US20080179220A1 - Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process - Google Patents
Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process Download PDFInfo
- Publication number
- US20080179220A1 US20080179220A1 US12/045,359 US4535908A US2008179220A1 US 20080179220 A1 US20080179220 A1 US 20080179220A1 US 4535908 A US4535908 A US 4535908A US 2008179220 A1 US2008179220 A1 US 2008179220A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- process according
- feed
- metal
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 28
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000003502 gasoline Substances 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 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 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C10G45/10—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 platinum group metals or compounds thereof
-
- 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
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J37/20—Sulfiding
-
- 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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—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
- 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
- B01J23/74—Iron group metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
-
- 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
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °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
- 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
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2400/02—Gasoline
Definitions
- the present invention relates to the oil refining industry, more particularly to the production of gasoline bases from different units for converting oil cuts, in particular cracking units.
- Thermal cracking units for example for visbreaking or cokefaction, or catalytic cracking, for example for fluidized bed catalytic cracking, produce unsaturated gasoline cuts comprising large quantities of aromatics and olefins.
- Such gasoline cuts generally have substantial levels of sulphur, for example in the range 200 to 3000 ppm by weight, which is incompatible with general specifications for gasoline fuel.
- Such cuts have to be deeply desulphurized to reduce the sulphur content to less than 30 ppm by weight or even 10 ppm by weight in accordance with current specifications, or to satisfy future specifications.
- Industrial processes that are in current use to carry out said operation are catalytic hydrodesulphurization processes.
- Said cuts typically have an end point of 260° C. or less. Thus, they are substantially free of heavy aromatics. Said fractions are also substantially free of metals such as nickel, vanadium or mercury which may poison the catalyst and/or prevent its regeneration. Deep hydrodesulphurization of said fractions, however, is very difficult because of a specific technical problem: those fractions have to be efficiently desulphurized without, however, substantially hydrogenating the olefins that are present. A reduction in the olefin content and thus a correlative increase in the paraffin content would result in an unacceptable drop in the octane number of the gasoline fuel, an essential parameter for selling price. Thus, a method for selective hydrodesulphurization of the treated fractions is sought, i.e. hydrodesulphurization which can eliminate sulphur with minimum hydrogenation of the olefins in the feed.
- Catalysts used industrially for that operation are typically based on alumina, typically comprising at least one metal or metallic compound of a metal from group VIII of the elements periodic table (group including nickel, iron and cobalt, by which the version of the elements periodic table which is used can be identified) and/or at least one metal from group VIB of that table (group comprising molybdenum and tungsten).
- group VIII of the elements periodic table group including nickel, iron and cobalt, by which the version of the elements periodic table which is used can be identified
- group VIB of that table group comprising molybdenum and tungsten
- Catalysts comprising a support constituted by ⁇ silicon carbide are already known: European patent EP-B1-0 313 480 describes a catalyst for hydrotreating oil distillation cuts, said catalyst comprising a support constituted by ⁇ silicon carbide (SiC).
- That support is described as advantageous in that it is resistant to poisoning by both coke and metals.
- Coke accumulation is described as being linked to the presence of high molecular weight aromatics, and the presence of metals (principally nickel and vanadium) is described as the result of the presence of said metals in heavy oil cuts.
- the desulphurizing activity is measured by comparison with other catalysts (comprising a catalyst with an alumina support with a specific surface area of 220 m 2 /g) in the case of thiophene.
- the SiC support can overcome problems connected with the presence of high molecular weight aromatics or metals in the feed. That patent, in contrast, does not indicate the advantage of using a SiC support in place of alumina with respect to hydrodesulphurization activity. Further, it neither mentions nor suggests any advantages in using such a catalyst for selective hydrodesulphurization of olefinic feeds in accordance with the invention (feeds substantially free of the undesirable compounds already mentioned).
- the Applicant has surprisingly discovered that for the selective hydrodesulphurization of olefinic feeds, the use of catalysts with a support essentially constituted by P has substantial advantages over known catalysts. It appears that the use of SiC is advantageous as it can produce a catalyst with improved selectivity, and can minimize the start up time for said catalyst by limiting the initial hydrogenating overactivity. Such a problem has been reported for commercial catalysts supported on alumina, and U.S. Pat. No. 4,149,965 teaches prior deactivation of the catalyst prior to its use in hydrotreating an olefinic feed, the deactivation treatment being selected so as to limit the hydrogenating activity of the catalyst.
- this effect could be considered to derive from the properties of the support, which could be both substantially non acidic and substantially non basic.
- the hydrogenating properties of catalysts are enhanced by the acidity of the support.
- the absence of acidity could contribute to explaining the results obtained, thanks to a relatively low hydrogenating activity of the catalyst with a ⁇ SiC support as regards olefins.
- This could encourage the hydrodesulphurization selectivity as regards olefin hydrogenation.
- the nature of the sulphide phase and thus its catalytic properties could be different, depending on whether it is formed on an alumina support or on a silicon carbide support.
- the ⁇ silicon carbide used in the invention typically has a specific surface area (measured by the BET technique) that is over 5 m 2 /g, preferably in the range 5 to 300 m 2 /g, and more preferably in the range 10 to 250 m 2 /g.
- the pore volume of the support is typically in the range 0.20 cm 3 /g to 1.0 cm 3 /g, preferably in the range 0.3 cm 3 /g to 0.8 cm 3 /g, and more preferably in the range 0.35 cm 3 /g to 0.65 cm 3 /g.
- the amount of group VI metal, in moles per gram of support is typically in the range 6.94 ⁇ 10 ⁇ 5 to 1.40 ⁇ 10 ⁇ 3 , preferably in the range 8.34 ⁇ 10 ⁇ 5 to 6.95 ⁇ 10 ⁇ 4 and highly preferably in the range 1.04 ⁇ 10 ⁇ 4 to 5.50 ⁇ 10 ⁇ 4 .
- the amount of group VIII metal, in moles per gram of support is generally in the range 4.0 ⁇ 10 ⁇ 5 to 1.1 ⁇ 10 ⁇ 3 , preferably in the range 5.34 ⁇ 10 ⁇ 5 to 5.34 ⁇ 10 ⁇ 4 , and highly preferably in the range 6.0 ⁇ 10 ⁇ 5 to 4.0 ⁇ 10 ⁇ 4 .
- the catalyst can also advantageously contain phosphorus the content of which, in moles per gram of support, can be in the range 1.64 ⁇ 10 ⁇ 5 to 1.64 ⁇ 10 ⁇ 3 , preferably in the range 8.2 ⁇ 10 ⁇ 5 to 1.31 ⁇ 10 ⁇ 3 , and highly preferably in the range 8.2 ⁇ 10 ⁇ 5 to 6.6 ⁇ 10 ⁇ 4 .
- the catalysts of the invention can be prepared using any standard preparation method that is known to the skilled person, the different metals of the active phase also possibly being deposited sequentially or simultaneously on the support.
- Non exhaustive examples which can be cited are dry impregnation preparation methods, exchange methods, or surface organometallic chemical methods.
- the catalysts can be presulphurized in situ or ex situ prior to use in the selective hydrodesulphurization process. Sulphurization can be carried out using any method that is known to the skilled person. As an example, the catalyst can be placed in an atmosphere of H 2 S diluted with a stream of hydrogen at a predetermined temperature for a predetermined period.
- the invention concerns the use of supported catalysts comprising at least one metal or metallic compound of a metal from the group formed by elements from groups VIII and/or VIB of the periodic table, deposited on a support essentially constituted by ⁇ silicon carbide, in a process for selective hydrodesulphurization of an olefinic hydrocarbon feed substantially free of polynuclear aromatics and metals.
- the feed has an end point of less than 260° C., and comprises at least 5% by weight of olefins.
- said feed boils in the gasoline range, i.e. in the ASTM boiling point range of about 30° C. to 230° C.
- the feed comprises at least 50% by weight of pyrolysis gasoline and/or fluid catalytic cracking gasoline, and may even be constituted by more than 90% by weight, or even entirely constituted by gasoline fractions or gasoline deriving from a steam cracker and/or a fluid catalytic cracker (FCC).
- FCC fluid catalytic cracker
- the selective hydrodesulphurization process is carried out under temperature conditions in the range 200° C. to 400° C., at a pressure in the range 0.5 to 4.0 MPa, with a H 2 /HC ratio in the range 100 to 600 (litre/litre under normal conditions) and with an hourly mass flow rate of feed per unit weight of catalyst (WHSV) in the range 1 to 15 h ⁇ 1 .
- WHSV hourly mass flow rate of feed per unit weight of catalyst
- the attached drawing comprises two graphs comparing catalysts containing Al 2 O 3 on the one hand versus SiC on the other hand at start up, with respect to hydrogenation (HTO) and hydrodesulphurization (HDS).
- HTO hydrogenation
- HDS hydrodesulphurization
- a catalyst A was obtained by using a synthesis method termed the OrganoMetallic Surface Chemical method (OMSC). Silicon carbide SiC extrudates (2 mm diameter) were supplied by SICAT Sarl; their principal characteristics are summarized in Table 11
- the pretreated solid was transferred into a reactor suitable for OMSC synthesis (Schlenk tube). This reactor had already been filled with solution so that the volume of the solution was 10 cm 3 /g of catalyst, then purged with argon to eliminate all traces of oxygen from the medium.
- the solution was constituted by an organometallic Co complex, cobalt biscyclopentadienyl Co(C 5 H 5 ) 2 diluted in n-heptane.
- the concentration of organometallic complex was selected to obtain a Co/(Co+Mo) atomic ratio of 0.4.
- the solid was left in solution for two hours at ambient temperature and hydrogen bubbled through, then washed in pure heptane and dried in a stream of argon at ambient temperature overnight. Finally, the solid was sulphurized by applying the same treatment as above. The characteristics of the catalyst following sulphurization are shown in Table 2.
- Catalyst B was obtained using the same synthesis protocol as for catalyst A, with an industrial alumina type support from Axens.
- the characteristics of the support are given in Table 3:
- catalyst B is essentially distinguished from catalyst A in the nature of the support used, and also by the dimensions of the grains.
- the catalysts were ground to the 300-500 micrometre fraction in the absence of air.
- the solids were then passivated in air at ambient temperature for 4 hours and loaded into the catalytic reactor.
- a constant temperature stage for sulphurization was carried out for 4 hours at 350° C. (temperature ramp-up 20° C./hour). After sulphurization, the temperature was reduced to 150° C.
- test conditions were as follows: total pressure: 1.5 MPa;
- the temperature was varied between 280° C. and 310° C. Each operating condition (temperature) was kept constant for at least 48 hours, and a reversal point ensured that the loss of desulphurizing activity of the catalyst was very small or even zero.
- the degrees of HDS and HDO are calculated respectively using the following formulae:
- hydrodesulphurization and hydrogenation activities were calculated by assuming an order of 1 (sulphur-containing compounds) and 0 (olefinic compounds) respectively for the reactants:
- Table 6 shows the results obtained for catalysts A and B. It appears that the catalyst supported on silicon carbide was much more selective than the catalyst supported on alumina since catalyst A was systematically less hydrogenating than catalyst B.
- the use of a silicon carbide support in place of alumina can reduce the hydrogenating activity of the catalyst while its desulphurizing activity remains constant or may even be slightly improved.
- catalyst B (not in accordance with the catalyst used in the invention) exhibited hydrogenating overactivity compared with its stabilized state, while its desulphurizing activity was essentially stable. Then, to achieve a similar sulphur content, catalyst B (not in accordance) resulted in hydrogenation of a surplus of olefins in the feed at the start of the test, and the quality of the gasoline obtained at the start of the cycle on catalyst B was thus lower in terms of octane number than that obtained for the same catalyst after stabilization.
- a partial deactivation treatment such as that proposed in U.S. Pat. No. 4,149,965 is thus recommended to limit its hydrogenating activity prior to passing the feed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention concerns the use of supported catalysts comprising at least one metal or metallic compound of a metal from group VI and/or group VIII deposited on a support essentially constituted by β silicon carbide in a process for selective hydrodesulphurization of an olefinic hydrocarbon feed that is substantially free of polynuclear aromatics and metals.
The invention can be used to carry out deep desulphurization of catalytically cracked gasoline cuts with very limited saturation of olefins and thus a minimum loss of octane number.
Description
- The present invention relates to the oil refining industry, more particularly to the production of gasoline bases from different units for converting oil cuts, in particular cracking units.
- Thermal cracking units, for example for visbreaking or cokefaction, or catalytic cracking, for example for fluidized bed catalytic cracking, produce unsaturated gasoline cuts comprising large quantities of aromatics and olefins. Such gasoline cuts generally have substantial levels of sulphur, for example in the range 200 to 3000 ppm by weight, which is incompatible with general specifications for gasoline fuel. Thus, such cuts have to be deeply desulphurized to reduce the sulphur content to less than 30 ppm by weight or even 10 ppm by weight in accordance with current specifications, or to satisfy future specifications. Industrial processes that are in current use to carry out said operation are catalytic hydrodesulphurization processes.
- Said cuts typically have an end point of 260° C. or less. Thus, they are substantially free of heavy aromatics. Said fractions are also substantially free of metals such as nickel, vanadium or mercury which may poison the catalyst and/or prevent its regeneration. Deep hydrodesulphurization of said fractions, however, is very difficult because of a specific technical problem: those fractions have to be efficiently desulphurized without, however, substantially hydrogenating the olefins that are present. A reduction in the olefin content and thus a correlative increase in the paraffin content would result in an unacceptable drop in the octane number of the gasoline fuel, an essential parameter for selling price. Thus, a method for selective hydrodesulphurization of the treated fractions is sought, i.e. hydrodesulphurization which can eliminate sulphur with minimum hydrogenation of the olefins in the feed.
- Catalysts used industrially for that operation are typically based on alumina, typically comprising at least one metal or metallic compound of a metal from group VIII of the elements periodic table (group including nickel, iron and cobalt, by which the version of the elements periodic table which is used can be identified) and/or at least one metal from group VIB of that table (group comprising molybdenum and tungsten). A variety of techniques have already been employed to increase the hydrodesulphurization selectivity: modifying the operating conditions in which desulphurization is carried out and/or modifying the hydrodesulphurization catalyst to improve selectivity. Several methods have been proposed to improve the selectivity of the catalyst. Non exhaustive examples which can be cited are:
-
- U.S. Pat. No. 4,140,626, concerning a process for hydrotreating cracked naphtha using a catalyst containing a metal from group VIB and from group VIII deposited on a support composed of at least 70% by weight magnesium oxide;
- U.S. Pat. No. 3,957,625, for a process for selective desulphurization of cracked gasoline using a cobalt-molybdenum/alumina type catalyst with a promoter selected from barium, magnesium, cadmium and rare earths;
- U.S. Pat. No. 5,348,928, concerning a method for preparing and formulating a selective hydrotreatment catalyst comprising a metal from group VIB containing 4% to 20% oxide equivalent by weight and a metal from group VIII containing 0.5% to 10% oxide equivalent by weight. The support contains 0.5% to 50% oxide equivalent by weight of magnesium and 0.02% to 10% oxide equivalent of an alkali with respect to the total catalyst mass.
- However, known prior art catalysts consume quantities of olefins which remain substantial and prejudicial to selling price of the fuel. This consumption depends on the treated feed, the hydrotreatment conditions, but also on the required degree of desulphurization. One aim of the invention is to use particular catalysts that can improve the hydrodesulphurization selectivity for light cuts comprising olefins. A further aim of the invention is to propose a process for selective hydrodesulphurization employing said catalysts.
- Catalysts comprising a support constituted by β silicon carbide are already known: European patent EP-B1-0 313 480 describes a catalyst for hydrotreating oil distillation cuts, said catalyst comprising a support constituted by β silicon carbide (SiC).
- That support is described as advantageous in that it is resistant to poisoning by both coke and metals. Coke accumulation is described as being linked to the presence of high molecular weight aromatics, and the presence of metals (principally nickel and vanadium) is described as the result of the presence of said metals in heavy oil cuts. The desulphurizing activity is measured by comparison with other catalysts (comprising a catalyst with an alumina support with a specific surface area of 220 m2/g) in the case of thiophene. Such a comparison shows that the desulphurizing activity (moles of thiophene transformed per gram of catalyst and per second) of the catalyst with a SiC support is substantially lower than that of the catalyst with an alumina support by a factor of close to 2 to 6 depending on the surface areas of the SiC support used and close to that of a catalyst based on alumina.
- The technical teaching of that patent is that the SiC support can overcome problems connected with the presence of high molecular weight aromatics or metals in the feed. That patent, in contrast, does not indicate the advantage of using a SiC support in place of alumina with respect to hydrodesulphurization activity. Further, it neither mentions nor suggests any advantages in using such a catalyst for selective hydrodesulphurization of olefinic feeds in accordance with the invention (feeds substantially free of the undesirable compounds already mentioned).
- In contrast, the Applicant has surprisingly discovered that for the selective hydrodesulphurization of olefinic feeds, the use of catalysts with a support essentially constituted by P has substantial advantages over known catalysts. It appears that the use of SiC is advantageous as it can produce a catalyst with improved selectivity, and can minimize the start up time for said catalyst by limiting the initial hydrogenating overactivity. Such a problem has been reported for commercial catalysts supported on alumina, and U.S. Pat. No. 4,149,965 teaches prior deactivation of the catalyst prior to its use in hydrotreating an olefinic feed, the deactivation treatment being selected so as to limit the hydrogenating activity of the catalyst.
- Without wishing to be bound to a particular theory, this effect could be considered to derive from the properties of the support, which could be both substantially non acidic and substantially non basic. It is known that the hydrogenating properties of catalysts are enhanced by the acidity of the support. The absence of acidity could contribute to explaining the results obtained, thanks to a relatively low hydrogenating activity of the catalyst with a β SiC support as regards olefins. This could encourage the hydrodesulphurization selectivity as regards olefin hydrogenation. It cannot be excluded that the nature of the sulphide phase and thus its catalytic properties could be different, depending on whether it is formed on an alumina support or on a silicon carbide support.
- The β silicon carbide used in the invention typically has a specific surface area (measured by the BET technique) that is over 5 m2/g, preferably in the range 5 to 300 m2/g, and more preferably in the
range 10 to 250 m2/g. The pore volume of the support is typically in the range 0.20 cm3/g to 1.0 cm3/g, preferably in the range 0.3 cm3/g to 0.8 cm3/g, and more preferably in the range 0.35 cm3/g to 0.65 cm3/g. - The amount of group VI metal, in moles per gram of support, is typically in the range 6.94×10−5 to 1.40×10−3, preferably in the range 8.34×10−5 to 6.95×10−4 and highly preferably in the range 1.04×10−4 to 5.50×10−4. The amount of group VIII metal, in moles per gram of support, is generally in the range 4.0×10−5 to 1.1×10−3, preferably in the range 5.34×10−5 to 5.34×10−4, and highly preferably in the range 6.0×10−5 to 4.0×10−4. The catalyst can also advantageously contain phosphorus the content of which, in moles per gram of support, can be in the range 1.64×10−5 to 1.64×10−3, preferably in the range 8.2×10−5 to 1.31×10−3, and highly preferably in the range 8.2×10−5 to 6.6×10−4.
- The manufacture of silicon carbide type supports which can be used in heterogeneous catalysis is already known and disclosed in patents such as EP-B1-0 440 569 or in U.S. Pat. No. 6,184,178, although this list is not exhaustive. That type of support is manufactured on an industrial scale, for example by SICAT Sarl (France).
- The catalysts of the invention can be prepared using any standard preparation method that is known to the skilled person, the different metals of the active phase also possibly being deposited sequentially or simultaneously on the support. Non exhaustive examples which can be cited are dry impregnation preparation methods, exchange methods, or surface organometallic chemical methods.
- The catalysts can be presulphurized in situ or ex situ prior to use in the selective hydrodesulphurization process. Sulphurization can be carried out using any method that is known to the skilled person. As an example, the catalyst can be placed in an atmosphere of H2S diluted with a stream of hydrogen at a predetermined temperature for a predetermined period.
- In general, the invention concerns the use of supported catalysts comprising at least one metal or metallic compound of a metal from the group formed by elements from groups VIII and/or VIB of the periodic table, deposited on a support essentially constituted by β silicon carbide, in a process for selective hydrodesulphurization of an olefinic hydrocarbon feed substantially free of polynuclear aromatics and metals.
- Typically, the feed has an end point of less than 260° C., and comprises at least 5% by weight of olefins. Generally, said feed boils in the gasoline range, i.e. in the ASTM boiling point range of about 30° C. to 230° C. As an example, the feed comprises at least 50% by weight of pyrolysis gasoline and/or fluid catalytic cracking gasoline, and may even be constituted by more than 90% by weight, or even entirely constituted by gasoline fractions or gasoline deriving from a steam cracker and/or a fluid catalytic cracker (FCC).
- Usually, the selective hydrodesulphurization process is carried out under temperature conditions in the range 200° C. to 400° C., at a pressure in the range 0.5 to 4.0 MPa, with a H2/HC ratio in the
range 100 to 600 (litre/litre under normal conditions) and with an hourly mass flow rate of feed per unit weight of catalyst (WHSV) in the range 1 to 15 h−1. - The attached drawing comprises two graphs comparing catalysts containing Al2O3 on the one hand versus SiC on the other hand at start up, with respect to hydrogenation (HTO) and hydrodesulphurization (HDS).
- A catalyst A was obtained by using a synthesis method termed the OrganoMetallic Surface Chemical method (OMSC). Silicon carbide SiC extrudates (2 mm diameter) were supplied by SICAT Sarl; their principal characteristics are summarized in Table 11
-
TABLE 1 Characteristics of SiC support Form Surface area: SBET m2/g Pore volume (Hg) cm3/g Extrudates 53 0.4 2 mm - An aqueous solution of ammonium heptamolybdate was impregnated using the pore volume method into the silicon carbide. The molybdenum (Mo) concentration in the solution was calculated to obtain the desired Mo content on the support, then the solid was left to mature for 12 hours. The solid was then oven dried at 120° C. for twelve hours, and calcined for two hours at 500° C. in a stream of dry air (1 l/h.g of catalyst). The solid was then sulphurized in a stream of gaseous H2S in hydrogen (15% by weight of H2S, total gas flow rate 1 l/h.g of catalyst) from ambient temperature to 400° C. (5° C./min ramp-up). The temperature was kept at 400° C. for two hours, then the system was cooled to 200° C. (ramp-down 5° C./min) and maintained at that temperature for an additional two hours in pure hydrogen, then finally cooled to ambient temperature, still in pure hydrogen. The pretreated solid was transferred into a reactor suitable for OMSC synthesis (Schlenk tube). This reactor had already been filled with solution so that the volume of the solution was 10 cm3/g of catalyst, then purged with argon to eliminate all traces of oxygen from the medium. The solution was constituted by an organometallic Co complex, cobalt biscyclopentadienyl Co(C5H5)2 diluted in n-heptane. The concentration of organometallic complex was selected to obtain a Co/(Co+Mo) atomic ratio of 0.4. The solid was left in solution for two hours at ambient temperature and hydrogen bubbled through, then washed in pure heptane and dried in a stream of argon at ambient temperature overnight. Finally, the solid was sulphurized by applying the same treatment as above. The characteristics of the catalyst following sulphurization are shown in Table 2.
-
TABLE 2 Characteristics of catalyst A (in accordance with use in the invention) Co/(Co + Mo) atomic ratio Mo content (wt %) Co content (wt %) (atom/atom) 3.1 0.7 0.37 - Catalyst B was obtained using the same synthesis protocol as for catalyst A, with an industrial alumina type support from Axens. The characteristics of the support are given in Table 3:
-
TABLE 3 Characteristics of industrial alumina support Form Surface area: SBET m2/g Pore volume (Hg) cm3/ g Beads 60 0.6 2.4-4 mm - The characteristics of the catalyst after sulphurization are shown in Table 4:
-
TABLE 4 Characteristics of catalyst B (comparative) Co/(Co + Mo) atomic ratio Mo content (wt %) Co content (wt %) (atom/atom) 3.2 0.7 0.36 - Thus, catalyst B is essentially distinguished from catalyst A in the nature of the support used, and also by the dimensions of the grains.
- In order to overcome diffusional limitation problems, the catalysts were ground to the 300-500 micrometre fraction in the absence of air. The solids were then passivated in air at ambient temperature for 4 hours and loaded into the catalytic reactor. The catalyst was then sulphurized in situ using a synthetic feed (6% by weight of dimethyldisulphide in n-heptane) under the following conditions: Total pressure=2.0 MPa, H2/feed=300 (litre/litre), mass flow rate of feed with respect to catalyst per hour (WHSV)=3 h−1. A constant temperature stage for sulphurization was carried out for 4 hours at 350° C. (temperature ramp-up 20° C./hour). After sulphurization, the temperature was reduced to 150° C. and the sulphurization feed was replaced with FCC gasoline to be treated, and the operating conditions were adjusted. In this example, the two catalysts were tested on a first olefinic feed constituted by a moderately sulphurized total FCC gasoline with the characteristics shown in Table 5.
-
TABLE 5 Characteristics of first olefinic feed Total S: 460 ppm by weight Density (25° C.): 0.76 PONA analysis (wt %): Paraffins: 28.4 Naphthenes; 8.1 Aromatics: 29.3 Olefins: 34.2 - The test conditions were as follows: total pressure: 1.5 MPa;
-
- H2/feed=300 (litre/litre), mass flow rate of feed with respect to catalyst per hour (WHSV)=9 h−1.
- The temperature was varied between 280° C. and 310° C. Each operating condition (temperature) was kept constant for at least 48 hours, and a reversal point ensured that the loss of desulphurizing activity of the catalyst was very small or even zero. The degrees of HDS and HDO are calculated respectively using the following formulae:
-
- HDS=100×(1−Sf/So), in which So and Sf respectively represent the concentrations in the feed and effluent (ppm);
- HDO=100×(1−Cf/Co) in which Co and Cf represent the concentrations of olefins in the feed and in the effluent respectively (wt %).
- The hydrodesulphurization and hydrogenation activities were calculated by assuming an order of 1 (sulphur-containing compounds) and 0 (olefinic compounds) respectively for the reactants:
-
- AHDS=Ln(100(100−HDS));
- AHDO=Co×HDO/100.
- Table 6 shows the results obtained for catalysts A and B. It appears that the catalyst supported on silicon carbide was much more selective than the catalyst supported on alumina since catalyst A was systematically less hydrogenating than catalyst B.
-
TABLE 6 selective hydrodesulphurization of a first olefinic feed Test Catalyst T(° C.) duration (h) HDS (%) HDO (%) AHDA AHDO A 280 96 74.5 12.1 1.37 0.040 B 280 96 73.3 15.2 1.31 0.051 A 290 144 86.8 19.2 2.02 0.063 B 290 144 86.2 24.3 1.97 0.081 A 300 192 94.0 29.4 2.81 0.097 B 300 192 93.2 33.3 2.66 0.111 - More precisely, the use of a silicon carbide support in place of alumina can reduce the hydrogenating activity of the catalyst while its desulphurizing activity remains constant or may even be slightly improved.
- The changes in hydrodesulphurization and hydrogenation during the first 96 hours of the test of Example 3 for catalyst A and catalyst B are shown in Table 7 and in
FIG. 1 . -
TABLE 7 Change in degree of hydrodesulphurization and hydrogenation during start up of catalysts A and B during selective hydrodesulphurization of a first olefinic feed Catalyst Test duration (h) HDS (%) HDO (%) A 10 75.0 12.8 B 12 74.5 20.1 A 24 74.8 12.5 B 24 74.5 18.2 A 36 74.6 12.2 B 38 73.9 17.1 A 48 74.5 12.1 B 48 73.5 16.3 A 72 74.2 12.3 B 72 73.2 15.4 A 96 74.5 12.1 B 96 73.3 15.2 - During the first hours of the test, catalyst B (not in accordance with the catalyst used in the invention) exhibited hydrogenating overactivity compared with its stabilized state, while its desulphurizing activity was essentially stable. Then, to achieve a similar sulphur content, catalyst B (not in accordance) resulted in hydrogenation of a surplus of olefins in the feed at the start of the test, and the quality of the gasoline obtained at the start of the cycle on catalyst B was thus lower in terms of octane number than that obtained for the same catalyst after stabilization. For this type of catalyst, a partial deactivation treatment such as that proposed in U.S. Pat. No. 4,149,965 is thus recommended to limit its hydrogenating activity prior to passing the feed. In contrast, this phenomenon is substantially reduced on catalyst A (in accordance with the use of the invention), which had no substantial hydrogenating overactivity at the start of the test and very rapidly reached its steady state. Thus it was not necessary to partially deactivate catalyst A prior to bringing it into contact with the feed.
- In this example, the two above catalysts were tested on a depentanized olefinic feed (Table 8) more sulphurized as above.
-
TABLE 8 Characteristics of second olefinic feed Total S: 2297 ppm by weight Density (25° C.): 0.77 PONA analysis (wt %): Paraffins: 24.5 Naphthenes; 8.4 Aromatics: 37.0 Olefins: 30.1 - The test conditions were as follows: total pressure: 1.8 MPa; H2/feed=350 (litre/litre), WHSV=7 h−1. The temperature was varied between 280° C. and 310° C. to vary the degree of desulphurization. Table 9 shows the results obtained for catalysts A and B:
-
TABLE 9 Selective hydrodesulphurization of a second olefinic feed Test Catalyst T (° C.) duration (h) HDS (%) HDO (%) AHDA AHDO A 280 96 77.9 13.7 1.51 0.046 B 280 96 77.1 16.7 1.47 0.056 A 290 144 87.3 18.0 2.06 0.060 B 290 144 86.7 20.5 2.02 0.068 A 300 192 92.9 22.2 2.65 0.074 B 300 192 92.5 25.0 2.59 0.083 A 310 240 95.8 26.5 3.17 0.088 B 310 240 95.6 30.1 3.12 0.100 - For this feed again, the catalyst supported on silicon carbide proved to be more selective. The best selectivity for catalyst A was again due to a lower hydrogenating activity for catalyst A, while the desulphurization activity of the two catalysts was substantially identical.
- Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
- In the foregoing and in the examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
- The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding French application No. 03/10.027, filed Aug. 19, 2003 is incorporated by reference herein.
- The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
- From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
Claims (20)
1-6. (canceled)
7. In a process comprising subjecting an olefinic hydrocarbon feed to selective catalytic hydrodesulphurization at 200-400° C.° wherein the olefinic hydrocarbon feed that is essentially free of polynuclear aromatics and metals, the improvement wherein the catalyst is a supported catalyst comprising at least one metal or metallic compound of a metal from the group formed by elements from group VIII and/or group VIB of the periodic table deposited on a support consisting essentially of β silicon carbide so as to lower the degree of hydrogenation of the olefins in the feed as compared to the use of a support of alumina having essentially the same surface area and catalytic components, thereby limiting initial hydrogenation over activity and minimizing startup time.
8. A process according to claim 7 , wherein the feed has an end point of less than 260° C., and comprises at least 5% by weight of olefins.
9. A process according to claim 7 , wherein the feed boils in the gasoline range.
10. In a process according to claim 9 , wherein the feed comprises at least 50% by weight of pyrolysis gasoline and/or fluid catalytic cracking gasoline.
11. A process according to claim 7 , in which the support has a specific surface area in the range of 5 to 300 m2/g.
12. A process according to claim 7 , carried out at a pressure in the range of 0.5 to 4 MPa, with a H feed ratio in the range 100 to 600 (litre/litre) and with an hourly mass flow rate of feed with respect to catalyst (WHSV) in the range of 1 to 15 h−1.
13. A process according to claim 11 , said catalyst having a specific surface in the range of 10 to 250 m2/g.
14. A process according to claim 7 , said catalyst having a pore volume of 0.20 cm3/g to 1.0 cm3/g.
15. A process according to claim 7 , said catalyst having a pore volume of 0.3 cm3/g to 0.8 cm3/g.
16. A process according to claim 7 , said catalyst having a pore volume of 0.35 cm3/g to 0.65 cm3/g.
17. A process according to claim 7 , wherein the amount of metals in mols per gram of support is 6.94×10−5 to 1.40×10−3 mols of the group VIB metal, and 4.0×10−5 to 1.1×10−3 mols of the group VIII metal.
18. A process according to claim 7 , wherein the group VIB metal is molybdenum and the group VIII metal is cobalt.
19. A process according to claim 7 , wherein the metals are sulfurized.
20. A process according to claim 18 , wherein the metals are sulfurized.
21. In a process comprising subjecting an olefinic hydrocarbon feed to selective catalytic hydrodesulphurization at 200-400° C.° wherein the olefinic hydrocarbon feed is free of polynuclear aromatics and metals, the improvement wherein the catalyst is a supported catalyst comprising at least one metal or metallic compound of a metal from the group formed by elements from group VIII and/or group VIB of the elements periodic table deposited on a support consisting of β silicon carbide so as to lower the degree of hydrogenation of the olefins in the feed as compared to the use of a support of alumina having essentially the same surface area and catalytic components, thereby limiting initial hydrogenation over activity and minimizing startup time.
22. A process according to claim 17 , wherein the group VIB metal is molybdenum and the group VIII metal is cobalt.
23. A process according to claim 22 , said catalyst having a pore volume of 0.35 cm3/g to 0.65 cm3/g.
24. A process according to claim 23 , wherein the group VIB metal is molybdenum and the group VIII metal is cobalt.
25. A process according to claim 24 , said catalyst having a specific surface in the range of 10 to 250 m2/g.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/045,359 US20080179220A1 (en) | 2003-08-19 | 2008-03-10 | Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0310027A FR2858980B1 (en) | 2003-08-19 | 2003-08-19 | USE OF A CATALYST COMPRISING A SILICON B FUEL SUPPORT IN A SELECTIVE HYDRODESULFURATION PROCESS |
FR03/10.027 | 2003-08-19 | ||
US10/921,301 US20050056568A1 (en) | 2003-08-19 | 2004-08-19 | Use of a catalyst comprising a beta silicon carbide support in a selective hydrodesulphurization process |
US12/045,359 US20080179220A1 (en) | 2003-08-19 | 2008-03-10 | Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/921,301 Continuation US20050056568A1 (en) | 2003-08-19 | 2004-08-19 | Use of a catalyst comprising a beta silicon carbide support in a selective hydrodesulphurization process |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080179220A1 true US20080179220A1 (en) | 2008-07-31 |
Family
ID=34043783
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/921,301 Abandoned US20050056568A1 (en) | 2003-08-19 | 2004-08-19 | Use of a catalyst comprising a beta silicon carbide support in a selective hydrodesulphurization process |
US12/045,359 Abandoned US20080179220A1 (en) | 2003-08-19 | 2008-03-10 | Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/921,301 Abandoned US20050056568A1 (en) | 2003-08-19 | 2004-08-19 | Use of a catalyst comprising a beta silicon carbide support in a selective hydrodesulphurization process |
Country Status (5)
Country | Link |
---|---|
US (2) | US20050056568A1 (en) |
EP (1) | EP1508370B1 (en) |
JP (1) | JP4927323B2 (en) |
DE (1) | DE602004018438D1 (en) |
FR (1) | FR2858980B1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7632962B2 (en) | 2006-04-26 | 2009-12-15 | Eastman Chemical Company | Hydrogenation process and catalysts |
FR2915743A1 (en) * | 2007-05-02 | 2008-11-07 | Sicat Sarl | COMPOSITE OF NANOTUBES OR NANOFIBERS ON BETA-SIC FOAM |
US8552236B2 (en) * | 2009-09-30 | 2013-10-08 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4255253A (en) * | 1979-01-03 | 1981-03-10 | The Standard Oil Company | Hydrogen processing of hydrocarbon feeds using coated catalysts |
US4914070A (en) * | 1987-10-19 | 1990-04-03 | Pechiney Electrometallurgie | Process for the production of silicon carbide with a large specific surface area and use for high-temperature catalytic reactions |
US6184178B1 (en) * | 1997-01-13 | 2001-02-06 | Pechiney Recherche | Catalyst support with base of silicon carbide with high specific surface area in granulated form having improved mechanical characteristics |
US6193877B1 (en) * | 1996-08-23 | 2001-02-27 | Exxon Research And Engineering Company | Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds |
US6372125B1 (en) * | 1999-08-23 | 2002-04-16 | Institut Francais Du Petrole | Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils |
US20020121459A1 (en) * | 2000-01-21 | 2002-09-05 | Pradhan Vivek R. | Sulfur removal process |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB899651A (en) * | 1958-07-25 | 1962-06-27 | British Petroleum Co | Improvements relating to the refining of gasoline |
GB1311473A (en) * | 1969-03-31 | 1973-03-28 | Gas Council | Desulphiding of hydrocarbons |
FR2621904B1 (en) * | 1987-10-19 | 1990-01-26 | Pechiney Electrometallurgie | PROCESS FOR PRODUCING LARGE SPECIFIC SILICON CARBIDE FOR CATALYST SUPPORT |
EP1152827A4 (en) * | 1999-01-12 | 2002-11-06 | Hyperion Catalysis Int | Carbide and oxycarbide based compositions and nanorods |
FR2790000B1 (en) * | 1999-02-24 | 2001-04-13 | Inst Francais Du Petrole | PROCESS FOR PRODUCING LOW SULFUR ESSENCE |
US20020148757A1 (en) * | 2001-02-08 | 2002-10-17 | Huff George A. | Hydrotreating of components for refinery blending of transportation fuels |
US7629289B2 (en) * | 2004-06-23 | 2009-12-08 | Uop Llc | Selective naphtha desulfurization process and catalyst |
-
2003
- 2003-08-19 FR FR0310027A patent/FR2858980B1/en not_active Expired - Lifetime
-
2004
- 2004-07-29 EP EP04291953A patent/EP1508370B1/en not_active Expired - Fee Related
- 2004-07-29 DE DE602004018438T patent/DE602004018438D1/en active Active
- 2004-08-19 JP JP2004239472A patent/JP4927323B2/en not_active Expired - Fee Related
- 2004-08-19 US US10/921,301 patent/US20050056568A1/en not_active Abandoned
-
2008
- 2008-03-10 US US12/045,359 patent/US20080179220A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4255253A (en) * | 1979-01-03 | 1981-03-10 | The Standard Oil Company | Hydrogen processing of hydrocarbon feeds using coated catalysts |
US4914070A (en) * | 1987-10-19 | 1990-04-03 | Pechiney Electrometallurgie | Process for the production of silicon carbide with a large specific surface area and use for high-temperature catalytic reactions |
US6193877B1 (en) * | 1996-08-23 | 2001-02-27 | Exxon Research And Engineering Company | Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds |
US6184178B1 (en) * | 1997-01-13 | 2001-02-06 | Pechiney Recherche | Catalyst support with base of silicon carbide with high specific surface area in granulated form having improved mechanical characteristics |
US6372125B1 (en) * | 1999-08-23 | 2002-04-16 | Institut Francais Du Petrole | Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils |
US20020121459A1 (en) * | 2000-01-21 | 2002-09-05 | Pradhan Vivek R. | Sulfur removal process |
Also Published As
Publication number | Publication date |
---|---|
FR2858980A1 (en) | 2005-02-25 |
JP4927323B2 (en) | 2012-05-09 |
US20050056568A1 (en) | 2005-03-17 |
JP2005059006A (en) | 2005-03-10 |
EP1508370B1 (en) | 2008-12-17 |
DE602004018438D1 (en) | 2009-01-29 |
FR2858980B1 (en) | 2006-02-17 |
EP1508370A1 (en) | 2005-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7981828B2 (en) | Process for hydrodesulphurizing gasoline cuts containing sulphur and olefins in the presence of a catalyst comprising at least one support, one group VIII and one group VIB element | |
US8926831B2 (en) | Process for hydrodesulphurizing gasoline employing a catalyst with controlled porosity | |
JP4798324B2 (en) | Method for desulfurizing gasoline comprising desulfurization of heavy and intermediate fractions resulting from fractionation into at least three fractions | |
JP4547922B2 (en) | Partially coked catalyst usable for hydrotreatment of fractions containing sulfur compounds and olefins | |
US5868921A (en) | Single stage, stacked bed hydrotreating process utilizing a noble metal catalyst in the upstream bed | |
US7993513B2 (en) | Two-step process for desulphurizing olefinic gasolines comprising arsenic | |
US4022682A (en) | Hydrodenitrogenation of shale oil using two catalysts in series reactors | |
JP2009517499A (en) | Selective naphtha hydrodesulfurization with high-temperature mercaptan decomposition | |
CZ267994A3 (en) | Catalysts, process of their preparation and use | |
JP2008525194A (en) | Hydrocracking catalyst for vacuum gas oil and demetallized blends | |
US7306714B2 (en) | Process for hydrodesulphurizing cuts containing sulphur containing compounds and olefins in the presence of a supported catalyst comprising group VIII and VIB elements | |
EP0950702B1 (en) | Hydrocracking catalyst and hydrocracking method for hydrocarbon oils | |
US7223333B2 (en) | Process for hydrodesulphurization of cuts containing sulphur containing compounds and olefins in the presence of a catalyst comprising an element of group VIII and tungsten | |
US20080179220A1 (en) | Use Of A Catalyst Comprising A Beta Silicon Carbide Support In A Selective Hydrodesulphurization Process | |
JPH0149399B2 (en) | ||
RU2666355C2 (en) | Used hydro-treating catalyst regeneration method | |
US11795405B2 (en) | Process for the hydrodesulfurization of sulfur-containing olefinic gasoline cuts using a regenerated catalyst | |
US4969989A (en) | Hydrocarbon conversion process with catalytic materials of controlled geometric mean electronegativity | |
WO2001074973A1 (en) | Process for hydrodesulfurization of light oil fraction | |
JP3544603B2 (en) | Hydrorefining method of hydrocarbon oil | |
KR20220035392A (en) | Process for producing gasoline with low sulfur and mercaptan content | |
NO970222L (en) | Catalyst, its use and process for its preparation | |
US20040040888A1 (en) | Process for hydrocracking into a stage of hydrocarbon feedstocks |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |