WO2004033593A1 - Rendement accru en huile de graissage par deparaffinage catalytique de cire paraffinique sous pression d'hydrogene faible ou nulle - Google Patents

Rendement accru en huile de graissage par deparaffinage catalytique de cire paraffinique sous pression d'hydrogene faible ou nulle Download PDF

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Publication number
WO2004033593A1
WO2004033593A1 PCT/US2003/031742 US0331742W WO2004033593A1 WO 2004033593 A1 WO2004033593 A1 WO 2004033593A1 US 0331742 W US0331742 W US 0331742W WO 2004033593 A1 WO2004033593 A1 WO 2004033593A1
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Prior art keywords
catalyst
hydrogen
zsm
dewaxing
zone
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PCT/US2003/031742
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English (en)
Inventor
Zhaozhong Jiang
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Exxonmobil Research And Engineering Company
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Priority claimed from US10/266,342 external-priority patent/US20040065583A1/en
Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to BR0314938-2A priority Critical patent/BR0314938A/pt
Priority to CA002498888A priority patent/CA2498888A1/fr
Priority to AU2003279863A priority patent/AU2003279863A1/en
Priority to JP2005501108A priority patent/JP2006502304A/ja
Priority to EP03773186A priority patent/EP1558703A1/fr
Publication of WO2004033593A1 publication Critical patent/WO2004033593A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • This invention relates to a process of catalytically dewaxing paraffin containing hydrocarbons. More particularly, this invention relates to the production of lube base oils and diesel range oils with a pre-determined or preselected pour point or cloud point by catalytic dewaxing in the substantial absence of added hydrogen, at low or no hydrogen partial pressures.
  • Dewaxing of paraffin containing feeds serves to decrease their pour and cloud points, mainly by isomerization of n-paraffins. Hydrocracking, however, is generally undesired in a dewaxing process, because it leads to low boiling, low viscosity, low value products such as short chain hydrocarbons, e.g., Cj-to C 4 hydrocarbons.
  • Hydrogen has always been used in catalytic dewaxing mainly for promoting extended catalytic life by, e.g., reductive coke removal, see U.S. 4,872, 968.
  • Hydrogen partial pressures in catalytic dewaxing ranges from about 200 psig (1480 kPa) to about 1,000 psig (6996 kPa) or more, e.g., see U.S. 5,614,079, and hydrogen partial pressures are usually in the higher end of the range for reasons of catalyst life.
  • U.S. 5,362,378 discloses hydrogen partial pressures ranging from 72 to 2,305 psig (598 to 15994 kPa) for use with the large pore catalyst zeolite beta.
  • This patent does not mention catalyst life or TIR, i.e., temperature increase required, necessary for maintaining product specifications, such as pour point or cloud point.
  • Large pore zeolite beta is typically not classified as a dewaxing catalyst, but as an isomerization catalyst, and products produced utilizing such catalysts in accordance with U.S. Patent 5,362,378 would need to be dewaxed in order to achieve the low pour and cloud points obtained from the instant process.
  • the invention relates to a catalytic dewaxing process which comprises reacting a paraffin containing feed stock over a catalyst comprising a molecular sieve with a one dimensional pore structure having an average diameter of 0.50 to 0.65 nm, and a metal dehydrogenation component, at dewaxing reaction conditions and in the substantial absence of added hydrogen.
  • a paraffin containing feed preferably a feed containing at least 80 wt n-paraffins
  • a molecular sieve catalyst with one dimensional pore structures having an average diameter of 0.50 nm to 0.65 nm, and the difference between the maximum, diameter and the minimum diameter is preferably ⁇ 0.05 nm.
  • the molecular sieve is exemplified by, for example, ZSM-23, ZSM-35, ZSM-48, ZSM-22, SSZ-32, zeolite beta, mordenite and rare earth ion exchanged ferrierite in conjunction with a dehydrogenation component.
  • the molecular sieve catalyst is ZSM-48 (ZSM-48 zeolites herein include EU-2, EU-11 and ZBM 30 which are structurally equivalent to ZSM-48) with a dehydrogenation component; and the process is carried out in the substantial absence of added hydrogen.
  • ZSM-48 zeolites herein include EU-2, EU-11 and ZBM 30 which are structurally equivalent to ZSM-48
  • the amount of inherent hydrogen in the paraffin containing feed is the amount that is present in a Fischer Tropsch hydrocarbon fraction. Such fraction is usually obtained by distillation, which distillation substantially removes dissolved gasses, and the amount of inherent hydrogen in the paraffin containing feeds is then the amount which is physically adsorbed by the liquid or waxy Fischer Tropsch hydrocarbon fraction.
  • the hydrogen partial pressure is preferably less than 100 psig (791 kPa), more preferably less than 70 psig (584 kPa).
  • the catalyst is stable, that is, it can meet a predetermined pour point for at least two weeks.
  • a cyclic process wherein catalytic dewaxing occurs in a first zone while in a second zone catalyst is regenerated or rejuvenated, after which the feed is switched to the second zone where catalyst has been regenerated and the catalyst in the first zone is regenerated.
  • a continuous catalytic dewaxing process may be provided.
  • Figure 1 is a schematic of a cyclic isomerization - catalyst regeneration process.
  • Figure 2 is a plot showing the effect of hydrogen pressure on lube yield for isomerization of a Fischer-Tropsch wax over Pt/ZSM-48. Pour point (°C) is on the abscissa and wt% on feed 700°F+ (371.1°C+) lube yield is on the ordinate.
  • the lines A, B, C, and D denote the results of processes that were run with varying amounts of added hydrogen, i.e., hydrogen partial pressures of 1000 psig (6996 kPa), 500 psig (3549 kPa), 300 psig (2170 kPa), and 0 psia (0 kPa, no (added) hydrogen), respectively.
  • Figure 3 is a plot showing the effect of hydrogen pressure on gas yield for isomerizing a Fischer-Tropsch wax over Pt/ZSM-48.
  • 700°F+ (371.1°C+) lube pour point (°C ) is on the abscissa and is plotted against wt% on feed C C 4 gas yield on the ordinate.
  • Lines A, B, C, and D denote the results of processes that were run with varying amounts of added hydrogen, i.e. hydrogen partial pressures of 1000 psig (6996 kPa), 500 psig (3549 kPa), 300 psig (2170 kPa), and 0 psia (0 kPa, no (added) hydrogen), respectively.
  • Figure 4 is a plot showing the effect of hydrogen pressure on lube viscosity for isomerization of a Fischer-Tropsch wax over Pt/ZSM-48. Pour point (°C) on the abscissa is plotted against kinematic viscosity @ 100°C in centistokes (cSt) on the ordinate. Lines A, B, and C denote 0 psia, 500 psig (3549 kPa), and 1000 psig (6996 kPa), respectively.
  • Figure 5 is a plot showing the effect of hydrogen pressure on lube viscosity index for isomerization of a Fischer-Tropsch wax over Pt/ZSM-48.
  • Pour point (°C) on the abscissa is plotted against 700°F+ (371.1°C+) lube viscosity index (VI) on the ordinate.
  • the dots represent 1000 psig (6996 kPa) hydrogen, the x's represent 500 psig hydrogen (3549 kPa), the filled triangles represent 300 psig (2170 kPa) hydrogen, and the open diamond represents 0 psia hydrogen (0 kPa, no hydrogen).
  • line 10 indicates a source of paraffin feed.
  • the feed is derived from a Fischer-Tropsch hydrocarbon synthesis process, particularly one that is operated in a non-shifting mode with a cobalt or ruthenium based catalyst, preferably a cobalt containing catalyst.
  • the feed is forwarded to first catalytic dewaxing zone 16 via open valve 12 and line 13.
  • Hydrogen to the extent desired, is fed through line 25.
  • a source of an oxygen containing gas i.e., oxygen, air, oxygen enriched air or oxygen in suitable proportion with inerts such as nitrogen, from source 30, is fed to a second zone 18 via open valve 32 and line 34 where deactivated catalytic dewaxing catalyst is regenerated. Regeneration off gases are removed through open valve 24 and line 26.
  • the catalytically dewaxed product from zone 16 is removed via open valve 44 through lines 40 and 48 to distillation zone 50 where products are recovered, e.g., diesel in line 52 and lube base stock in line 54.
  • valves 12 and 44 are closed, oxygen from source 30 is fed to zone 16 via open valve 38 and line 36. Regeneration off gases are removed through open valve 20 and line 22.
  • zone 16 when zone 16 is being regenerated, valve 12 is closed and paraffin feed is delivered to zone 18 for catalytic dewaxing via open valve 14 and line 15. Hydrogen to the extent desired is fed through line 27. Product is recovered in line 42 and fed via open valve 46 and line 48 to distillation zone 50.
  • Catalytic dewaxing of paraffin containing feeds is accomplished at relatively low hydrogen partial pressures without substantial effect on the life of a ZSM-48 catalyst.
  • the dewaxing process is essentially an isomerization process in which some hydrogen will be produced indigenously.
  • the feed that is employed in this invention is a paraffin containing feed, preferably a feed that contains greater than 80 wt% n-paraffins, more preferably greater than 90 wt% n-paraffins, still more preferably greater than 95 wt% n-paraffins and still more preferably 98 wt % n-paraffins.
  • the feed generally boils in the range 430°F+ (221.1°C+), preferably 450°F+ (232.2°C+), more preferably 450-1200°F (232.2-648.9°C) (minor amounts, e.g., less than about 10% of 1200°F+, or 648.9°C+, material may be present).
  • the feed is preferably low in unsaturates, that is, low in both aromatics and olefins.
  • the unsaturates level is less than 10 wt%, preferably less than 5 wt%, more preferably less than 2 wt%.
  • the feed is relatively low in nitrogen and sulfur, e.g., less than 200 ppm, preferably less than 100 ppm, such as less than 50 wppm of each. Where a Fischer-Tropsch derived feed is employed, there is no need to pre-sulfide the catalyst, and indeed, pre- sulfiding should be avoided.
  • the feed is the product of a Fischer-Tropsch reaction that produces essentially n-paraffins, and still more preferably the Fischer- Tropsch process is conducted with a non-shifting catalyst, e.g., cobalt or ruthenium, preferably a cobalt containing catalyst.
  • a non-shifting catalyst e.g., cobalt or ruthenium, preferably a cobalt containing catalyst.
  • the catalyst employed in the catalytic dewaxing step comprises a molecular sieve with one dimensional pore structure and a metal dehydrogenation component.
  • the molecular sieves include such as ZSM-23, ZSM-35, ZSM-22, SSZ-32, zeolite beta, mordenite and rare earth ion exchanged ferrierite, preferably a ZSM-48 catalyst, containing a metal dehydrogenation functionality, preferably supplied by the presence of platinum or palladium or both platinum and palladium, more preferably platinum.
  • the catalyst may be sulfided or unsulfided and is preferably unsulfided when sulfur can negatively interfere with associated processes, such as a Fischer-Tropsch process.
  • ZSM-48 is characterized by the X-ray diffraction pattern shown in Table 1 below.
  • the material is further characterized by the fact that it exhibits a single line within the range of 11.8 ⁇ 0.2 Angstrom units, i.e., (11.8 ⁇ 0.2) x 10 "10 m.
  • the presence of a single line at the indicated spacing structurally distinguishes ZSM-48 from closely related materials such as ZSM-12 (described in U.S. Patent No.
  • ZSM-48 an methods for its preparation are described in U.S. Patent Nos. 4,375,573; 4,397,827; 4,448,675; 4,423,021 ; and 5,075,269.
  • the method of preparation described in U.S. Patent No. 5,075,269 is particularly preferred, and is incorporated herein by reference. This method is for preparing a catalyst particularly suitable for the catalytic dewaxing process.
  • the zeolite, ZSM-48, and other utilizable zeolites such as ZSM-23, ZSM-35, ZSM-22, SSZ-32, zeolite beta, mordenite and rare earth ion exchanged ferrierite, are usually employed with a dehydrogenation component in an amount of about 0.01 to 5.0 wt%, the component being manganese, tungsten, vanadium, zinc, chromium, molybdenum, rhenium, Group VIII metals such as nickel, cobalt, or the noble metals platinum and palladium.
  • the noble metals are preferred components.
  • Such component can be exchanged into the composition, impregnated thereon, or physically intimately admixed therewith.
  • Such component can be impregnated in or onto the zeolite such as, for example, in the case of platinum, by treating the zeolite with a platinum metal-containing ion.
  • suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum tetra-ammonia complex. Platinum and palladium are preferred hydrogenation components.
  • the compounds of the useful platinum or other metals can be divided into compounds in which the metal is present in the cation of the compound and compounds in which it is present in the anion of the compound. Both types of compounds which contain the metal in the ionic state can be used.
  • the ZSM-48 catalyst Prior to its use, the ZSM-48 catalyst should be dehydrated at least partially. This can be done by heating to a temperature in the range of from about 100°C to about 600°C in an inert atmosphere, such as air, nitrogen, etc., and at atmospheric or subatmospheric pressures for between 1 and 48 hours. Dehydration can also be performed at lower temperature merely by placing the catalyst in a vacuum, but a longer time is required to obtain sufficient amount of dehydration. ZSM-48 is formed in a wide variety of particle sizes.
  • the particles can be in the form of a powder, a granule, or a molded product, such as extrudate having a particle size sufficient to pass through a 2 mesh (Tyler) screen (10 mm pore size) and be retained on a 400 mesh (Tyler) screen (0.038 mm pore size).
  • the crystalline silicate can be extruded before drying, or dried or partially dried and then extruded.
  • the ZSM-48 may be desired to incorporate the ZSM-48 with a matrix material which is resistant to the temperatures and other conditions employed in the dewaxing process herein.
  • matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with the ZSM-48, i.e., combined therewith, which is active, may enhance the conversion and/or selectivity of the catalyst herein.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • crystalline silicate materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength since in a petroleum refinery the catalyst is often subject to rough handling which tends to break the catalyst down into powder-like materials which cause problems in processing.
  • Naturally occurring clays which can be composited with ZSM-48 include the montmorillonite and kaolin families which include the sub- bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • ZSM-48 can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica- zirconia, silica- thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina- magnesia and silica-magnesia-zirconia.
  • the matrix can be in the form of a cogel. Mixtures of these components can also be used.
  • reaction conditions for dewaxing may vary widely even when the hydrogen partial pressures are maintained at low levels, e.g., 0 psig hydrogen.
  • start of run temperatures may vary between about 550-650°F (288-343°C).
  • End of run conditions can be defined by the nature of the product being produced, for example, when color specifications can no longer be met (an indication of catalyst deactivation), or when the pre-determined pour point can no longer be obtained, or the selectivity to isomerization is reduced as evidenced by an increase in methane yield due to hydrocracking.
  • end of run temperatures should be less than about 800°F (427°C), preferably less than about 750°F (399°C), more preferably less than about 725°F (385°C).
  • Catalyst deactivation is believed to be a result of coke formation on the surface of the catalyst, the coke covering or blocking access to the catalytic metal, as well as blocking the pores of the zeolite.
  • the catalyst may be regenerated by known methods including hot hydrogen stripping, coke removal by oxygen treatment or a combination of hydrogen stripping and oxygen treatment.
  • Figure 1 illustrates a process where oxygen treatment is used to regenerate the catalyst).
  • hydrogen stripping can be carried out with hydrogen or a mixture of hydrogen and an inert gas such as nitrogen, at isomerization reaction temperatures for a period of time sufficient to allow the catalyst to regain at least about 80%, preferably at least about 90% of its original lined out activity.
  • Oxygen treatment can be carried out at calcining conditions, e.g., using air at temperatures from about 500°C to 650°C, again for a period of time sufficient to allow the catalyst to regain at least about 80%, preferably at least about 90% of initial lined out activity after subsequent reduction.
  • other gases may be present, too, and will not interfere with the reaction.
  • Such other gases may be nitrogen, methane, or other light hydrocarbons (that may be produced during the reaction).
  • Total pressure may range up to 2000 psia (13790 kPa), preferably 100-2000 psia (690-13790 kPa), more preferably 150-1000 psia (1034-6895 kPa), still more preferably 150-500 psia (1034-3448 kPa).
  • Hydrogen can make up 50-100% of total gas, preferably 70-100%, more preferably 70-90%.
  • small amounts of olefins and aromatics may form when the isomerilzation is carried out in the substantial absence of hydrogen; and hydrofinishing, at well known conditions, may be necessary to remove these components.
  • the liquid hourly space velocity is generally between about 0.1 and about 10, and preferably is generally between about 0.5 and 4 volume of feed per volume of catalyst per hour.
  • the hydrogen to feed (where hydrogen is used) ratio is generally between about 100 (17.8 liter/liter) and about 10,000 (1781 liter/liter), and preferably between about 800 (142.5 liter/liter) and about 4,000 (712.4 liter/liter) standard cubic feet (scf) of hydrogen per barrel of fuel.
  • the Alpha Value of the catalyst prior to metal loading is preferably in the range of about 10 to about 50.
  • a Fischer-Tropsch wax having the properties shown in Table 2 below was used as feedstock for all isomerization reactions.
  • Wax isomerization was performed using a micro unit equipped with a three zone furnace and a downflow trickle bed tubular reactor (0.5 inch ID). The unit was heat traced to avoid freezing of the high melting point feed wax.
  • the catalyst extrudates were crushed and sized to 60-80 mesh (0.180-0.250 mm).
  • the reactor was loaded with a mixture of 15cc sized catalyst and 5cc of 80-120 mesh (0.125-0.180 mm) sand, which was then dried and reduced at 400°F (204.4°C) for one hour at one atmosphere, 240 cc/min hydrogen flow. Isomerization was conducted at 1.0 hr "1 LHSV and at pressures indicated.
  • TLP's were distilled into IBP-330°F (initial boiling point- 165.6°C) naphtha, 330-700°F ( 165.6-371.1 °C) distillate, and 700°F+ (371.1°C+) lube fractions.
  • the lube fractions were analyzed further by simulated distillation (simdis) to ensure accuracy of the actual distillation operations.
  • Pour point and cloud point of 700°F+ (371.1°C) lubes were measured using D97 and D2500 methods, respectively; viscosities were determined at both 40°C and 100°C according to D 445-3 and D 445-5 methods, respectively.
  • Lube base stock viscosity at a given, or pre-de termined, pour point was higher, too, at lower hydrogen pressure, and reached a maximum with no hydrogen as co-feed; i.e., 0 kPa (zero psia) hydrogen.
  • 0 kPa zero psia
  • the 700°F+ (371.1°C+) lube base stock obtained without co-feeding hydrogen had a KV at 100°C of 7.7 cSt which is significantly higher than the 6.7 cSt base stock obtained with a 1000 psig (6996 kPa) hydrogen pressure, as shown in Figure 4.
  • the viscosity of the feed is better preserved, while at the same time the pour and cloud point is decreased.
  • Viscosity and viscosity index are two key properties of lube base stocks.
  • Figure 5 shows that lowering hydrogen partial pressure, even to 0 psia (0 kPa), essentially had no effect on viscosity index of the lube base stocks.
  • Table 3 shows the results of isomerizing a Fischer-Tropsch wax, i.e., catalytic dewaxing in the substantial absence of added hydrogen. "MB” refers to material balance. TBP x% indicates a final boiling temperature, at which x wt% light fraction of a hydrocarbon sample boils.

Abstract

Cette invention concerne un déparaffinage catalytique de charges renfermant de la paraffine et présentant une certaine structure des pores. Ce déparaffinage des charges, qui sont de préférence produites à partir de gaz de synthèse au moyen d'un catalyseur Fischer-Tropsch non suractivé, se fait sans adjonction sensible d'hydrogène. Est décrit un processus cyclique d'isomérisation/régénération du catalyseur.
PCT/US2003/031742 2002-10-08 2003-10-07 Rendement accru en huile de graissage par deparaffinage catalytique de cire paraffinique sous pression d'hydrogene faible ou nulle WO2004033593A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR0314938-2A BR0314938A (pt) 2002-10-08 2003-10-07 Processo de desparafinação catalìtica, e, uso do mesmo
CA002498888A CA2498888A1 (fr) 2002-10-08 2003-10-07 Rendement accru en huile de graissage par deparaffinage catalytique de cire paraffinique sous pression d'hydrogene faible ou nulle
AU2003279863A AU2003279863A1 (en) 2002-10-08 2003-10-07 Enhanced lube oil yield by low or no hydrogen partial pressure catalytic dewaxing of paraffin wax
JP2005501108A JP2006502304A (ja) 2002-10-08 2003-10-07 パラフィンワックスを低またはゼロ水素分圧で接触脱ロウすることによる潤滑油収率の増大
EP03773186A EP1558703A1 (fr) 2002-10-08 2003-10-07 Rendement accru en huile de graissage par deparaffinage catalytique de cire paraffinique sous pression d'hydrogene faible ou nulle

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/266,342 2002-10-08
US10/266,342 US20040065583A1 (en) 2002-10-08 2002-10-08 Enhanced lube oil yield by low or no hydrogen partial pressure catalytic dewaxing of paraffin wax
US10/652,345 US20040065586A1 (en) 2002-10-08 2003-08-29 Enhanced lube oil yield by low or no hydrogen partial pressure catalytic dewaxing of paraffin wax
US10/652,345 2003-08-29

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WO2006011988A1 (fr) * 2004-06-25 2006-02-02 Exxonmobil Research And Engineering Company Processus dans une usine integree permettant de produire des huiles de base a haut poids moleculaire a partir de cire de fischer-tropsch
GB2416774B (en) * 2003-05-12 2008-08-13 Chevron Usa Inc Process for upgrading fischer-tropsch products using dewaxing and hydrofinishing
CN101768466A (zh) * 2004-07-22 2010-07-07 雪佛龙美国公司 生产白油的方法
US7815789B2 (en) 2003-06-23 2010-10-19 Shell Oil Company Process to prepare a lubricating base oil
EP2248585A1 (fr) * 2008-02-08 2010-11-10 JX Nippon Oil & Energy Corporation Catalyseur d'hydroisomérisation, son procédé de fabrication, procédé de déparaffinage d'une huile hydrocarbonée et procédé de fabrication d'une huile de base lubrifiante

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US8747656B2 (en) * 2008-10-10 2014-06-10 Velocys, Inc. Process and apparatus employing microchannel process technology

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US7815789B2 (en) 2003-06-23 2010-10-19 Shell Oil Company Process to prepare a lubricating base oil
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EP2248585A4 (fr) * 2008-02-08 2011-08-17 Jx Nippon Oil & Energy Corp Catalyseur d'hydroisomérisation, son procédé de fabrication, procédé de déparaffinage d'une huile hydrocarbonée et procédé de fabrication d'une huile de base lubrifiante
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AU2003279863A1 (en) 2004-05-04
CA2498888A1 (fr) 2004-04-22

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