EP0649896B1 - Procédé pour la production conjointe de distillats moyens et d'huiles lubrifiantes à partir de coupes pétrolières lourdes - Google Patents
Procédé pour la production conjointe de distillats moyens et d'huiles lubrifiantes à partir de coupes pétrolières lourdes Download PDFInfo
- Publication number
- EP0649896B1 EP0649896B1 EP94402284A EP94402284A EP0649896B1 EP 0649896 B1 EP0649896 B1 EP 0649896B1 EP 94402284 A EP94402284 A EP 94402284A EP 94402284 A EP94402284 A EP 94402284A EP 0649896 B1 EP0649896 B1 EP 0649896B1
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- EP
- European Patent Office
- Prior art keywords
- process according
- range
- catalyst
- group
- alumina
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 47
- 239000003921 oil Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000003208 petroleum Substances 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 3
- 229910021476 group 6 element Inorganic materials 0.000 claims 2
- 229910021472 group 8 element Inorganic materials 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 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
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment 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
- 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
Definitions
- the invention relates to a process for the joint production, from heavy petroleum fractions, middle distillates and bases of high viscosity oils, that is to say oils having viscosity indices (VI) of between 95 and 150 , and more particularly between 120 and 140.
- the fillers have boiling points above 380 ° C. These are for example vacuum distillates, deasphalted oils or their mixtures.
- FR-A- 2,077,334 describes another process for producing a lubricating oil with high viscosity index.
- this process allows a greater production of middle distillates while retaining similar oil characteristics.
- the Applicant has developed a flexible process, adaptable to various cuts, and allowing the operator to control the conversion and viscosity.
- the object of the invention is a process for treating heavy hydrocarbon petroleum fractions, with a higher boiling point of 380 ° C., for the improved production of middle distillates together with the production of oil bases having a viscosity index. between 95 and 150, process in which, in a first step , the cut is brought into contact, in the presence of hydrogen, with at least one catalyst containing on an amorphous support, at least one element of group VI and at least one element of group VIII, at a temperature between 350 and 430 ° C, under a pressure between 5 and 20 MPa, the space speed being between 0.1 and 5h -1 and the amount of hydrogen introduced such as the ratio hydrogen / hydrocarbon volume is between 150 to 2,000, said process being characterized in that the product resulting from said first step, which has a viscosity index between 90 and 130, is brought to contact in a second step, with at least one catalyst containing a support, at least with the element of group VI, at least one element with group VIII, the total amount of oxides of these elements
- the charge and the added hydrogen are brought into contact with a first catalyst.
- the amount of hydrogen supplied is such that the volume ratio H 2 / hydrocarbons is between 150 and 2,000 and preferably 500 and 1,500.
- the catalyst of the first stage essentially consists of a support which is not zeolitic and at least one metal or metal compound having a hydrodehydrogenating function.
- the support preferably consists essentially of (based on) alumina or silica amorphous alumina; it may also contain boron oxide, magnesia, zirconia, titanium oxide, clay, or a combination of these oxides.
- Function hydro-dehydrogenating agent is preferably filled with at least one metal or composed of metal of the molybdenum group, tungsten, nickel and cobalt.
- This catalyst may advantageously contain phosphorus; indeed he is known in the prior art that the compound provides two advantages to hydrotreatment catalysts : ease of preparation during the impregnation of nickel solutions and molybdenum, and better hydrogenation activity.
- NiMo catalysts on alumina NiMo on alumina doped with boron and / or phosphorus and NiMo on alumina silica are preferred.
- the total concentration of oxides of metals from groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of group VI on metal (or metals) of group VIII is between 20 and 1.25 and preferably between 10 and 2.
- the concentration of phosphorus oxide P 2 O 5 will be less than 15% by weight and preferably 10% by weight.
- this operation is carried out in this first step with temperatures between 350 and 430 ° C, and preferably between 370 and 410 ° C, with pressures between 5 and 20 MPa, and preferably 7 and 15 MPa, with space velocities between 0.1 and 5 h -1 , and preferably 0.3 and 1.5 h -1 .
- the operator will choose the temperature for this first stage by function of the viscosity index that it wishes to obtain on the oil base at the outlet of this step, which will preferably be between 90 and 120, and better between 90 and 110.
- the product obtained at the end of this first step is sent to a second catalyst in a second step.
- the effluent is sent in the second step without intermediate separation of ammonia and hydrogen sulfide. Such a separation may, in another embodiment of the method, be provided.
- the second stage catalyst essentially consists of a zeolite, a support and a hydro-dehydrogenating function.
- the hydro-dehydrogenating function consists of a combination of metals of groups VI (in particular molybdenum and / or tungsten) and metals of group VIII (cobalt and / or nickel in particular) of the periodic table of the elements.
- This catalyst may also advantageously contain phosphorus.
- the total concentration of metal oxides of GVIII and VI is between 8% and 40% by weight and preferably between 8 and 30% and advantageously between 10-40% and better still 10-30%.
- the weight ratio expressed as metal oxides between metal (or metals) of group VI over metal (or metals) of group VIII is between 20 and 1.25 and preferably between 10 and 2.
- the concentration of phosphorus oxide (P 2 O 5 ) will be less than 15% and preferably 10% by weight.
- the support is chosen from the group consisting of alumina, silica, silica alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, clay, alone or in mixtures.
- the zeolite content by weight is between 2 and 25% and preferably between 3 and 25% compared to the final catalyst.
- the zeolite can optionally be doped with metallic elements such as example the metals of the rare earth family, in particular lanthanum and cerium, or group VIII noble or non-noble metals, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals like manganese, zinc, magnesium.
- metallic elements such as example the metals of the rare earth family, in particular lanthanum and cerium, or group VIII noble or non-noble metals, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals like manganese, zinc, magnesium.
- An acidic HY zeolite is particularly advantageous and is characterized by different specifications: a SiO 2 / Al 2 O 3 molar ratio of between 12 and 40: a sodium content of less than 0.15% by weight determined on the zeolite calcined at 1100 ° C a crystalline parameter has elementary mesh between 24.55 x 10 -10 m and 24.24 x 10 -10 m and preferably between 24.38 x 10 -10 m and 24.26 x 10 -10 m ; a CNa capacity for taking up sodium ions, expressed in grams of Na per 100 grams of modified zeolite, neutralized then calcined, greater than approximately 0.85 a specific surface area determined by the BET method greater than approximately 400 m 2 / g and preferably greater than 550 m 2 / g, a water vapor adsorption capacity at 25 ° C for a partial pressure of 2.6 torrs (i.e.
- a porous distribution comprising between 1 and 20% and preferably between 3 and 15% of the pore volume contained in pores with a diameter between 20 x 10 -10 m and 80 x 10 -10 m, the rest of the pore volume being contained in pores with a smaller diameter at 20.10 -10 m.
- a preferred catalyst contains nickel, molybdenum, a Y zeolite such as previously defined and alumina.
- the pressure will be maintained between 5 and 20 MPa and preferably 7 to 15 MPa, the space speed will be between 0.1 h -1 and 5 h -1 and preferably between 0.3 and 1.5 h -1 .
- the temperature is adjusted on the second step, so as to obtain the desired viscosity and VI. It is between 350 and 430 ° C, and in general it is advantageously between 370 and 410 ° C, even 390 ° C.
- the Applicant has surprisingly found that the viscosity of the residue is less reduced than on amorphous catalysts for the same level of conversion.
- the product from the second stage is then fractionated so as to obtain, on the one hand, the middle distillates and on the other hand the residue containing the oil bases.
- the process is carried out without recirculation of the residue so as to avoid an accumulation of polyaromatic compounds.
- the process can nevertheless be implemented with recycling of part of the residue to level of the second stage.
- the recycled fraction is then mixed with the product from the first stage.
- a 12% Mo, 4% Ni, 10% zeolite Y catalyst is loaded into a second reactor located after this first reactor on alumina.
- the product from the first reactor is introduced into the second reactor.
- the pressure is 14 MPa and the product circulates at a space speed of 1 h -1 .
- the 380 ° C + residue is recovered and is then distilled under vacuum.
- Table 2 makes it possible to compare the process according to the invention with a one-step process on an amorphous catalyst, for the production of oils of high viscosity with high viscosity index (VI) (VI> 125) and of middle distillates to from vacuum distillate.
- a residue is released under deasphalted vacuum (the viscosity of which at 100 ° C. is generally between 25.10 - 4 to 90.10 -4 m 2 / s).
- the characteristics of the oil bases obtained from a residue of viscosity 50 10 -4 m 2 / s are given in Table II as a function of the temperature.
- the 380 ° C + residue is distilled so as to obtain the highly viscous "bright stock" oil (viscosity at 100 ° greater than or equal to 32.10 -4 m 2 / s).
- Example 3 The product from Example 3 is treated in the same way as in Example 2.
- the results are presented in Table II.
- Table II makes it possible to compare the process according to the invention with a one-step process on an amorphous catalyst, for the production of very viscous "brightstock” oils (viscosity ⁇ 32.10 -4 m 2 / s) and middle distillates to from deasphalted vacuum residue.
- distillation temperatures suitable allow these oils to be obtained very viscous.
- the quantities of middle distillates produced are established in a large range.
- Example 1 The product obtained at the end of Example 1 is passed through a second reactor containing a 15% Mo, 5% Ni and silica-alumina catalyst (48% alumina and 32% silica). The pressure is 14 MPa and the space speed 1 h -1 .
- the characteristics of the product obtained are given in Table I. This test, conducted under the conditions of US Pat. No. 3,642,612 of the prior art, shows that the invention described in the present application brings new and surprising results compared to the known technique.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Les charges présentent des points d'ébullition supérieurs à 380 °C. Ce sont par exemple des distillats sous vide, des huiles désasphaltées ou leurs mélanges.
La demanderesse a constaté de façon surprenante que la viscosité du résidu est moins abaissée que sur les catalyseurs amorphes pour un même niveau de conversion.
Les caractéristiques des huiles obtenues sont reportées dans le tableau 1 en fonction des températures.
Le produit issu du premier réacteur est introduit dans le second réacteur.
La pression est de 14 MPa et le produit circule à une vitesse spatiale de 1 h-1.
Le résidu 380 °C+ est récupéré puis est distillé sous vide.
Le tableau 2 permet de comparer le procédé selon l'invention avec un procédé à une seule étape sur catalyseur amorphe, pour la production d'huiles de haute viscosité à haut indice de viscosité (VI) (VI>125) et de distillats moyens à partir de distillat sous vide.
- Pour une conversion identique (68,7 %) l'huile obtenue avec le procédé selon l'invention a une viscosité plus élevée (5.10-4m2/s en lieu de 4,5.10-4 m2/s) et est de plus obtenue à des températures nettement inférieures.
Charge | Exemple 2 | Exemple 1 | Exemple 5 | ||||
Températures | |||||||
1ère étape | 390 °C | 390 °C | 390 °C | 410 °C | 395 °C | 395 °C | |
2e étape | 380 °C | 375 °C | 370 °C | - | - | 390 °C | |
Conversion % poids | 90 % | 80 % | 68,7 % | 68,7 % | 56,2 % | 68,7 % | |
Bilan matière (% poids) | |||||||
H2S + NH3 | 3,0 | 3,0 | 3,0 | 3,0 | 3,0 | 3,0 | |
C1-C4 | 4,1 | 3,6 | 2,5 | 3,6 | 2,4 | 3,5 | |
C5-150 | 26,9 | 21,8 | 15,7 | 13,5 | 9,6 | 13,0 | |
150-380 | 56,0 | 51,6 | 47,5 | 48,7 | 41,2 | 49,2 | |
380+ | 100 | 12,8 | 22,6 | 33,7 | 33,7 | 46,0 | 33,65 |
Total | 100 | 102,8 | 102,6 | 102,4 | 102,4 | 102,2 | 102,35 |
Résidu 380 déparaffiné | |||||||
d15/4 | 0,935 | ||||||
V100 °C (m2/s) | 9,5.10-4 | 3,6.10-4 | 4,5.10-4 | 5,0.10-4 | 4,5.10-4 | 5,0.10-4 | 4,5.10-4 |
VI | 50 | 132 | 133 | 125 | 134 | 125 | 133 |
Point d'écoulement (°C) | -18 | -18 | -18 | -18 | -18 | -18 | -18 |
- Une même base d'huile (viscosité 5,0.10-4 m2/s et VI = 125) est obtenue avec conjointement une production en distillats moyens nettement supérieure dans le procédé selon l'invention (47,5 % contre 41,2 %, soit un gain de plus de 15 %) ;
- L'augmentation du rendement de conversion dans le procédé selon l'invention ne se fait pas au détriment de la viscosité de la base d'huile déparaffinée : le rendement en distillats moyens peut augmenter de 10 % sans que la viscosité soit modifiée.
Les caractéristiques des bases d'huiles obtenues à partir d'un résidu de viscosité 50 10-4 m2/s sont données dans le tableau II en fonction de la température. Le résidu 380°C+ est distillé de façon à obtenir l'huile "bright stock" très visqueuse (viscosité à 100 ° supérieure ou égale à 32.10-4 m2/s).
Les résultats sont présentés dans le tableau II.
Le tableau II permet de comparer le procédé selon l'invention avec un procédé à une seule étape sur catalyseur amorphe, pour la production d'huiles très visqueuses "brightstock" (viscosité ≥ 32.10-4 m2/s) et de distillats moyens à partir de résidu sous vide désasphalté.
Ainsi le point de fumée des kérosènes obtenus dans les exemples 2 et 4 est supérieur à 25 mm, alors qu'il est de l'ordre de 20 dans les exemples 1 et 3.
La teneur en aromatiques des gasoils est inférieure à 10 % dans les exemples 2 et 4 alors qu'elle est de 20 % dans les exemples 1 et 3.
La pression est de 14 MPa et la vitesse spatiale de 1 h-1.
Les caractéristiques du produit obtenu sont données dans le tableau I.
Cet essai, mené dans les conditions du brevet US.3,642,612 de l'art antérieur, montre que l'invention décrite dans la présente demande apporte des résultats nouveaux et surprenants par rapport à la technique connue.
Claims (17)
- Procédé de traitement de coupes pétrolières lourdes hydrocarbonées à point d'ébullition supérieur à 380 °C, pour la production améliorée de distillats moyens conjointement à la production de bases huiles ayant un indice de viscosité compris entre 95 et 150, procédé dans lequel, dans une première étape, la coupe est mise au contact, en présence d'hydrogène, avec au moins un catalyseur contenant sur un support amorphe au moins un élément du groupe VI et au moins un élément du groupe VII à une température comprise entre 350 et 430 °C, sous une pression comprise entre 5 et 20 MPa, la vitesse spatiale horaire étant comprise entre 0,1 et 5 h-1 et la quantité d'hydrogène introduite telle que le rapport volumique hydrogène/hydrocarbures soit compris entre 150 et 2 000, ledit procédé étant caractérisé en ce que le produit issu de ladite première étape, qui présente un indice de viscosité entre 90 et 130, est mis au contact dans une seconde étape, avec au moins un catalyseur contenant un support, 2 à 25 % pds d'une zéolithe Y de rapport molaire silice/alumine de 12 à 70, et au moins un élément du groupe VI, au moins un élément du groupe VIII, la quantité totale en oxydes de ces éléments dans le catalyseur étant de 8-40 % pds, à une temperature comprise entre 350 et 430 °C, à une pression comprise entre 5 et 20 MPa, la vitesse spatiale horaire étant comprise entre 0,1 et 5 h-1, et que le produit issu de ladite seconde étape est fractionné en d'une part les distillats moyens et d'autre part le résidu contenant les bases huiles.
- Procédé selon la revendication 1, caractérisé en ce que les coupes lourdes sont choisies dans le groupe formé par les distillats sous vide, les huiles désasphaltées, leurs mélanges.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le support amorphe est choisi dans le groupe formé par l'alumine, la silice-alumine.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le support amorphe renferme au moins l'un des composés choisis dans le groupe formé par l'oxyde de bore, la magnésie, le zircone, l'oxyde de titane et l'argile.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le catalyseur de la première étape contient également du phosphore, à raison de moins de 15% en poids d'oxyde de phosphore.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le catalyseur de la première étape renferme au moins un métal du GVIII choisi parmi le nickel et le cobalt, et au moins un métal du GVI choisi parmi le molybdène et le tungstène.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que dans le catalyseur de la première étape, la concentration totale en oxydes de métaux des groupes VI et VIII est comprise entre 5 et 40% en poids et en ce que le rapport pondéral exprimé en oxyde métallique du GVI sur oxyde métallique de GVIII est compris entre 20 et 1,25.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que dans la première étape, la température est de 370 à 410°C, la pression de 7 à 15 MPa, la vitesse spatiale de 0,3 à 1,5 h-1 et le rapport volumique H2/hydrocarbures compris entre 500 et 1500.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le catalyseur de la seconde étape renferme au moins un métal du GVIII choisi parmi le nickel et le cobalt. et au moins un métal du GVI choisi parmi le molybdène et le tungstène.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le catalyseur de la seconde étape renferme également du phosphore.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que dans le catalyseur de la seconde étape, le rapport pondéral exprimé en oxyde métallique du GVI sur oxyde métallique du GVIII est compris entre 20 et 1,25.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que , pour le catalyseur de la seconde étape, le support est choisi dans le groupe constitué par l'alumine, la silice, la silice-alumine, l'alumine-oxyde de bore, la magnésie, la silice-magnésie, la zircone, l'oxyde de titane et l'argile, seuls ou en mélanges.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la zéolithe est dopée par des éléments métalliques choisis dans le groupe formé par les métaux de la famille des terres rares, les métaux du GVIII, le manganèse, le zinc et le magnésium.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la dans la seconde étape, la température est comprise entre 370 et 410°C, la pression entre 7 et 15 MPa et la vitesse spatiale entre 0,3 et 1,5 h-1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le rendement en produits à point d<ébullition d'au moins 380°C est d'au moins 12,8 % pds.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le catalyseur contient 3-25% pds de zéolite Y.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la zéolite Y présente un rapport molaire silice/alumine de 12 à 40.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9312856A FR2711667B1 (fr) | 1993-10-25 | 1993-10-25 | Procédé pour la production améliorée de distillats moyens conjointement à la production d'huiles ayant des indices de viscosité et des viscosités élevés, à partir de coupes pétrolières lourdes. |
FR9312856 | 1993-10-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0649896A1 EP0649896A1 (fr) | 1995-04-26 |
EP0649896B1 true EP0649896B1 (fr) | 2000-05-03 |
Family
ID=9452297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94402284A Revoked EP0649896B1 (fr) | 1993-10-25 | 1994-10-11 | Procédé pour la production conjointe de distillats moyens et d'huiles lubrifiantes à partir de coupes pétrolières lourdes |
Country Status (9)
Country | Link |
---|---|
US (1) | US5525209A (fr) |
EP (1) | EP0649896B1 (fr) |
JP (1) | JP3564581B2 (fr) |
KR (1) | KR100309488B1 (fr) |
CA (1) | CA2134281C (fr) |
DE (1) | DE69424247T2 (fr) |
ES (1) | ES2148297T3 (fr) |
FR (1) | FR2711667B1 (fr) |
RU (1) | RU2135549C1 (fr) |
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US8557106B2 (en) | 2010-09-30 | 2013-10-15 | Exxonmobil Research And Engineering Company | Hydrocracking process selective for improved distillate and improved lube yield and properties |
EP3018189A1 (fr) | 2014-11-04 | 2016-05-11 | IFP Energies nouvelles | Procede de conversion de charges petrolieres comprenant une etape de viscoreduction, une etape de maturation et une etape de separation des sediments pour la production de fiouls a basse teneur en sediments |
WO2016192893A1 (fr) | 2015-06-01 | 2016-12-08 | IFP Energies Nouvelles | Procédé de conversion de charges comprenant une étape de viscoréduction, une étape de précipitation et une étape de séparation des sédiments pour la production de fiouls |
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US5935416A (en) * | 1996-06-28 | 1999-08-10 | Exxon Research And Engineering Co. | Raffinate hydroconversion process |
US5935417A (en) * | 1996-12-17 | 1999-08-10 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
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FR2778343B1 (fr) * | 1998-05-06 | 2000-06-16 | Inst Francais Du Petrole | Catalyseur a base de zeolithe y non globalement desaluminee, de bore et/ou de silicium et procede d'hydrocraquage |
FR2778345B1 (fr) * | 1998-05-06 | 2000-11-24 | Inst Francais Du Petrole | Catalyseur a base de zeolithe y contenant du bore et/ou du silicium, utilisable en hydrocraquage |
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FR2808028B1 (fr) * | 2000-04-21 | 2003-09-05 | Inst Francais Du Petrole | Procede flexible de production de bases huiles avec une zeolithe zsm-48 |
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CA2833085A1 (fr) | 2011-04-21 | 2012-10-26 | Shell Internationale Research Maatschappij B.V. | Procede de conversion d'une biomasse solide |
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US20130118059A1 (en) | 2011-11-14 | 2013-05-16 | Shell Oil Company | Process for conversion of a cellulosic material |
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-
1993
- 1993-10-25 FR FR9312856A patent/FR2711667B1/fr not_active Expired - Lifetime
-
1994
- 1994-10-11 ES ES94402284T patent/ES2148297T3/es not_active Expired - Lifetime
- 1994-10-11 EP EP94402284A patent/EP0649896B1/fr not_active Revoked
- 1994-10-11 DE DE69424247T patent/DE69424247T2/de not_active Revoked
- 1994-10-24 US US08/330,820 patent/US5525209A/en not_active Expired - Lifetime
- 1994-10-24 KR KR1019940027109A patent/KR100309488B1/ko not_active IP Right Cessation
- 1994-10-24 RU RU94037956A patent/RU2135549C1/ru active
- 1994-10-25 JP JP26010594A patent/JP3564581B2/ja not_active Expired - Lifetime
- 1994-10-25 CA CA002134281A patent/CA2134281C/fr not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8557106B2 (en) | 2010-09-30 | 2013-10-15 | Exxonmobil Research And Engineering Company | Hydrocracking process selective for improved distillate and improved lube yield and properties |
US9487714B2 (en) | 2010-09-30 | 2016-11-08 | Exxonmobil Research And Engineering Company | Hydrocracking process selective for improved distillate and improved lube yield and properties |
EP3018189A1 (fr) | 2014-11-04 | 2016-05-11 | IFP Energies nouvelles | Procede de conversion de charges petrolieres comprenant une etape de viscoreduction, une etape de maturation et une etape de separation des sediments pour la production de fiouls a basse teneur en sediments |
WO2016192893A1 (fr) | 2015-06-01 | 2016-12-08 | IFP Energies Nouvelles | Procédé de conversion de charges comprenant une étape de viscoréduction, une étape de précipitation et une étape de séparation des sédiments pour la production de fiouls |
Also Published As
Publication number | Publication date |
---|---|
DE69424247T2 (de) | 2000-09-07 |
KR100309488B1 (ko) | 2001-12-28 |
DE69424247D1 (de) | 2000-06-08 |
JPH07179864A (ja) | 1995-07-18 |
FR2711667B1 (fr) | 1996-02-02 |
CA2134281C (fr) | 2005-08-02 |
ES2148297T3 (es) | 2000-10-16 |
CA2134281A1 (fr) | 1995-04-26 |
FR2711667A1 (fr) | 1995-05-05 |
JP3564581B2 (ja) | 2004-09-15 |
RU94037956A (ru) | 1996-09-10 |
RU2135549C1 (ru) | 1999-08-27 |
KR950011594A (ko) | 1995-05-15 |
US5525209A (en) | 1996-06-11 |
EP0649896A1 (fr) | 1995-04-26 |
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