrogen oil volume ratio was 750, the content of each impurity in the produced oil was measured after 500 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 3 comparison of hydrogenation performance of catalysts
As can be seen from the data in Table 3, the hydrodecarbonization catalyst activated by the method of the present invention has higher hydrodesulfurization activity, hydrodenitrogenation activity and hydrodecarbonization activity than the comparative catalyst.
Claims (18)
1. A boron modified alumina support characterized by: the carrier is a composite carrier of boron modified alumina flake alumina and boron modified granular alumina, the total boron content is 3.5-8.5 wt% calculated by elements, the boron content on the boron modified flake alumina is 3.5-10 wt% calculated by elements, and the boron content on the boron modified granular alumina is 1.0-2.5 wt% calculated by elements.
2. The boron-modified alumina support of claim 1, wherein: the grain size of the boron modified flaky alumina is 100-500 nm, and the grain size of the boron modified granular alumina is 20-100 nm.
3. A method for preparing the boron-modified alumina carrier of claim 1 or 2, comprising the following steps: (1) preparing boron modified gamma-phase alumina powder; (2) Preparing flaky boron modified flaky pseudo-boehmite P1 by taking the boron modified gamma-phase alumina powder in the step (1) as a raw material; (3) And kneading the boron modified sheet pseudo-boehmite P1 and pseudo-boehmite P2 to form, drying, roasting, soaking in boric acid aqueous solution again, drying and roasting to obtain the boron modified alumina carrier.
4. A method according to claim 3, characterized in that: the boron content of the boron modified gamma-phase alumina powder in the step (1) is 5-8wt% calculated by elements.
5. A method according to claim 3, characterized in that: the preparation process of the boron modified sheet pseudo-boehmite in the step (2) comprises the steps of mixing boron modified alumina powder with propylene oxide aqueous solution, performing hydrothermal treatment, and performing liquid-solid separation and drying on the treated material; wherein the mass percentage concentration of the epoxypropane aqueous solution is 2.5-12%, and the mass ratio of the epoxypropane aqueous solution to the boron modified gamma-phase alumina powder is 3:1-10:1, a step of; the hydrothermal treatment is carried out in a closed container, the treatment temperature is 110-180 ℃, the treatment time is 4-8 hours, and the pressure in the closed container is autogenous pressure during the hydrothermal treatment; the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
6. A method according to claim 3, characterized in that: the boron modified sheet pseudo-boehmite P1 prepared in the step (2) has the following properties:1.0<F 1 ≤1.5，1.5<F 2 ≤1.8，F 1 =D（120）/ D（031），F 2 =d (120)/D (020); the D (120) represents the crystal grain size of a crystal face corresponding to a (120) peak in an XRD spectrum of pseudo-boehmite crystal grain; d (031) represents the grain size of a crystal face corresponding to the (031) peak in the pseudo-boehmite crystal grain XRD spectrum; d (020) represents a crystal grain size of a crystal face corresponding to a (020) peak in the pseudo-boehmite crystal grain XRD spectrum; the 120 peaks refer to characteristic peaks with 2 theta of 25.5-29.9 degrees in an XRD spectrum; the 031 peak is a characteristic peak with the 2 theta of 36.3-40.5 degrees in an XRD spectrum; the 020 peak is a characteristic peak with 2 theta of 12.0-16.2 degrees in an XRD spectrum, D=Kλ/(Bcosθ), K is Scherrer constant, λ is diffraction wavelength of a target material, B is half-peak width of the diffraction peak, and θ is diffraction angle.
7. A method according to claim 3, characterized in that: the pseudo-boehmite P2 in the step (3) has the following properties: 0.6<F 1 <1.0，1.0<F 2 <1.5, preferably pseudo-boehmite having a pore size of 8 to 15nm, the pseudo-boehmite P2 having a particulate form.
8. A method according to claim 3, characterized in that: the mass ratio of the boron modified sheet pseudo-boehmite P1 to the pseudo-boehmite P2 in the step (3) is 1:3-1:1.
9. a method according to claim 3, characterized in that: adding a peptizing agent and/or an extrusion aid in the kneading molding process in the step (3); the peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid, and the mass percentage concentration of the peptizing agent is 0.5% -2%; the extrusion aid is sesbania powder, and the addition amount of the extrusion aid is 1-3% of the weight of the final alumina carrier.
10. A method according to claim 3, characterized in that: the boron content of the boric acid aqueous solution in the step (3) is 0.5g/100mL-5g/100mL calculated by elements, and the solution dosage is the saturated water absorption capacity of the alumina carrier.
11. A method according to claim 3, characterized in that: the drying temperature in the step (3) is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 450-750 ℃, preferably 500-650 ℃ and the roasting time is 4-6 hours.
12. A hydrodecarbonization catalyst is characterized in that: comprising a hydrogenation-active metal component and the boron-modified alumina support of claim 1 or 2.
13. The catalyst of claim 12, wherein: the content of the hydrogenation active metal component is 10 to 30 weight percent calculated by oxide, and the content of the boron modified alumina carrier is 70 to 90 weight percent; wherein the hydrogenation active metal component is a metal of a VIB group and a metal of a VIII group, the metal of the VIB group is selected from W and/or Mo, and the metal of the VIII group is selected from Co and/or Ni.
14. The catalyst of claim 12, wherein: specific surface area of 240-330m 2 The pore volume per gram is 0.7-1.1mL/g, and the pores with the diameters of 8-15nm account for 55-80% of the total pore volume.
15. The catalyst of claim 12, wherein: the total acid content of the catalyst is 0.35-0.5 mmol/g, the acid content of B is 0.05-0.15 mmol/g, and the acid content of L is 0.3-0.4 mmol/g.
16. A method for preparing the hydrodecarbonization catalyst as claimed in claim 12, characterized by comprising the following contents: loading the boron-modified alumina carrier of claim 1 or 2 with an active metal component to obtain the hydrodecarbonization catalyst.
17. The method according to claim 16, wherein: the loading process adopts an impregnation mode, and drying and roasting are carried out after impregnation; the impregnation can be equal volume impregnation or over volume impregnation; the impregnating solution is a solution containing VIB group metal and VIII group metal; the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co; the content of the metal of the VIB group is 6.5-20.5g/100mL calculated by oxide, and the content of the metal of the VIII group is 1.5-10.0g/100mL calculated by oxide; the drying temperature is 100-160 ℃, and the drying time is 6-10 hours; roasting temperature is 450-550 ℃ and roasting time is 4-6 hours.
18. Use of the hydrodecarbonization catalyst of any of claims 12-15 in heavy oil hydroprocessing processes.
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