CN111097458A - Hydrodemetallization catalyst and preparation method thereof - Google Patents
Hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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- CN111097458A CN111097458A CN201811246100.7A CN201811246100A CN111097458A CN 111097458 A CN111097458 A CN 111097458A CN 201811246100 A CN201811246100 A CN 201811246100A CN 111097458 A CN111097458 A CN 111097458A
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- active metal
- catalyst
- metal component
- hydrogenation active
- rod
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 159
- 239000002184 metal Substances 0.000 claims abstract description 159
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 86
- 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 71
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 18
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 17
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 238000004898 kneading Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 94
- 238000005470 impregnation Methods 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 26
- 150000002739 metals Chemical class 0.000 claims description 24
- -1 VIB group metals Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007598 dipping method 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [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
- 238000002386 leaching Methods 0.000 claims description 2
- 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 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 239000003921 oil Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 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 4
- 239000000126 substance Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 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
- 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
-
- 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
- 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
- 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
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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 hydrodemetallization catalyst and a preparation method thereof. The method comprises the following steps: (1) kneading and molding a physical pore-expanding agent, pseudo-boehmite and a first hydrogenation active metal component source, drying and roasting to obtain an alumina carrier intermediate; (2) immersing the alumina carrier intermediate obtained in the step (1) into an ammonium bicarbonate solution, then carrying out sealing heat treatment, and drying and roasting the heat-treated material to obtain a modified alumina carrier; (3) and (3) respectively impregnating and loading the second hydrogenation active metal component and the third hydrogenation active metal component on the modified alumina-based carrier obtained in the step (2) to prepare the hydrodemetallization catalyst. The catalyst obtained by the method has strong metal deposition resistance and carbon deposition resistance, good activity and stability, and is suitable for the hydrotreating process of heavy oil.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a hydrodemetallization catalyst and a preparation method thereof.
Background
With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. During the processing of heavy oil, the metal compounds therein are decomposed, and the metal impurities are deposited on the inner and outer surfaces of the catalyst to block the pore channels, even cause the catalyst to be poisoned and deactivated, so that the metal impurities contained therein must be removed firstly during the catalytic cracking of heavy oil. The hydrodemetallization catalyst mainly removes metal impurities including nickel and vanadium in raw oil, so as to protect downstream catalysts from losing activity due to deposition of a large amount of metals.
At present, most of the commercial Hydrodemetallization (HDM) catalysts are made of Al2O3Being a support, the pore structure of the support can significantly affect its catalytic activity as well as its stability. The results of previous studies show that: suitable Al2O3The pore size distribution of the carrier can provide a proper diffusion rate of metal compounds, the existence of a certain proportion of super-large pores in the alumina carrier can promote the diffusion and deposition of macromolecular asphaltene molecules, reduce the blockage of coke deposition to orifices, and even under the condition of serious nickel and vanadium deposition, the large pores can also allow the macromolecules to pass through, thereby improving the stability of the catalyst.
CN1160602A discloses a macroporous alumina carrier suitable for use as a hydrodemetallization catalyst carrier and a preparation method thereof. The preparation method of the macroporous alumina carrier comprises the steps of mixing the pseudo-boehmite dry glue powder with water or aqueous solution, kneading into a plastic body, extruding the obtained plastic body into a strip-shaped object on a strip extruding machine, drying and roasting to obtain a product; in the above-mentioned process also the carbon black powder is added as physical pore-expanding agent and chemical pore-expanding agent containing phosphorus, silicon or boron compound which can produce chemical action with pseudo-boehmite or alumina. Wherein the amount of the carbon black powder is 3-10% (based on the weight of the alumina). The prepared alumina carrier can be used for preparing heavy oil, in particular a heavy oil hydrodemetallization and/or hydrodesulfurization catalyst.
US4448896 proposes the use of carbon black as a pore-enlarging agent. Uniformly mixing a pore-expanding agent and pseudo-boehmite dry rubber powder, adding a nitric acid aqueous solution with the mass fraction of 4.3% into the mixture, kneading for 30 minutes, then adding an ammonia aqueous solution with the mass fraction of 2.1%, kneading for 25 minutes, extruding into strips and forming after uniform kneading, and roasting the formed carrier to obtain the final alumina carrier. Wherein the addition amount of the carbon black powder is preferably more than 20% of the weight of the activated alumina or the precursor thereof.
CN102441436A discloses a preparation method of an alumina carrier. The method for preparing the alumina carrier comprises the following steps: the pseudo-boehmite dry glue powder and the extrusion aid are mixed uniformly, then the aqueous solution in which the physical pore-enlarging agent and the chemical pore-enlarging agent are dissolved is added, the mixture is mixed uniformly, the mixture is extruded on a strip extruder to be formed, and the alumina carrier is prepared after drying and roasting.
The physical pore-expanding agent can increase the proportion of macropores, but in the case of industrial catalysts, certain specific surface area and mechanical strength are required in order to improve the activity of the catalyst. However, the specific surface area and the mechanical strength are reduced while the macropores are increased, so that the physical pore-expanding agent is limited by other performance requirements of the catalyst when being used for pore expansion, and the physical pore-expanding agent cannot be taken into consideration.
CN103785396A and CN102861617A disclose a preparation method of a dual pore structure alumina carrier for heavy oil hydrodemetallization catalyst. The method comprises the following steps: weighing a certain amount of pseudo-boehmite dry glue powder, uniformly mixing the pseudo-boehmite dry glue powder with a proper amount of peptizer and extrusion aid, then adding a proper amount of ammonium bicarbonate aqueous solution into the materials, kneading the obtained materials into a plastic body, extruding the plastic body into strips for forming, placing the formed materials into a sealed container, carrying out hydrothermal treatment, and roasting to obtain the alumina carrier. The heavy oil hydrodemetallization catalyst is prepared by taking the alumina as a carrier and loading active metal components Mo and Ni by an impregnation method. Although the catalyst prepared by the technology has double-pore distribution, the pore diameter of a large-pore part is larger, so that the time for reaction molecules to stay in a pore channel is shorter, the utilization rate of a carrier is reduced, and the stability needs to be further improved.
CN106140183A discloses a preparation method of zirconium-containing hydrodemetallization catalyst, which comprises: respectively dipping the physical pore-expanding agent by using dipping liquid containing the hydrogenation active component and solution containing zirconium; mixing and kneading the impregnated physical pore-enlarging agent, pseudo-boehmite, a chemical pore-enlarging agent, an extrusion aid and a peptizing agent into a plastic body, extruding strips, drying and roasting to prepare a modified alumina carrier; the modified alumina carrier is impregnated by hydrogenation active component impregnating solution, and the zirconium-containing hydrogenation demetallization catalyst is prepared after drying and roasting. The activity and long-term running stability of the catalyst prepared by the method are still to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrodemetallization catalyst and a preparation method thereof. The catalyst prepared by the method has strong metal deposition resistance and carbon deposition resistance, good activity and stability, and is suitable for the hydrotreating process of heavy oil.
The first aspect of the present invention provides a preparation method of a hydrodemetallization catalyst, comprising:
(1) kneading and molding a physical pore-expanding agent, pseudo-boehmite and a first hydrogenation active metal component source, drying and roasting to obtain an alumina carrier intermediate;
(2) immersing the alumina carrier intermediate obtained in the step (1) into an ammonium bicarbonate solution, then carrying out sealing heat treatment, and drying and roasting the heat-treated material to obtain a modified alumina carrier;
(3) and (3) respectively impregnating and loading the second hydrogenation active metal component and the third hydrogenation active metal component on the modified alumina-based carrier obtained in the step (2) to prepare the hydrodemetallization catalyst.
In the method, the physical pore-enlarging agent in the step (1) can be one or more of activated carbon and wood chips, the particle size of the physical pore-enlarging agent is about 2-10 mu m, preferably about 3-8 mu m, and the mass ratio of the added amount of the physical pore-enlarging agent to the pseudo-boehmite is 1:8-1: 5.
In the method of the present invention, the pseudoboehmite described in the step (1) may be a pseudoboehmite prepared by any method, for example, prepared by a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method, and the like.
In the method, the first hydrogenation active metal component source in the step (1) is a compound containing VIB group and/or VIII group metals. The source of the first hydrogenation-active metal component is preferably a soluble compound containing a group VIB and/or group VIII metal. The group VIB metal is preferably one or more of W, Mo and the soluble group VIB metal containing compound is preferably at least one of ammonium molybdate, ammonium paramolybdate, ammonium tungstate, ammonium metatungstate. The VIII group metal is preferably one or more of Co and Ni, and the soluble compound containing the VIII group metal is at least one of nickel nitrate and cobalt nitrate. Preferably, the first hydrogenation active metal component source is a soluble compound containing VIB group and VIII group metals, and the mass ratio of the addition amount of the VIB group metals to the addition amount of the VIII group metals is 1:1-4: 1.
In the method, the kneading molding in the step (1) is carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids such as one or more of peptizing agents, extrusion aids and the like can be added according to needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the addition amount of the peptizing agent is 0.5-3 wt% of the weight of the alumina carrier intermediate. The extrusion aid is sesbania powder; the addition amount of the extrusion aid is 0.1-0.5 wt% of the weight of the alumina carrier intermediate.
In the method, the roasting temperature in the step (1) is 600-; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere. The shape of the alumina carrier intermediate can be the shape of a conventional alumina carrier, such as a sphere, the particle size of the alumina carrier intermediate is generally 0.5-8.0mm, such as a strip, clover and the like, the diameter of the alumina carrier intermediate is about 0.2-3.0mm, and the length of the alumina carrier intermediate is about 0.5-8.0 mm.
In the method, the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the added alumina carrier intermediate in the step (2) is 6:1-12:1, and the mass concentration of the ammonium bicarbonate solution is 15-25%.
In the method of the invention, the sealing heat treatment temperature in the step (2) is 120-.
In the method, the step (2) is preferably carried out before the sealing heat treatment, the sealing pretreatment is carried out, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min lower than that before the pretreatment, preferably at least 5 ℃/min lower.
In the method, the roasting temperature in the step (2) is 550-750 ℃, and the roasting time is 4-6 hours.
In the step (3), the second hydrogenation active metal component and the third hydrogenation active metal component are hydrogenation active metal components adopted by a conventional residual oil hydrotreating catalyst, and are generally group VIB metals and/or group VIII metals, the group VIB metals are generally selected from one or two of Mo and W, and the group VIII metals are generally selected from one or two of Co and Ni.
The first active metal component, the second active metal component and the third active metal component may adopt the same active metal component or different active metal components.
The first hydrogenation active metal component is preferably Mo and Ni, the second hydrogenation active metal component is preferably Mo and Ni, and the third hydrogenation active metal component is preferably Mo and Ni.
In the method, the total content of the added active metals is 2.3-28.0 percent by metal oxide, preferably the content of VIB group metals is 2.0-20.0 percent by metal oxide and the content of VIII group metals is 0.3-8.0 percent by metal oxide based on the weight of the hydrodemetallization catalyst. The mass ratio of the added first active metal component, the added second active metal component and the added third active metal component in terms of oxides is (35-85): (140-240): 1.
in the step (3), the modified alumina-based carrier obtained in the step (2) is respectively impregnated and loaded with a second hydrogenation active metal component and a third hydrogenation active metal component, wherein the impregnation and loading of the second hydrogenation active metal component adopts supersaturation impregnation or saturated impregnation, and the impregnation and loading of the third hydrogenation active metal component adopts an unsaturated spray-impregnation method. The impregnation loading sequence of the second hydrogenation active metal component and the third hydrogenation active metal is not limited, and the second hydrogenation active metal component may be loaded first and then the third hydrogenation active metal is loaded, or the third hydrogenation active metal component may be loaded first and then the second hydrogenation active metal is loaded, and after each impregnation loading, the next impregnation loading is performed after drying and roasting treatment. The impregnation liquid containing the hydrogenation active metal component can be one of an acid solution, an aqueous solution or an ammonia solution containing the hydrogenation active component.
In the method, when the second hydrogenation active metal component is impregnated and loaded in the step (3), an impregnation liquid I containing the second hydrogenation active metal component is adopted. The following are preferred: the impregnation liquid I containing the second hydrogenation active metal component simultaneously contains VIB group metals and VIII group metals, wherein the content of the VIB group metals is 5.5-15.0g/100mL calculated by metal oxides, and the content of the VIII group metals is 1.0-3.5g/100mL calculated by metal oxides.
In the method, when the third hydrogenation active metal component is loaded in the step (3) by impregnation, impregnation liquid II containing the third hydrogenation active metal component is adopted. The following are preferred: the impregnation liquid II containing the third hydrogenation active metal component simultaneously contains VIB group metals and VIII group metals, wherein the content of the VIB group metals in the impregnation liquid II is 0.4-2.0g/100mL calculated by metal oxides, and the content of the VIII group metals in the impregnation liquid II is 0.3-1.0g/100mL calculated by metal oxides. And (3) loading a third hydrogenation active metal by using an unsaturated spray-leaching method, wherein the dosage of the impregnation liquid II is 5-10% of the saturated water absorption capacity of the modified alumina-based carrier added in the step (3) according to the volume fraction.
In the step (3), the calcination is generally performed in an oxygen-containing atmosphere, and the calcination time is 4-6 hours at 450-550 ℃.
The drying can be carried out by a conventional method, the drying is generally carried out until the material has no obvious weight loss phenomenon, and the drying condition can be drying for 6-10 hours at the temperature of 80-160 ℃.
In the method of the present invention, an auxiliary agent, such as one or more of phosphorus, boron, silicon, and the like, may also be added. The weight content of the auxiliary agent in the catalyst is less than 10.0 percent, preferably 0.1 to 10.0 percent in terms of oxide.
In a second aspect, the present invention provides a hydrodemetallization catalyst prepared by the process of the first aspect.
The hydrodemetallization catalyst comprises a main body part and a rod-shaped part, wherein the main body part is provided with micron-sized pore channels, at least part of the rod-shaped part is distributed on the outer surface of the main body part and in the micron-sized pore channels with the pore diameter D of 3-10 mu m, the length of the rod-shaped part is 1-12 mu m, and the diameter of the rod-shaped part is 100-300 nm.
The content of the hydrogenation active metal on the rod-shaped part of the outer surface of the main body part of the hydrogenation demetallization catalyst is higher than that in the catalyst bulk phase. The ratio of the content of the hydrogenation active metal on the rod-like portion of the outer surface of the main body portion to the content of the hydrogenation active metal in the catalyst bulk is 1.02:1 to 1.5:1 by weight.
The micron-sized pore channels in the invention refer to micron-sized pore channels with the pore diameter of 3-10 μm.
In the hydrodemetallization catalyst of the invention, the content of the hydrogenation active metal in the rod-like part of the outer surface of the main body part refers to the average content of the hydrogenation active metal in the rod-like part of the outer surface of the main body part of the catalyst, and the content of the hydrogenation active metal in the catalyst bulk phase refers to the average content of the hydrogenation active metal in the catalyst except for the rod-like part of the outer surface of the main body part.
In the modified alumina-based carrier, the rod-shaped parts are basically distributed on the outer surface of the main body part and in the micron-sized pore channels. The rod-shaped parts distributed on the outer surface of the main body part and in the micron-sized pore channels account for more than 95 percent of the total weight of all the rod-shaped parts, and preferably more than 97 percent.
In the modified alumina-based carrier, the length of the rod-shaped part in the micron-sized pore channel is mainly 0.3D-0.9D (which is 0.3-0.9 time of the diameter of the micron-sized pore channel), namely the length of more than 85 percent of the rod-shaped part in the micropore is 0.3D-0.9D by weight; the length of the outer surface rod-like parts is predominantly 3-8 μm, i.e. more than about 85% by weight of the rod-like parts on the outer surface have a length of 3-8 μm.
In the modified alumina-based carrier, rod-shaped parts are distributed in a disordered and mutually staggered state in micron-sized pore channels of a main body part. Wherein at least one end of the rod-like part in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel and is integrated with the main body part.
In the modified alumina-based carrier of the present invention, the rod-like portions are distributed in a disordered and mutually staggered state on the outer surface of the main body portion. Wherein one end of the rod-like portion on the outer surface of the main body portion is bonded to the outer surface of the main body portion, and the other end thereof is extended outwardly to be integral with the main body portion.
In the modified alumina-based carrier, the coverage rate of the rod-shaped part in the micron-sized pore channel of the main body part is 70-95%, wherein the coverage rate refers to the percentage of the surface of the inner surface of the micron-sized pore channel of the main body part, which is occupied by the rod-shaped part, in the inner surface of the micron-sized pore channel of the main body part. The coverage rate of the rod-shaped part on the outer surface of the main body modified alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the outer surface of the main body part occupied by the rod-shaped part on the outer surface of the main body part.
The hydrodemetallization catalyst of the invention has the following properties: the specific surface area is 150-280m2(iv)/g, pore volume of 0.75-1.6mL/g, crush strength of 10-20N/mm.
In the hydrodemetallization catalyst, the pores formed by the rod-shaped parts which are staggered with each other in a disordered way are concentrated between 100 and 800 nm.
The pores of the hydrodemetallization catalyst are distributed as follows: the pore volume of the pores with the pore diameter of less than 10nm accounts for less than 15 percent of the total pore volume, the pore volume of the pores with the pore diameter of 15-35nm accounts for 35-55 percent of the total pore volume, and the pore volume of the pores with the pore diameter of 100-800nm accounts for 15-30 percent of the total pore volume.
The method of the invention has the following advantages:
1. the residual oil hydrodemetallization catalyst prepared by the invention has a specific shape, and comprises a main body part and a rod-shaped part, wherein the main body part is provided with micron-sized pore channels, at least part of the rod-shaped part is distributed on the outer surface of the main body part and in the micron-sized pore channels with the pore diameter D of 3-10 mu m, the length of the rod-shaped part is 1-12 mu m, and the diameter of the rod-shaped part is 100-300 nm. The rod-shaped parts are distributed in a disordered and staggered manner, so that the penetrability of the micron-sized pore channels is maintained, and meanwhile, the specific surface area of the carrier is increased and the mechanical strength is enhanced.
2. In the preparation method, the carrier plays a certain role in reaming the nano-scale pore canal in the alumina carrier during heat treatment in the ammonium bicarbonate solution, and the penetration and the uniformity of the nano-scale pore canal are further promoted. Therefore, the catalyst of the invention overcomes the problem that the large aperture and the specific surface area and the mechanical strength are not compatible because of adopting a physical pore-expanding agent.
3. In the process of preparing the modified alumina-based carrier, the modified alumina-based carrier is pretreated at a certain temperature before sealing heat treatment, the pretreatment condition is relatively mild, and NH is slowly formed on the outer surface of the alumina carrier in the sealed and hydrothermal mixed atmosphere of carbon dioxide and ammonia gas4Al(OH)2CO3Crystal nuclei, raising the reaction temperature NH during the post-heat treatment4Al(OH)2CO3The crystal nucleus continues to grow evenly to make rod-shaped NH4Al(OH)2CO3Having uniform diameter and length while increasing rod-like NH4Al(OH)2CO3And (3) coverage rate on the outer surface of the modified alumina-based carrier and the inner surface of the micron-sized pore channel.
4. According to the invention, part of active metal components are added in advance when the intermediate of the alumina carrier is formed, the active metal components are loaded on the surface of the alumina carrier in an oxide form during roasting, and when the carrier is subjected to sealing heat treatment in an ammonium bicarbonate water solution, the active metal is redispersed on the surface of the carrier, and simultaneously the action of the active metal and the carrier is improved, so that the activity of the final catalyst is improved.
5. The second and third hydrogenation active components are impregnated by adopting two-step impregnation, so that the content of active metal at the rod-shaped structure on the surface of the catalyst is increased, the activity of the surface of the catalyst is improved, meanwhile, an open pore channel is formed between the rod-shaped structure and the aluminum oxide on the surface of the catalyst, and the metal deposition resistance and the carbon deposition resistance of the catalyst are improved.
6. The catalyst of the invention is suitable for the hydrotreating process of heavy raw oil, is especially suitable for serving as a hydrogenation protective agent, a demetallization agent and the like, has high activity and good stability, and can prolong the running period of a device.
Drawings
FIG. 1 is an SEM image of the hydrodemetallization catalyst prepared in example 1.
Wherein the reference numbers are as follows: 1-main body part, 2-rod-shaped part and 3-micron-sized pore channel.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. Wherein, in the present invention, wt% represents a mass fraction.
The BET method: application N2Physical adsorption-desorption characterization of the pore structures of the catalysts in the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 50nm is obtained according to a BJH model.
Mercury pressing method: the mercury porosimeter is used for representing the pore diameter distribution of the catalysts in the examples and the comparative examples, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. Drying the sample, weighing, loading into an dilatometer, and maintainingDegassing for 30 minutes under the vacuum condition given by the instrument, and filling mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution of pore diameters above 100nm is determined by mercury intrusion.
A scanning electron microscope is used for representing the microstructure of the aluminum oxide catalyst, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.
The method for analyzing the content of active metal in the catalyst by using the electronic probe comprises the following specific operations: the content of active metal in the catalyst bulk and surface rod-like part was measured with a Japanese electronic JXA-8230 electron probe, and the acceleration voltage selected for the measurement was 15KV, and the probe current was 8X 10-8A, the beam spot size is 3 μm, and 5 points are randomly selected in the measurement process to obtain an average value.
Example 1
(1) Weighing 33 g of activated carbon particles with the particle size of 7 mu m, 200 g of pseudo-boehmite (produced by Shandong aluminum Co., Ltd.), 0.3 g of sesbania powder, 3.6 g of ammonium heptamolybdate and 4.3 g of nickel nitrate hexahydrate, uniformly mixing the above materials physically, adding a proper amount of acetic acid aqueous solution with the mass concentration of 1.5%, kneading, extruding into strips, drying the formed product at 100 ℃ for 6 hours, and roasting the dried product at 700 ℃ for 5 hours in an air atmosphere to obtain an alumina carrier intermediate.
(2) Weighing 100 g of the material in the step (1), placing the material in 720 g of ammonium bicarbonate solution with the mass concentration of 22.5%, transferring the mixed material into a high-pressure kettle, sealing, heating to 95 ℃ at the speed of 15 ℃/min, keeping the temperature for 3 hours, heating to 135 ℃ at the speed of 10 ℃/min, keeping the temperature for 5 hours, drying the carrier at 120 ℃ for 6 hours, and roasting at 650 ℃ for 5 hours to obtain the modified aluminum oxide-based carrier S-1.
(3) Weighing 50 g of the modified alumina-based carrier obtained in the step (2), and adding 100mLMo-Ni-P solution (MoO in impregnation liquid)3The resulting solution was immersed in NiO at a concentration of 6.23g/100mL and 2.43g/100mL for 2 hours, the excess solution was filtered off, dried at 120 ℃ for 6 hours, and then calcined at 500 ℃ for 5 hours.
(4) Putting the catalyst in the step (3) into a spray-dip rolling pot, and adding 4.2mLMo-Ni-P solution (MoO in a dipping solution)3The concentration is 0.82g/100mL, the NiO concentration is 0.57g/100mL, the catalyst is sprayed and dipped, the dipped material is dried for 6 hours at 120 ℃, and then is roasted for 5 hours at 500 ℃ to prepare the hydrodemetallization catalyst C1, the content of molybdenum oxide in the catalyst is 8.14 weight percent, the content of nickel oxide in the catalyst is 3.41 weight percent, wherein the ratio of the content of hydrogenation active metal on the rod-shaped part on the surface of the main part to the content of hydrogenation active metal in the catalyst bulk phase is 1.10:1 by weight of oxide.
The properties of catalyst C1 are shown in Table 1. In the catalyst C1, the length of the rod-shaped part in the micron-sized pore channel is mainly 4-6.3 μm, and the length of the rod-shaped part on the outer surface of the main body part is mainly 3-8 μm. The coverage of the rod-shaped part in the micron-sized pore channels of the main body part is 86%, and the coverage of the rod-shaped part on the outer surface of the main body part is 95%. The pores formed by the rod-like portions crossing each other in a random order were concentrated between 100-800 nm.
Example 2
The same as example 1 except that the particle size of the activated carbon in the step (1) was 5 μm, and the amount of the activated carbon added was 40 g. The adding amount of ammonium heptamolybdate is 3.1 g, and the adding amount of nickel nitrate hexahydrate is 5.4 g; and (3) in the step (2), the concentration of the ammonium bicarbonate solution is 24%, the adding amount of the solution is 630 g, the sealing pretreatment temperature is 100 ℃, the treatment time is 2 hours, the heat treatment temperature is 145 ℃, and the treatment time is 6.5 hours, so that the modified alumina-based carrier S-2 is prepared. MoO in active component impregnation liquid in step (3)3The concentration is 5.78g/100mL, the NiO concentration is 2.54g/100 mL; MoO in the active metal impregnation liquid in the step (4)3The concentration of 0.75g/100mL, the concentration of NiO of 0.46g/100mL and the dosage of active metal impregnation liquid of 3.5mL, the hydrodemetallization catalyst C2 was prepared, the content of molybdenum oxide in the catalyst was 8.04wt%, the content of nickel oxide was 3.38wt%, wherein the ratio of the content of the hydrogenation active metal on the rod-like part of the surface of the main part to the content of the hydrogenation active metal in the bulk phase of the catalyst, calculated as the weight of the oxide, was 1.18: 1.
The properties of catalyst C2 are shown in Table 1. In the catalyst C2, the length of the rod-shaped part in the micron-sized pore channel is mainly 2-4.5 μm, and the length of the rod-shaped part on the outer surface of the main body part is mainly 3-8 μm. The coverage of the rod-shaped part in the micron-sized pore channels of the main body part is 88%, and the coverage of the rod-shaped part on the outer surface of the main body part is 90%. The pores formed by the rod-like portions crossing each other in a random order were concentrated between 100-600 nm.
Example 3
The same as example 1 except that the particle size of the activated carbon in the step (1) was 8 μm, and the amount of the activated carbon added was 29 g. 4.1 g of ammonium heptamolybdate and 3.88 g of nickel nitrate hexahydrate; and (3) in the step (2), the concentration of the ammonium bicarbonate solution is 18.5 percent, the adding amount of the solution is 850 g, the heat treatment temperature is 125 ℃, and the treatment time is 7 hours, so that the modified alumina carrier S-3 is prepared. MoO in active component impregnation liquid in step (3)3The concentration is 5.89g/100mL, and the NiO concentration is 2.65g/100 mL; MoO in the active metal impregnation liquid in the step (4)3The concentration of 0.69g/100mL, the concentration of NiO of 0.62g/100mL and the dosage of the active metal impregnation solution of 4.8mL, the hydrodemetallization catalyst C3 was prepared, the content of molybdenum oxide in the catalyst was 8.11wt%, the content of nickel oxide was 3.56wt%, wherein the ratio of the content of the hydrogenation active metal on the rod-like part of the surface of the main part to the content of the hydrogenation active metal in the bulk phase of the catalyst, calculated as the weight of the oxide, was 1.10: 1.
The properties of catalyst C3 are shown in Table 1. In the catalyst C3, the length of the rod-shaped part in the micron-sized pore channel is mainly 3-7 μm, and the length of the rod-shaped part on the outer surface of the main body part is mainly 3-7 μm. The coverage of the rod-shaped part in the micron-sized pore channels of the main body part is 86%, and the coverage of the rod-shaped part on the outer surface of the main body part is 88%. The pores formed by the rod-like portions crossing each other in a random order were concentrated between 100-800 nm.
Example 4
The same as example 1 except that the particle size of the activated carbon in the step (1) was 3 μm, and the amount of the activated carbon added was 25 g. The adding amount of ammonium heptamolybdate is 2.5 g, and the adding amount of nickel nitrate hexahydrate is 7.8 g; and (3) in the step (2), the concentration of the ammonium bicarbonate solution is 16%, the adding amount of the solution is 1130 g, the heat treatment temperature is 155 ℃, and the treatment time is 4 hours, so that the modified alumina carrier S-4 is prepared. MoO in active component impregnation liquid in step (3)3The concentration is 6.14g/100mL, the NiO concentration2.71g/100 mL; MoO in the active metal impregnation liquid in the step (4)3The concentration of 0.73g/100mL, the concentration of NiO of 0.52g/100mL and the dosage of the active metal impregnation solution of 3mL, the hydrodemetallization catalyst C4 was prepared, the content of molybdenum oxide in the catalyst was 8.17wt%, the content of nickel oxide was 3.94wt%, wherein the ratio of the content of the hydrogenation active metal on the rod-like part of the surface of the main part to the content of the hydrogenation active metal in the catalyst bulk phase was 1.11:1 by weight of the oxide.
The properties of catalyst C4 are shown in Table 1. In the catalyst C4, the length of the rod-shaped part in the micron-sized pore channel is mainly 1-2.5 μm, and the length of the rod-shaped part on the outer surface of the main body part is mainly 4-8 μm. The coverage of the rod-shaped part in the micron-sized pore channels of the main body part is 88%, and the coverage of the rod-shaped part on the outer surface of the main body part is 92%. The pores formed by the rod-like portions crossing each other in a random order are concentrated between 100-700 nm.
Comparative example 1
Comparative alumina carrier S-5 and comparative catalyst C5 were prepared as in example 1 except that the alumina carrier intermediate of step (2) was not heat treated in an aqueous ammonium bicarbonate solution but in distilled water, and the same mass of ammonium bicarbonate was added as the alumina carrier was shaped, and the properties of the catalysts are shown in Table 1, with a molybdenum oxide content of 8.17wt% and a nickel oxide content of 3.46 wt%.
The microstructure of comparative catalyst C5 was observed by scanning electron microscopy, in which only the main part was observed in the catalyst, with micron-sized channels and no rod-like parts on the surface of the alumina carrier. Comparative example 2
Comparative alumina support S-6 and comparative catalyst C6 were prepared as in example 1 except that the ammonium bicarbonate in step (2) was changed to the same amount of ammonium carbonate, and the properties of the catalysts are shown in Table 1, with a molybdenum oxide content of 8.13wt% and a nickel oxide content of 3.39 wt%.
The microstructure of comparative catalyst C6 was observed by scanning electron microscopy, in which only the main part was observed in the catalyst, with micron-sized channels and no rod-like parts on the surface of the alumina carrier.
Comparative example 3
As in example 1, except that the alumina carrier intermediate was not subjected to the heat treatment in the ammonium hydrogencarbonate aqueous solution of step (2), step (3) and step (4) were directly conducted to obtain a comparative alumina carrier S-7 and a comparative catalyst C7. The properties of the catalyst are shown in Table 1, with a molybdenum oxide content of 8.16wt% and a nickel oxide content of 3.42 wt%.
The microstructure of comparative catalyst C7 was observed by scanning electron microscopy, in which only the main part was observed in the catalyst, with micron-sized channels and no rod-like parts on the surface of the alumina carrier.
TABLE 1 Properties of the catalysts
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Numbering | C1 | C2 | C3 | C4 | C5 | C6 | C7 |
| Specific surface area, m2/g | 213 | 188 | 196 | 181 | 191 | 169 | 204 |
| Pore volume, mL/g | 0.93 | 0.91 | 0.89 | 0.90 | 0.82 | 0.79 | 0.85 |
| Pore distribution:, v% | |||||||
| ≤10nm | 7 | 11 | 9 | 10 | 25 | 21 | 29 |
| 15-35nm | 36 | 42 | 39 | 34 | 25 | 21 | 19 |
| 100-800nm | 27 | 24 | 26 | 22 | 9 | 6 | 11 |
| Over 3 mu m | - | - | - | - | 11 | 9 | 12 |
| Crush strength, N/mm | 10.7 | 10.9 | 10.4 | 11.6 | 8.4 | 8.6 | 8.9 |
Evaluation of catalytic performance:
the hydrodemetallization catalyst (C1-C7) prepared above was evaluated for its catalytic performance by the following method:
the vacuum residue listed in Table 2 was used as a raw material, and the catalytic performance of C1-C7 was evaluated on a fixed bed residue hydrogenation reactor, the catalyst diameter was 2-3mm long strips, the reaction temperature was 375 deg.C, the hydrogen partial pressure was 13MPa, and the liquid hourly volume space velocity was 1.0 hr-1The volume ratio of hydrogen to oil was 1000, the content of each impurity in the produced oil was measured after 2000 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
| Item | |
| Density (20 ℃ C.), g/cm3 | 0.99 |
| S，wt% | 2.61 |
| N，wt% | 0.52 |
| Ni，µg/g | 51.4 |
| V，µg/g | 93.6 |
| CCR，wt% | 16.8 |
TABLE 3 comparison of catalyst hydrogenation performance
| Catalyst numbering | C1 | C2 | C3 | C4 | C5 | C6 | C7 |
| V + Ni removal ratio, wt% | 63.4 | 64.7 | 62.4 | 61.2 | 44.6 | 43.9 | 41.8 |
As can be seen from the data in Table 3, the catalyst of the present invention has higher hydrodemetallization activity and stability than the catalyst of the comparative example.
Claims (27)
1. A method for preparing a hydrodemetallization catalyst, comprising:
(1) kneading and molding a physical pore-expanding agent, pseudo-boehmite and a first hydrogenation active metal component source, drying and roasting to obtain an alumina carrier intermediate;
(2) immersing the alumina carrier intermediate obtained in the step (1) into an ammonium bicarbonate solution, then carrying out sealing heat treatment, and drying and roasting the heat-treated material to obtain a modified alumina carrier;
(3) and (3) respectively impregnating and loading the second hydrogenation active metal component and the third hydrogenation active metal component on the modified alumina-based carrier obtained in the step (2) to prepare the hydrodemetallization catalyst.
2. The method of claim 1, wherein: the physical pore-enlarging agent in the step (1) is one or more of activated carbon and sawdust, the particle size of the physical pore-enlarging agent is 2-10 mu m, preferably 3-8 mu m, and the mass ratio of the added amount of the physical pore-enlarging agent to the pseudo-boehmite is 1:8-1: 5.
3. The method of claim 1, wherein: the first hydrogenation active metal component source in the step (1) is a compound containing VIB group and/or VIII group metals; preferably soluble compounds containing group VIB and/or group VIII metals; the group VIB metal is preferably one or more of W, Mo, and the soluble compound containing the group VIB metal is at least one of ammonium molybdate, ammonium paramolybdate, ammonium tungstate and ammonium metatungstate; the VIII group metal is preferably one or more of Co and Ni, and the soluble compound containing the VIII group metal is at least one of nickel nitrate and cobalt nitrate; further preferred is the following: the first hydrogenation active metal component source is a soluble compound containing VIB group and VIII group metals, and the mass ratio of the addition amount of the VIB group metals to the addition amount of the VIII group metals is 1:1-4: 1.
4. The method of claim 1, wherein: adding a forming auxiliary agent in the kneading and forming process in the step (1), wherein the forming auxiliary agent is one or more of a peptizing agent and an extrusion assisting agent; the peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid; the extrusion aid is sesbania powder.
5. The method of claim 1, wherein: the roasting temperature in the step (1) is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
6. The method of claim 1, wherein: the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the alumina carrier intermediate added in the step (2) is 6:1-12:1, and the mass concentration of the ammonium bicarbonate solution is 15% -25%.
7. The method of claim 1, wherein: the sealing heat treatment temperature in the step (2) is 120-160 ℃, the constant temperature treatment time is 4-8 hours, the heating rate is 5-20 ℃/min, and the sealing heat treatment is carried out in a high-pressure reaction kettle.
8. The method of claim 1 or 7, wherein: and (2) performing sealing pretreatment before sealing heat treatment, wherein the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min lower than that before the pretreatment, preferably at least 5 ℃/min lower.
9. The method of claim 1, wherein: the roasting temperature in the step (2) is 550-750 ℃, and the roasting time is 4-6 hours.
10. The method of claim 1, wherein: in the step (3), the second hydrogenation active metal component and the third hydrogenation active metal component are both VIB group metals and/or VIII group metals, the VIB group metals are selected from one or two of Mo and W, and the VIII group metals are selected from one or two of Co and Ni.
11. The method of claim 1, wherein: the first active metal component, the second active metal component and the third active metal component adopt the same active metal component or different active metal components; the first hydrogenation active metal component is preferably Mo and Ni, the second hydrogenation active metal component is preferably Mo and Ni, and the third hydrogenation active metal component is preferably Mo and Ni.
12. The method of claim 1, wherein: based on the weight of the obtained hydrodemetallization catalyst, the total content of the added active metals is 2.3-28.0 percent calculated by metal oxides, preferably the content of VIB group metals is 2.0-20.0 percent calculated by metal oxides, and the content of VIII group metals is 0.3-8.0 percent calculated by metal oxides; the mass ratio of the added first active metal component, the second active metal component and the third active metal component in terms of oxides is (35-85): (140-240): 1.
13. the method of claim 1, wherein: in the step (3), the modified alumina-based carrier obtained in the step (2) is respectively impregnated and loaded with a second hydrogenation active metal component and a third hydrogenation active metal component, wherein the impregnation and loading of the second hydrogenation active metal component adopts supersaturation impregnation or saturated impregnation, and the impregnation and loading of the third hydrogenation active metal component adopts an unsaturated spray-impregnation method; the dipping load sequence of the second hydrogenation active metal component and the third hydrogenation active metal is not limited, after each dipping load, the next dipping load is carried out after drying and roasting treatment; the dipping solution containing the hydrogenation active metal component is one of acid solution, water solution or ammonia solution containing the hydrogenation active component.
14. A method according to claim 1 or 13, characterized by: when the second hydrogenation active metal component is loaded in the impregnation in the step (3), an impregnation liquid I containing the second hydrogenation active metal component is adopted; the following are preferred: the impregnation liquid I containing the second hydrogenation active metal component simultaneously contains VIB group metals and VIII group metals, wherein the content of the VIB group metals is 5.5-15.0g/100mL calculated by metal oxides, and the content of the VIII group metals is 1.0-3.5g/100mL calculated by metal oxides; when the third hydrogenation active metal component is impregnated and supported, the impregnation liquid II containing the third hydrogenation active metal component is adopted, and the following is preferable: the impregnation liquid II containing the third hydrogenation active metal component simultaneously contains VIB group metals and VIII group metals, wherein the content of the VIB group metals in the impregnation liquid II is 0.4-2.0g/100mL calculated by metal oxides, and the content of the VIII group metals in the impregnation liquid II is 0.3-1.0g/100mL calculated by metal oxides; and (3) loading a third hydrogenation active metal by using an unsaturated spray-leaching method, wherein the dosage of the impregnation liquid II is 5-10% of the saturated water absorption capacity of the modified alumina-based carrier added in the step (3) according to the volume fraction.
15. The method of claim 1, wherein: the roasting in the step (3) is carried out in an oxygen-containing atmosphere and is carried out for 4-6 hours at the temperature of 450-550 ℃.
16. The method of claim 1, wherein: the drying conditions in the steps (1) to (3) are drying at 80 to 160 ℃ for 6 to 10 hours.
17. A hydrodemetallization catalyst, characterized in that: the hydrodemetallization catalyst is prepared by a process according to any one of claims 1 to 16.
18. The catalyst of claim 17, wherein: the added hydrogen demetalization catalyst comprises a main body part and a rod-shaped part, wherein the main body part is provided with micron-sized pore channels, at least part of the rod-shaped part is distributed in the micron-sized pore channels with the pore diameter D of 3-10 mu m and the rod-shaped part is 1-12 mu m in length and 100-300 nm in diameter.
19. The catalyst of claim 18, wherein: the content of the hydrogenation active metal in the rod-like portion of the outer surface of the main body portion is higher than the content of the hydrogenation active metal in the catalyst bulk phase.
20. A catalyst as claimed in claim 18 or 19, wherein: the ratio of the content of the hydrogenation active metal on the rod-like portion of the outer surface of the main body portion to the content of the hydrogenation active metal in the catalyst bulk is 1.02:1 to 1.5:1 by weight.
21. The catalyst of claim 18, wherein: the length of the rod-shaped part in the micron-sized pore canal is mainly 0.3D-0.9D; the length of the rod-like portion on the outer surface is mainly 3 to 8 μm.
22. The catalyst of claim 18, wherein: in the micron-sized pore canal of the main body part, the rod-shaped parts are distributed in a disordered and mutually staggered state; wherein at least one end of the rod-like part in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel and is integrated with the main body part.
23. The catalyst of claim 18, wherein: on the outer surface of the main body portion, the rod-like portions are distributed in a disordered mutually staggered state; wherein one end of the rod-like portion on the outer surface of the main body portion is bonded to the outer surface of the main body portion, and the other end thereof is extended outwardly to be integral with the main body portion.
24. The catalyst of claim 18, wherein: the coverage rate of the rod-shaped part in the micron-sized pore channel of the main body part is 70-95%, and the coverage rate of the aluminum of the rod-shaped part on the outer surface of the main body part is 70-95%.
25. The catalyst of claim 18, wherein: the properties of the catalyst are as follows: the specific surface area is 150-280m2(iv)/g, pore volume of 0.75-1.6mL/g, crush strength of 10-20N/mm.
26. The catalyst of claim 18, wherein: in the catalyst, the pores formed by the rod-shaped parts staggered with each other in a random order are concentrated at 100-800 nm.
27. The catalyst of claim 18, wherein: the pore distribution of the catalyst is as follows: the pore volume of the pores with the pore diameter of less than 10nm accounts for less than 15 percent of the total pore volume, the pore volume of the pores with the pore diameter of 15-35nm accounts for 35-55 percent of the total pore volume, and the pore volume of the pores with the pore diameter of 100-800nm accounts for 15-30 percent of the total pore volume.
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