US3393148A - Hydrofining catalyst and process using same - Google Patents
Hydrofining catalyst and process using same Download PDFInfo
- Publication number
- US3393148A US3393148A US510656A US51065665A US3393148A US 3393148 A US3393148 A US 3393148A US 510656 A US510656 A US 510656A US 51065665 A US51065665 A US 51065665A US 3393148 A US3393148 A US 3393148A
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- United States
- Prior art keywords
- catalyst
- range
- alumina
- weight percent
- hydrocarbon
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 98
- 238000000034 method Methods 0.000 title claims description 42
- 150000002430 hydrocarbons Chemical group 0.000 claims description 52
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 13
- 230000000737 periodic effect Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 description 48
- 229910052751 metal Inorganic materials 0.000 description 43
- 239000002184 metal Substances 0.000 description 43
- 239000004215 Carbon black (E152) Substances 0.000 description 41
- 239000002808 molecular sieve Substances 0.000 description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 38
- 229910052750 molybdenum Inorganic materials 0.000 description 27
- 239000011733 molybdenum Substances 0.000 description 27
- 229910017052 cobalt Inorganic materials 0.000 description 26
- 239000010941 cobalt Substances 0.000 description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 25
- 239000007789 gas Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 150000002739 metals Chemical class 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000009835 boiling Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000010763 heavy fuel oil Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- -1 molybdenum metals Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001683 gmelinite Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of particles
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- 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
- B01J23/90—Regeneration or reactivation
-
- 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
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
Definitions
- This invention relates to the hydroprocessing of heavy gas oils and hydrocarbon residua. More particularly, it relates to a novel catalyst for the hydroprocessing of heavy gas oils and hydrocarbon residua and a process employing same.
- Petroleum crudes are composed of a large variety of hydrocarbons, which include heavy distillates and hydrocarbon residua. Heavy dist-illates boil at temperatures above about 570 F. and include the heavy gas oils and light lubricating oils.
- the hydrocarbon residua which are made up of saturates, monoaromatics, polyaromatics, resins and asphalt, are found to have molecular weights ranging from about 600 to about 1200 or above. At this time, the complete composition of petroleum is not known. There are many areas in the makeup of the crude where the molecular compositions of the compounds remain unknown. This is particularly true in the case of the heavy and residual fractions.
- a primary object of the present invention is to provide a catalyst that can be used effectively to convert the refractory, higher-boiling gas oils and residual hydrocarbons to more useable products and a process using such a catalyst.
- Hydrocarbon residua are, for the most part, byproducts of processes which are primarily used to obtain other petroleum products.
- the residual fuel oils are examples of such hydrocarbon residua.
- Commercial residual fuel oils have gravities which may vary between 8.9 and 235 API, flash points within the range of about 150 to about 450 F., and pour points within a range of about -55 to about 50 F.
- Their Conradson carbon residues may fall within a range of about 0.1 to about 11.5% and their boiling points may fall within a range of about 300 to about 1100 F.
- Such residual fuel oils have been used generally to supply heat.
- the heavier fractions of the various petroleum crudes will contain appreciable amounts of sulfur and nitrogen, as well as certain so-called heavy metals.
- a vacuum reduced crude may be found to contain as much as 100 parts per million nickel. Metals such as these deleteriously affect the life of any catalyst over which the hydrocarbons containing such metals are being processed.
- Hydroprocessing may be used in the upgrading of heavier petroleum fractions to usable petroleum products. It comprises the contacing of the hydrocarbon material that is being processed with a suitable catalyst under suitable conditions in the presence of hydrogen.
- the outstanding growth of catalytic reforming and the large amounts of hydrogen resulting therefrom have advanced the economic attractivenes of hydroprocessing. In such a process, not only are a great deal of the sulfur and a large percentage of the nitrogen removed from the hydrocarbon material being processed, but also the hydrocarbon material is hydrocracked to yield some usable hydrocarbon products.
- Hydrocracking is a general term which is applied to petroleum refining process employing destructive hydrogenation wherein hydrocarbon feed stocks which have relatively high molecular weights are converted to lowermolecular-weight hydrocarbons at elevated temperature and pressure in the presence of a suitable catalyst and a hydrogen-containing gas. Hydrogen is consumed in the conversion of organic nitrogen to ammonia and sulfur to hydrogen sulfide, in the splitting of high-molecularweight compounds into lower-molecular-weight compounds, and in the saturation of olefins and other unsaturated compounds.
- Suitable catalysts have been developed for the hydroprocessing of hydrocarbon fractions boiling at temperature within the light-gas-oil boiling range.
- the feed stock is destructively hydrogenated to lower-molecular-weight material.
- catalysts comprise cobalt, molybdenum, and their oxides and sulfides on a solid inorganic-oxide support such as alumina.
- these catalysts will not convert in an efiicient manner such refractory hydrocarbon materials as the heavy gas oils and hydrocarbon residua.
- This catalyst is a solid catalytic composition which comprises at least one hydrogenation component on a solid inorganic-oxide support comprising a large-pore-diameter alumina having a surface area within the range of about 150 to about 500 square meters per gram and an average pore diameter within the range of about to about 200 angstroms.
- this catalyst comprises a hydrogenation metal of Group VI-A of the Periodic Table and a hydrogenation metal of Group VIII of the Periodic Table on a large-pore-diameter alumina having a surface area within the range of about to about 500 square meters per gram and an average pore diameter within the range of about 100 to about 200 angstroms.
- the Periodic Table to which We have referred is published on page 2 of Modern Aspects of Inorganic Chemistry, H. J. Emeleus and I. S. Anderson, D. Van Nostrand Company, Inc., New York, N.Y., 1949.
- This catalyst typically comprises a hydrogenation metal of Group VI-A of the Periodic Table and a hydrogenation metal of Group VIII of the Periodic Table on a solid inorganic-oxide support comprising a large-porediameter alumina having a surface area Within the range of about 150 to about 500 square meters per gram and an average pore diameter within the range of about 100 to about 200 angstroms. It is desirable that such an alumina be in one of the well-known catalytically active forms, such as gamma-alumina.
- Such alumina may be pure, it may contain also minor amounts of other oxides that are inert under the conditions at which it will be used.
- Such an alumina can contain a small amount of silica for stability without creating undesirable effects in our process. Desirably, the amount of silica is within the range of about 1 to about weight percent. It is essential that the alumina in our catalyst have large pore diameters.
- the average pore diameter of the alumina should be within the range of about 100 to about 200 angstroms, suitably within the range of about 125 to about 180 angstroms, and preferably within the range of about 135 to about 160 angstroms; the surface area should be within the range of about 150 to about 500 square meters per gram, suitably within the range of about 300 to about 350 square meters per gram, and preferably within the range of about 320 to 340 square meters per gram.
- Suitable aluminas can be purchased from manufacturers of reforming catalysts. For example, Nalco HF-type aluminas having surface areas within the range of about 300 to about 350 square meters per gram are available from the Nalco Chemical Company.
- HF-type aluminas can be obtained with pore volumes varying from as low as 0.54 cubic centimeters per gram to as high as 2.36 cubic centimeters per gram and corresponding average pore diameters within the range of about 72 to about 305 angstroms. Therefore, those Nalco HF-type aluminas which have the desired physical properties are suitable as the inorganic-oxide support of our catalyst.
- the alumina desired as a support in our catalyst has a much higher average pore diameter than the aluminas used in conventional catalyst.
- the use of the alumina having a large average pore diameter as a support in a catalyst for hydroprocessing heavy gas oils and hydrocarbon residua results in a catalyst having improved denitrogenation activity, improved desulfurization activity, and improved hydrocarbon-conversion activity.
- a suitable embodiment of our solid catalytic composition comprises a hydrogenation metal of Group VI-A of the Periodic Table and a hydrogenation metal of Group VIII of the Periodic Table on an inorganic-oxide support of a large-pore-diameter alumina having an average pore diameter within the range of about 100 to about 200 angstroms and a surface area within the range of about 150 to about 500 square meters per gram.
- the combined amounts of the hydrogenation metals are within the range of about 3 to about 35 weight percent based upon said composition.
- the hydrogenation metal of Group VIA is molybdenum and the hydrogenation metal of Group VIII is cobalt.
- the molybdenum should be present in an amount within the range of about 4.5 to about 26 weight percent, calculated as molybdenum trioxide and based upon said composition, and the cobalt should be present in an amount Within the range of about 1.3 to about 5.2 weight percent, calculated as cobalt oxide and based upon said composition.
- a typical embodiment of our catalyst comprises 3 weight percent cobalt and 14 weight percent molybdenum,
- both metals being calculated as the oxides, on a largepore-diameter alumina having an average pore diameter within the range of about to about 200 angstroms and a surface area Within the range of about 1.50 to about 500 square meters per gram.
- a preferred embodiment of our catalyst comprises 3 Weight percent cobalt and 14 weight percent molybdenum, both metals being calculated as the oxides, on a large-pore-diameter alumina having an average pore diameter within the range of about to about angstroms, .and a surface area within the range of about 300 to about 350 square meters per gram.
- a zeolitic molecular sieve is suspended in the matrix of the alumina.
- the molecular sieve may be present in an amount within the range of about 1 to about 50 weight percent based upon the combined weight of sieve and alumina.
- the molecular sieve is present in an amount within the range of about 5 to about 30 weight percent based upon the combined weight of sieve and alumina.
- Zeolitic molecular sieves are composed of porous crystalline metal alumino-silicates.
- the zeolitic structure excavities, which are interconnected by numerous smaller pores. These pores have essentially a uniform diameter at their narrowest cross section. Generally, this uniform diameter falls within the range of 4 to 15 angstroms.
- the network of cavities is a rigid S-dimensional and ionic network of silica and alumina tetrahedra. These tetrahedra are cross-linked by the sharing of oxygen atoms.
- Cations are included in the crystal structure to balance the electrovalence of the tetrahedra. Examples of such cations are a metal ion, an ammonium ion and a hydrogen ion.
- One cation may be exchanged either entirely or partially by another cation. This cation exchange is conveniently accomplished through the use of ion-exchange techniques.
- Crystalline alumino-silicate clays e.g., bentonite
- Amorphous aluminosilicates e.g., a synthetic silica-alumina cracking catalyst, have random structures.
- the iutracrystalline pores can be varied in size by replacing at least a part of exchangeable cations with other suitable ions.
- Such zeolities may be used for drying purposes, for catalytic purposes, and for hydrocarbon-type-separation purposes.
- Either natural or synthetic molecular sieves may be used I in our proposed catalyst.
- natural molecular sieves are erionite, mordenite, chabazite, faujasite, gmelinite, and the calcium form of analcite.
- synthetic zeolitic molecular sieves are Type X, Type Y, Type A, Type D, Type L, Type R, Type S and Type T molecular sieves.
- Zeolitic molecular sieves can be activated by driving out of the sieves a major portion of the water of hydration. The characteristics of both natural and synthetic molecular sieves and the methods for preparing them have been presented in the chemical art.
- the catalyst for hydroprocessing heavy gas oils and hydrocarbon residua can be prepared by incorporating the cobalt and molybdenum metals into the alumina support through the use of an aqueous solution of a heat-decomposable compound of the particular metal.
- a solution of cobalt nitrate, cobalt acetate, cobalt formate, or a solution of such metal compound and a soluble complexing agent can be used to impregnate the cobalt on the alumina support.
- an aqueous solution of ammoniumhepta-molybdate or a solution of molybdenum trioxide in ethanolamine may be used to impregnate the molybdenum on the support. Following these impregnations the resulting material is dried and calcined.
- the catalyst support is prepared by reducing the zeolite to a small particle size, blending the zeolite particles with the alumina hydrogel, and drying the resultng blend.
- the cobalt and molybdenum may be impregnated then on the support comprising the molecular sieve suspended in the alumina by techniques discussed above.
- the resultant catalyst can be used under suitable hydroprocessing conditions to convert the refractory high-boiling hydrocarbons into lowermolecular-weight compounds, some of which may be used in motor fuels and heating fuels.
- our catalyst is particularly suitable for the hydroprocessing of heavy gas oils and hydrocarbon residua, it may be used also to hydroprocess light gas oil, light catalytic cycle oils, and the like.
- Such a ctalyst as discussed above may be used in a process for hydroprocessing heavy gas oils and hydrocarbon residua.
- heavy metals such as vanadium and nickel need not be removed from the feed stock.
- the nitrogen does not have to be removed from the feed stock prior to our process. The total nitrogen content of more than 6,000 parts per million can be tolerated.
- Our process is carried out at a temperature within the range of about 750 to about 850 F., preferably, within a range of about 770 to about 825 F., and at an operating pressure within the range of about 1,000 to about 3,000 p.s.i.g., preferably, within the range of about 1,200 to about 2,200 p.s.i.g.
- the hydrocarbon feed is added at a liquid hourly space velocity within the range of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, preferably, within the range of about 0.5 to about 1.5 volumes of hydrocarbon per hour per volume of catalyst.
- Hydrogen is added to our process at a rate within the range of about 3,000 to about 50,000 standard cubic feet of hydrogen per barrel of hydrocarbon, preferably within the range of 6,000 to 20,000 standard cubic feet of hydrogen per barrel of hydrocarbon.
- the hydrogen partial pressure is at least 80% of the operating pressure.
- Our process can be used to upgrade high-boiling-hydrocarbon fractions. It is particularly useful in converting those hydrocarbon feeds which are composed mainly of hydrocarbons which boil above 650 F.
- An example of such a hydrocarbon feed stock is a Cyrus Crude which contains 69.8 volume percent material boiling at a temperature of at least 650 F. and which has a gravity of 8.9" API, a sulfur content of 4.5 weight percent and which contains 230 parts per million vanadium and 70 parts per milion nickel.
- a similar feed stock was used in the example set forth hereinafter.
- the heavy metals in these various higher-boiling hydrocarbon feed stocks exist in compounds. During the hydroprocessing reactions, these compounds which contain metals are decomposed and the metals are subsequently deposited on the catalyst and in the coke. The coke and metals may be removed by suitable regeneration techniques; or, if the appropriate conditions exist, the spent catalyst advantageously may be discarded.
- Catalyst A was prepared by blending 29.5 grams of cobalt nitrate with 2,770 grams of the required alumina sol in 300 milliliters of water.
- this blend were added 51 grams of ammonium heptamolybdate in 300 milliliters of hot water.
- the addition of this molybdenum-containing solution gelled the alumina sol.
- the gel was dried in air at a temperature of about 250 F. for 16 hours.
- the resulting powder was pelletted into /s x A pellets. These pellets were subsequently calcined in air at a temperature of about 1000 F. for about 6 hours.
- Catalyst B contains 3 weight percent cobalt and 14 weight percent molybdenum, calculated as the metals, on a support of alumina which has suspended therein 25 weight percent of an ammonium-exchanged Type-Y molecular sieve based upon said support.
- Catalyst B was prepared by blending 41.5 grams of ammonium-exchanged type-Y molecular sieve with 2,080 grams of alumina sol of the type prepared in United States Patent Reissue 22,196. A cobalt solution containing 29.5 grams of cobalt nitrate was then added to the resulting blend. This was followed by the addition of a molybdate solution having been previously prepared by adding 49 grams of ammonium hepta molybdate to 500 milliliters of Water.
- the molybdate solution gelled the sol.
- the resulting gel was dried in air at a temperature of about 250 F. for 16 hours.
- the resulting powder was pelletted with Sterotex and subsequently calcined in air at a temperature of about 1000" F. for 6 hours.
- Catalyst C contains 3 weight percent cobalt and 14 weight percent molybdenum, calculated as the metals, on a support of Nalco HF-type alumina.
- Catalyst C was prepared by increasing the cobalt content and the molybdenum content of a catalyst containing 3 weight percent cobalt-oxide and 14 weight percent molybdenum trioxide which had been obtained from the Nalco Chemical Company.
- a solution was prepared by adding 18.2 grams of ammonium hepta-rmolybdate and 6.8 grams of cobalt nitrate to about milliliters of water; then 189 grams of the Nalco catalyst were impregnated with this solution. The impregnated catalyst was then dried in air at a temperature of about 250 F. for about 16 hours and subsequently calcined in air at a temperature of 1000 F. for 6 hours.
- Catalyst D contains 3 weight percent cobalt and 14 weight percent molybdenum, calculated as the metals, on a support of alumina into the matrix of which ammonium-exchanged type-Y molecular sieves have been suspended.
- the molecular-sieve content of the support was 5 weight percent.
- This catalyst was prepared by blending 114 grams of ammonium-exchanged type-Y molecular sieves with 1770 grams of Nalco I-lF-type alumina hydrogel (weight is on a dry basis). After sufficient blending, the resulting blend was spray dried at 250 F. Cobalt and molybdenum were impregnated into the preparation by conventional commercial techniques.
- Catalyst E contains 3 weight percent cobalt and 14 weight percent molybdenum, calculated as the metals, on a support of alumina into which ammonium-exchanged type-Y molecular sieves have been suspended.
- the molecular-sieve content of the support was 10 weight percent.
- the catalyst was prepared by blending 340 grams of ammonium-exchanged type-Y molecular sieve with 1544 grams of Nalco HF-type alumina hydrogel (weight is on a dry basis). After sufiicient blending, the resulting blend was spray dried at 250 F. Cobalt and molybdenum were impregnated into the preparation by conventional commercial techniques.
- Catalyst F contains 3 weight percent cobalt and 14 weight percent molybdenum, calculated as the metals, on a support of alumina into which ammoniumexchanged type-Y molecular sieves have been suspended.
- the support contained 25 weight percent molecular sieves.
- Catalyst F was prepared by blending 5 68 grams of ammonium-exchanged type-Y molecular sieves with 1316 grams of Nalco HF-type alumina hydrogel (weight is on a dry basis). The resulting blend was then spray dried at a temperature of about 250 F. Cobalt and molybdenum were impregnated into the preparation by conventional commercial techniques.
- Alumina I -1 5.4 Calcium 20 Iron p I 18 Magnesium 6.2 Sodium 75 Nickel 41 Vanadium 66
- the reactor of the micro unit was A3" in diameter; and when it was filled with 40 cc.s of catalyst, the catalystbed depth was 8.4 inches.
- a particular catalyst was charged, to this reactor. It is presumed that the cobalt and molybdenum in each of these catalyst was present in the oxide form, since the catalyst had been calcined in air at 1000 F. prior to the charging. When a particular catalyst had been put in the reactor, the catalyst was heated to a temperature of about 700 F. in nitrogen at,” near-atmospheric pressure.
- rate constants could be calculated for denitrogenation and desulfurization occurring in a particular test. Either the denitrogenation activity or the desulfurization activity was calculated as 100 times the ratio of the observed rate constant for the particular reaction from a particular test divided by a standard rate constant.
- Catalysts were evaluated for the maintenance of the activ- Catalyst C has a Nalco HF-type alumina support.
- Catalyst C and Catalyst B containing the prior-art alumina and 25 Weight-percent molecular sieves based upon the support, have almost similar denitrogenation.activitiesyhowever, Catalyst'F, which contains Nalco HF-type alumina and 25 weight percent molecular sieves based upon'the support, has a denitrogenation activity which is far superior to those of the other three. catalysts.
- Q
- Nalco HF-type alumina barrels per stream day (BSD) of an atmospheric reduced crude fraction of a Cyrus Crude are introduced into the reaction-zone.
- the raw crude hasasulfur content of 3.6 Weight-percent sulfur and a gravity of 17.7 API; the atmospheric reduced crude fraction, a sulfur content of 4.5 weight percent sulfur and a gravity of 93 ARI.
- Also introduced into thereaction zone are 125 million standard cubic feet ofhydrogen vper day and 6,000 standard cubic feet of recycle ,gasper barrel of hydrocarbonprocessed.
- Operating. conditions in the reaction zone include a temperatureof about 800 F,, a pressure of 1500 p.s.i.g., and a liquid hourly space velocity of 0 .7. 4 volumes,,of
- Thecatalyst employed is a catalystpomprising ,3 weight percent cobalt and 14 weight percent molybdenum, calculatedas the oxides, on a support of NalcoHF-typealumina.
- Approximately 104,250 BSD of reconstituted Cyrus Crude are obtained.
- This reconstituted Cyrus Crude has 'a sulfur level of 1.5 weight percent sulfur and agravity of 28.9 API. Whilethe atmospheric reduced crude charged to-the reaction zone is about 95% material boiling at a temperature of at least 650 F., the product is only about 67% material boiling at a temperature of at least 650 F.
- a solid catalytic composition for the hydroproce ssing of heavy gas oils and hydrocarbon residue w'hich composition comprises a hydrogenation metal of Group VI-A of the Periodic Table and a hydrogenation metal of Group VIII of the Period Table on a solid inorganicoxide support comprising a large-pore-diameter alumina having a surface area Within the range of'ab'out' 150 to about 500 square meters per gram and an average pore diameter within the range of about to about 200 angstroms.
- composition of claim 1 further characterized in that said metal of Group VIA and said metal of Group VIII are present in a total amount within the range of about 3 to about 35 weight percent based upon said composition.
- composition of claim 1 wherein said metal of Group VIA is molybdenum.
- composition of claim 1 wherein said metal of Group VI-A is molybdenum and is present in an amount within the range of about 4.5 to about 26 weight percent, calculated as molybdenum trioxide and based upon said composition.
- composition of claim 1 wherein said metal of Group VI-A is molybdenum and is present in an amount within the range of about 4.5 to about 26 weight percent, calculated as molybdenum trioxide and based upon said composition, and wherein said metal of Group VIII is cobalt and is present in an amount within the range of about 1.3 to about 5.2 Weight percent, calculated as cobalt oxide and based upon said composition.
- composition of claim 1 wherein said support is further characterized in that a zeolitic molecular sieve is admixed with said alumina.
- composition of claim 8 wherein said molecular sieve is present in an amount within the range of about 1 to about 50 weight percent based upon said support.
- composition of claim 8 wherein said molecular sieve has been ion-exchanged with a salt selected from the group consisting of alkali-metal salts and alkalineearth-metal salts.
- composition of claim 8 wherein said molecular sieve is present in the hydrogen form.
- composition of claim 8 further characterized in that said metal of Group VI-A is molybdenum and is present in an amount Within the range of about 4.5 to about 26 weight percent, calculated as molybdenum trioxide and based upon said composition, said metal of Group VIII is cobalt and is present in an amount within the range of about 1.3 to about 5.2 weight percent, calculated as cobalt oxide and based upon said composition, and said molecular sieve is the hydrogen form of a Type-Y molecular sieve and is present in an amount within the range of about 1 to about 30 weight percent based upon said support.
- composition of claim 8 further characterized in that said metal of Group VI-A is molybdenum and is present in an amount of 21 weight percent, calculated as molydenum trioxide and based upon said composition, said metal of Group VIII is cobalt present in an amount of 3.8 weight percent, calculated as cobalt oxide and based upon said composition, and said molecular sieve is the hydrogen form of a Type-Y molecular sieve and is present in an amount within the range of about to about 25 weight percent based upon said support.
- a process for the hydroprocessing of a feed stock selected from the group consisting of heavy gas oils, hydrocarbon residue, and mixtures thereof which process comprises contacting said feed stock under suitable hydroprocessing conditions with a catalyst comprising a metallic hydrogenation component on a solid inorganicoxide support comprising a large-pore-diameter alumina having a surface area within the range of about 150 to about 500 square meters per gram and an average pore diameter within the range of about 100 to about 200 angstroms.
- said catalyst comprises a hydrogenation metal of Group VIA of the Periodic Table and a hydrogenation metal of Group VIII of the Periodic Table on a solid inorganic-oxide support comprising a large-pore-diameter alumina having a surface area within the range of about 150 to about 500 square meters per gram and an average pore diameter within the range of about 100 to about 200 angstroms.
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US510656A US3393148A (en) | 1965-11-30 | 1965-11-30 | Hydrofining catalyst and process using same |
FR85284A FR1503063A (fr) | 1965-11-30 | 1966-11-28 | Catalyseur pour l'hydrogénation d'hydrocarbures et procédé utilisant ce catalyseur |
DE1545397A DE1545397C3 (de) | 1965-11-30 | 1966-11-29 | Verfahren zur hydrierenden Entfernung von Stickstoff- und Schwefelverbindungen aus einem Kohlenwasserstoffrückstände enthaltenden schwermetallhaltigen Erdölausgangsmaterial |
DK617166AA DK129945B (da) | 1965-11-30 | 1966-11-29 | Fast katalysator til hydrogenbehandling af tunge gasolier og carbonhydridrester indeholdende metal- og nitrogenforureninger. |
SE16390/66A SE335896B (US20100012521A1-20100121-C00001.png) | 1965-11-30 | 1966-11-30 | |
NL666616849A NL139246B (nl) | 1965-11-30 | 1966-11-30 | Werkwijze voor de behandeling van zware gasolien en koolwaterstofresiduen met waterstof. |
BE690488D BE690488A (US20100012521A1-20100121-C00001.png) | 1965-11-30 | 1966-11-30 | |
ES0333965A ES333965A1 (es) | 1965-11-30 | 1966-11-30 | Procedimiento catalitico para hidrorrefinar hidrocarburos pesados. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US510656A US3393148A (en) | 1965-11-30 | 1965-11-30 | Hydrofining catalyst and process using same |
Publications (1)
Publication Number | Publication Date |
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US3393148A true US3393148A (en) | 1968-07-16 |
Family
ID=24031628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US510656A Expired - Lifetime US3393148A (en) | 1965-11-30 | 1965-11-30 | Hydrofining catalyst and process using same |
Country Status (8)
Cited By (31)
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US3471399A (en) * | 1967-06-09 | 1969-10-07 | Universal Oil Prod Co | Hydrodesulfurization catalyst and process for treating residual fuel oils |
US3509044A (en) * | 1967-06-26 | 1970-04-28 | Exxon Research Engineering Co | Hydrodesulfurization of petroleum residuum |
US3548020A (en) * | 1969-10-29 | 1970-12-15 | Standard Oil Co | Process for the disproportionation of petroleum hydrocarbons |
US3617526A (en) * | 1969-09-05 | 1971-11-02 | Texaco Inc | Hydrodesulfurization of a vacuum gas oil and vacuum residuum |
DE2136796A1 (de) * | 1970-07-27 | 1972-02-10 | Institut Francais Du Petrole Des Carburants Et Lubrifiants, Rueil-Malmaison, Hauts-De-Seine (Frankreich) | Verfahren zur selektiven Hydrierung von Petroleum-Fraktionen, die im Bereich der Benzine sieden |
US3669873A (en) * | 1970-03-31 | 1972-06-13 | Chevron Res | Hydrofining-hydrocracking process |
DE2246658A1 (de) * | 1971-09-24 | 1973-03-29 | Standard Oil Co | Verbessertes hydrobehandlungsverfahren fuer petroleumkohlenwasserstoffoele und katalysator, der dabei verwendet wird |
JPS4840683A (US20100012521A1-20100121-C00001.png) * | 1971-09-24 | 1973-06-14 | ||
US3793186A (en) * | 1971-07-19 | 1974-02-19 | Chevron Res | Lube oil improvement |
US3893947A (en) * | 1973-09-10 | 1975-07-08 | Union Oil Co | Group VI-B metal catalyst preparation |
US3923638A (en) * | 1971-12-10 | 1975-12-02 | Standard Oil Co | Two-catalyst hydrocracking process |
US3926786A (en) * | 1972-11-20 | 1975-12-16 | Texaco Inc | Production of lubricating oils |
US3928176A (en) * | 1974-04-01 | 1975-12-23 | Exxon Research Engineering Co | Heavy crude conversion |
US3944482A (en) * | 1973-08-08 | 1976-03-16 | Gulf Research & Development Company | Process for the cracking of high metals content feedstocks |
US3977961A (en) * | 1974-02-07 | 1976-08-31 | Exxon Research And Engineering Company | Heavy crude conversion |
US3977962A (en) * | 1974-02-07 | 1976-08-31 | Exxon Research And Engineering Company | Heavy crude conversion |
US4069139A (en) * | 1975-12-29 | 1978-01-17 | Exxon Research & Engineering Co. | Hydrodesulfurization of oil utilizing a narrow pore size distribution catalyst |
US4082695A (en) * | 1975-01-20 | 1978-04-04 | Mobil Oil Corporation | Catalyst for residua demetalation and desulfurization |
DE2813571A1 (de) * | 1977-03-30 | 1978-10-05 | Exxon France | Weissoele und verfahren zu ihrer herstellung |
US4191635A (en) * | 1977-12-21 | 1980-03-04 | Standard Oil Company (Indiana) | Process for the cracking of heavy hydrocarbon streams |
US4242236A (en) * | 1979-03-29 | 1980-12-30 | Chevron Research Company | 65-130 Angstrom mean radius silica-alumina catalyst support |
US4257922A (en) * | 1979-03-13 | 1981-03-24 | Electric Power Research Institute, Inc. | Process for coal liquefaction and catalyst |
US4301037A (en) * | 1980-04-01 | 1981-11-17 | W. R. Grace & Co. | Extruded alumina catalyst support having controlled distribution of pore sizes |
EP0042461A1 (en) * | 1980-06-23 | 1981-12-30 | Exxon Research And Engineering Company | Process for catalytic hydrogenation of hydrogenatable compounds in a hydrocarbon feedstock, and hydrogenated hydrocarbon products |
EP0070125A2 (en) * | 1981-07-09 | 1983-01-19 | Exxon Research And Engineering Company | Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst |
US4431526A (en) * | 1982-07-06 | 1984-02-14 | Union Oil Company Of California | Multiple-stage hydroprocessing of hydrocarbon oil |
US4460707A (en) * | 1982-12-28 | 1984-07-17 | Union Oil Company Of California | Hydroprocessing catalyst and method for preparing it |
US4548710A (en) * | 1982-12-28 | 1985-10-22 | Union Oil Company Of California | Hydrocarbon processing |
US4780446A (en) * | 1982-09-30 | 1988-10-25 | W. R. Grace & Co. | Alumina-silica cogel |
US4913797A (en) * | 1985-11-21 | 1990-04-03 | Mobil Oil Corporation | Catalyst hydrotreating and dewaxing process |
US20090255850A1 (en) * | 2008-04-10 | 2009-10-15 | Opinder Kishan Bhan | Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained |
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US3449456A (en) * | 1968-06-03 | 1969-06-10 | Exxon Research Engineering Co | Startup procedure of isomerizing polymethylbenzene |
FR2390493B1 (fr) * | 1977-05-12 | 1985-04-26 | Linde Ag | Procede de preparation d'olefines |
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- 1966-11-28 FR FR85284A patent/FR1503063A/fr not_active Expired
- 1966-11-29 DE DE1545397A patent/DE1545397C3/de not_active Expired
- 1966-11-29 DK DK617166AA patent/DK129945B/da not_active IP Right Cessation
- 1966-11-30 NL NL666616849A patent/NL139246B/xx not_active IP Right Cessation
- 1966-11-30 SE SE16390/66A patent/SE335896B/xx unknown
- 1966-11-30 ES ES0333965A patent/ES333965A1/es not_active Expired
- 1966-11-30 BE BE690488D patent/BE690488A/xx not_active IP Right Cessation
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US3143491A (en) * | 1962-02-20 | 1964-08-04 | Socony Mobil Oil Co Inc | Catalytic conversion of hydrocarbons with a silica-alumina and crystalline zeolite catalyst composite |
US3242101A (en) * | 1962-07-24 | 1966-03-22 | Sinclair Research Inc | Nickel-molybdenum-alumina hydrocarbon conversion catalyst |
US3277018A (en) * | 1964-01-24 | 1966-10-04 | Mobil Oil | Selective cracking catalyst |
US3322666A (en) * | 1964-08-25 | 1967-05-30 | Gulf Research Development Co | Chemical process for hydrocracking and hydrorefining of hydrocarbon oils |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471399A (en) * | 1967-06-09 | 1969-10-07 | Universal Oil Prod Co | Hydrodesulfurization catalyst and process for treating residual fuel oils |
US3509044A (en) * | 1967-06-26 | 1970-04-28 | Exxon Research Engineering Co | Hydrodesulfurization of petroleum residuum |
US3617526A (en) * | 1969-09-05 | 1971-11-02 | Texaco Inc | Hydrodesulfurization of a vacuum gas oil and vacuum residuum |
US3548020A (en) * | 1969-10-29 | 1970-12-15 | Standard Oil Co | Process for the disproportionation of petroleum hydrocarbons |
US3669873A (en) * | 1970-03-31 | 1972-06-13 | Chevron Res | Hydrofining-hydrocracking process |
DE2136796A1 (de) * | 1970-07-27 | 1972-02-10 | Institut Francais Du Petrole Des Carburants Et Lubrifiants, Rueil-Malmaison, Hauts-De-Seine (Frankreich) | Verfahren zur selektiven Hydrierung von Petroleum-Fraktionen, die im Bereich der Benzine sieden |
US3793186A (en) * | 1971-07-19 | 1974-02-19 | Chevron Res | Lube oil improvement |
JPS4840683A (US20100012521A1-20100121-C00001.png) * | 1971-09-24 | 1973-06-14 | ||
DE2246658A1 (de) * | 1971-09-24 | 1973-03-29 | Standard Oil Co | Verbessertes hydrobehandlungsverfahren fuer petroleumkohlenwasserstoffoele und katalysator, der dabei verwendet wird |
US3882049A (en) * | 1971-09-24 | 1975-05-06 | Standard Oil Co | Catalyst for hydrotreating petroleum hydrocarbon oils and catalyst employed therein |
JPS5550996B2 (US20100012521A1-20100121-C00001.png) * | 1971-09-24 | 1980-12-22 | ||
US3923638A (en) * | 1971-12-10 | 1975-12-02 | Standard Oil Co | Two-catalyst hydrocracking process |
US3926786A (en) * | 1972-11-20 | 1975-12-16 | Texaco Inc | Production of lubricating oils |
US3944482A (en) * | 1973-08-08 | 1976-03-16 | Gulf Research & Development Company | Process for the cracking of high metals content feedstocks |
US3893947A (en) * | 1973-09-10 | 1975-07-08 | Union Oil Co | Group VI-B metal catalyst preparation |
US3977961A (en) * | 1974-02-07 | 1976-08-31 | Exxon Research And Engineering Company | Heavy crude conversion |
US3977962A (en) * | 1974-02-07 | 1976-08-31 | Exxon Research And Engineering Company | Heavy crude conversion |
US3928176A (en) * | 1974-04-01 | 1975-12-23 | Exxon Research Engineering Co | Heavy crude conversion |
US4082695A (en) * | 1975-01-20 | 1978-04-04 | Mobil Oil Corporation | Catalyst for residua demetalation and desulfurization |
US4069139A (en) * | 1975-12-29 | 1978-01-17 | Exxon Research & Engineering Co. | Hydrodesulfurization of oil utilizing a narrow pore size distribution catalyst |
DE2813571A1 (de) * | 1977-03-30 | 1978-10-05 | Exxon France | Weissoele und verfahren zu ihrer herstellung |
US4191635A (en) * | 1977-12-21 | 1980-03-04 | Standard Oil Company (Indiana) | Process for the cracking of heavy hydrocarbon streams |
US4257922A (en) * | 1979-03-13 | 1981-03-24 | Electric Power Research Institute, Inc. | Process for coal liquefaction and catalyst |
US4242236A (en) * | 1979-03-29 | 1980-12-30 | Chevron Research Company | 65-130 Angstrom mean radius silica-alumina catalyst support |
US4301037A (en) * | 1980-04-01 | 1981-11-17 | W. R. Grace & Co. | Extruded alumina catalyst support having controlled distribution of pore sizes |
EP0042461A1 (en) * | 1980-06-23 | 1981-12-30 | Exxon Research And Engineering Company | Process for catalytic hydrogenation of hydrogenatable compounds in a hydrocarbon feedstock, and hydrogenated hydrocarbon products |
EP0070125A3 (en) * | 1981-07-09 | 1983-07-20 | Exxon Research And Engineering Company | Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst |
EP0070125A2 (en) * | 1981-07-09 | 1983-01-19 | Exxon Research And Engineering Company | Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst |
US4431526A (en) * | 1982-07-06 | 1984-02-14 | Union Oil Company Of California | Multiple-stage hydroprocessing of hydrocarbon oil |
US4780446A (en) * | 1982-09-30 | 1988-10-25 | W. R. Grace & Co. | Alumina-silica cogel |
US4460707A (en) * | 1982-12-28 | 1984-07-17 | Union Oil Company Of California | Hydroprocessing catalyst and method for preparing it |
US4548710A (en) * | 1982-12-28 | 1985-10-22 | Union Oil Company Of California | Hydrocarbon processing |
US4913797A (en) * | 1985-11-21 | 1990-04-03 | Mobil Oil Corporation | Catalyst hydrotreating and dewaxing process |
US20090255850A1 (en) * | 2008-04-10 | 2009-10-15 | Opinder Kishan Bhan | Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained |
US8114806B2 (en) * | 2008-04-10 | 2012-02-14 | Shell Oil Company | Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained |
US8450538B2 (en) | 2008-04-10 | 2013-05-28 | Shell Oil Company | Hydrocarbon composition |
Also Published As
Publication number | Publication date |
---|---|
DK129945B (da) | 1974-12-02 |
BE690488A (US20100012521A1-20100121-C00001.png) | 1967-05-02 |
DE1545397B2 (de) | 1979-10-18 |
FR1503063A (fr) | 1967-11-24 |
DK129945C (US20100012521A1-20100121-C00001.png) | 1975-05-12 |
NL6616849A (US20100012521A1-20100121-C00001.png) | 1967-05-31 |
SE335896B (US20100012521A1-20100121-C00001.png) | 1971-06-14 |
NL139246B (nl) | 1973-07-16 |
ES333965A1 (es) | 1967-10-16 |
DE1545397A1 (de) | 1970-01-29 |
DE1545397C3 (de) | 1984-05-30 |
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