EP1556463A1 - Lube hydroisomerization system - Google Patents
Lube hydroisomerization systemInfo
- Publication number
- EP1556463A1 EP1556463A1 EP03770719A EP03770719A EP1556463A1 EP 1556463 A1 EP1556463 A1 EP 1556463A1 EP 03770719 A EP03770719 A EP 03770719A EP 03770719 A EP03770719 A EP 03770719A EP 1556463 A1 EP1556463 A1 EP 1556463A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- wax
- beta
- lube
- zsm
- 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.)
- Withdrawn
Links
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
- C10G45/58—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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- the present invention relates to a process for converting waxy feeds to lube basestocks with a reduced viscosity.
- a typical process is a two-stage process that hydroisomenzes wax to a waxy isoparaffms mixture in the first step, followed by either solvent dewaxing or catalytic dewaxing the waxy isoparaffms mixture in the second step to remove residual wax and achieve a target lube pour point.
- hydroisomerization catalysts disclosed previously such as Pt supported on amorphous aluminosilicate or Zeolite Beta (Beta), normally possess large pores that allow the formation of branch structures during paraffin isomerization.
- examples of other large pore molecular sieves include ZSM-3, ZSM-12, ZSM-20, MCM-37, MCM-68, ECR-5, SAPO-5, SAPO-37 and USY.
- these large pore catalysts are not selective enough to preferentially convert normal and lightly branched paraffin waxes in the presence of multi-branched isoparaffin molecules.
- the isoparaffin products derived from wax often contain residual wax that needs to be dewaxed in order to meet target lube cloud points or pour points.
- the cloud point of a lube is the temperature at which the first trace of wax starts to separate, causing the lube to become turbid or cloudy (e.g., ASTM D2500).
- the pour point of a lube is the temperature at which lube and wax crystallize together as a whole and will not flow when poured (e.g., ASTM D97).
- Dewaxing can be achieved by additionally using either a solvent dewaxing process or a catalytic dewaxing process.
- the present invention relates to a process for converting wax to high quality lube basestocks by contacting the wax with a unidimensional molecular sieve catalyst with a near circular pore structure having an average diameter of 0.50 nm to 0.65 nm wherein the difference between the maximum diameter and the minimum is ⁇ 0.05 nm (e.g., ZSM-48) followed by a second molecular sieve catalyst (e.g., Zeolite Beta).
- Both catalysts comprise one or more Group VlII metals (i.e., Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Ni).
- Figure 1 is a plot of lube yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- Figure 2 is a plot of lube viscosity versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- Figure 3 is a plot of viscosity index (VI) versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- Figure 4 is a plot of light gas yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- Figure 5 is a plot of naphtha yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- Figure 6 is a plot of diesel yield versus lube pour point for isomerization of C80 wax over Pt/ZSM-48 followed by Pt/Beta, and standalone Pt/ZSM-48 catalyst systems.
- the invention provides high isomerization and dewaxing selectivity of a wax. over an unidimensional catalyst with a near circular pore structure having an average pore diameter of 0.50-0.65 nm (5.0-6.5 angstroms) wherein the maximum diameter - minimum diameter ⁇ 0.05 nm (0.5 angstroms), followed by a molecular sieve catalyst to form a lubricant.
- Group VIII metals on the two catalysts are preferred and platinum is the most preferred.
- the invention improves lube basestock products and their properties (e.g., pour point, cloud point).
- This method effectively reduces average lube molecular weight and potentially reduces lube product cloud point without sacrificing lube yield.
- This process allows improved use of the heavy end of lubes and is especially suited for waxes with 1,000°F+ fractions and preferably 1,100°F+ fractions. These fractions may comprise the higher molecular weight or boiling point tail of the feeds. It would be difficult to create enough branches with minimal cracking for very large molecular weight feeds if only one of the above catalysts was used.
- This invention is preferably used for processing heavy lube or lubes with a heavy component (e.g., with >5 wt% heavy raffinate) where the Beta catalyst selectively cracks the heavy end.
- a heavy component e.g., with >5 wt% heavy raffinate
- This invention can give a lighter lube with yields similar to those obtained over ZSM-48 alone.
- wax feed is first passed over a ZSM-48 catalyst.
- the resulting intermediate product is then passed over a single Zeolite Beta catalyst to form the final lube.
- These first and second stages can be separated or preferably are integrated process steps (e.g., cascaded).
- the unidimensional molecular sieve catalyst with near-circular pore structures does most of the dewaxing.
- the pores are smaller than in large pore molecular sieves thereby excluding bulkier (e.g., highly branched) molecules.
- Unidimensional means that the pores are essentially parallel to each other.
- the pores of the catalyst have an average diameter of 0.50 nm to 0.65 nm wherein the difference between a minimum diameter and a maximum diameter is ⁇ 0.05 nm.
- the pores may not always have a perfect circular or elliptical cross-section.
- the minimum diameter and maximum diameter are generally only measurements of an ellipse of a cross-sectional area equal to the cross-sectional area of an average pore.
- the pores can alternatively be defined by finding the center of the pore cross-section and using half of the minimum diameter and half of the maximum diameter to sweep an average cross- sectional pore shape from the center.
- the preferred unidimensional molecular sieve catalyst is an intermediate pore molecular sieve catalyst of which the preferred version is ZSM-48.
- U.S. Patent 5,075,269 describes the procedures for making ZSM-48 and is incorporated by reference herein.
- ZSM-48 is roughly 65% zeolite crystal and 35% alumina. Of the crystals, at least 90%, preferably at least 95%, and most preferably 98-99% are ideal crystals.
- the ZSM-48 is preferably in the protonated form though some sodium is acceptable.
- ZSM-48 is more robust than other catalysts with similar functions and helps to protect the second catalyst (e.g., Zeolite Beta).
- the unidimensional intermediate pore molecular sieve catalyst (e.g., Pt/ZSM-48) is preferably kept at 500-800°F (260-427°C), more preferably at 600-700°F (316-371°C), and most preferably at 630-660°F (332-349°C).
- ZSM-48 catalysts used in the invention preferably have an Alpha value of about 10 to about 50 prior to the Group VIII metal loading.
- Zeolite Beta catalysts are 12 ring acidic silica/alumina zeolites with or without boron (replacing some of the aluminum atoms).
- Zeolite Y USY
- Pre-sulfided Zeolite Beta is preferred when some residual sulfur in the product is acceptable.
- Zeolite Betas used in the invention preferably have an Alpha value below 15, more preferably below 10, at least prior to metal loading.
- Alpha is an acidity metric that is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst.
- Alpha is a relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time).
- Alpha is based on the activity of the highly active silica-alumina cracking catalyst taken as an Alpha of 1 in U.S. Patent 3,354,078 (incorporated by reference) and measured at 538°C as described in the Journal of Catalysis, vol. 4, p. 527 (1965); vol. 6, p. 278 (1966); and vol. 61, p. 395 (1980). Feeds with minimal nitrogen content will require low Alpha value of this catalyst.
- catalysts with high Alpha values are used for less selective cracking. Alpha values may be reduced by steaming.
- the Beta catalyst when contacting the intermediate product, is most preferably kept at temperatures of 400-700°F (204-371°C), more preferably at 500-650°F (260-343°C), and most preferably at 520-580°F (271-304°C).
- each catalyst is preferably controlled independently. Temperature choice partly depends on the feed liquid hourly space velocity of which 0.1-20 h “1 is preferred, 0.5-5 h “1 is more preferred, and 0.5-2 h "1 is most preferred.
- the contact time for both catalysts is preferably similar to each other. It is understood that the space velocity can be different.
- the pressure for both catalysts is preferably similar to each other. Hydrogen co-feed flow rate is 100-10,000 scf/bbl (17.8-1,780 n.L.L "1 ), more preferably 1,000-6,000 scf/bbl (178-1,068 n.L.L -1 ), and most preferably 1,500-3,000 scfTbbl (267-534 n.L.L '1 ).
- Each catalyst comprises 0.01-5 wt% of at least one Group VIII metal (i.e., Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Ni). Platinum and palladium are most preferred. Platinum or palladium blended with each other or other group VIII metals follow in preference. Nickel may also be blended with group VIII precious metals and is included in the scope of the invention whenever group VIII blends, alloys, or mixtures are mentioned. Platinum is the most preferred metal. Preferred metal loading on both catalysts are 0.1-1 wt% with approximately 0.6 wt% most preferred.
- the feed preferably is a wax with a melting point over 50°C, less than 7,000 ppm sulfur, and less than 50 ppm nitrogen.
- the nitrogen is more preferably less than 10 ppm nitrogen if hydrogen pressure is below 500 psig (34 arm).
- a heavy raffinate can be blended with a Fischer- Tropsch wax or similar clean waxy feed (e.g., to lower sulfur and/or nitrogen levels).
- the feed is converted by the first catalyst to form an intermediate product which is then preferably passed directly from the first catalyst to the second catalyst.
- a cascaded two- bed catalyst system consisting of a first bed catalyst followed by a second bed catalyst allows a highly selective process for wax isomerization and lube hydrodewaxing with minimal gas formation.
- the intermediate product preferably directly passes from the first bed to the second bed without inter-stage removal of light products.
- light byproducts e.g., methane, ethane
- More branching in feeds facilitates the present invention and improves final lube yield.
- U.S. Patent 6,090,989 describes typical branching indices and is incorporated by reference.
- the feed is preferably mixed with hydrogen and preheated before contacting it with the first catalyst.
- Preferably, at least 95% of the wax is in liquid form before contacting it with the first catalyst.
- the preferred measurements are described in this paragraph. Where there are two values, the value in parenthesis is approximate metric conversion of the first value.
- the weight percent of paraffins may be measured by high-resolution ⁇ H-NMR, for example, by the method described in ASTM standard D5292, in combination with GC-MS. This approach may also be used to determine the weight percentage of unsaturates, alcohols, oxygenates, and other organic components.
- the iso- to normal-paraffin ratio may be measured by performing gas chromatography (GC) or GC-MS in combination with l ⁇ C-NMR.
- Sulfur may be measured by XRF (X-Ray Fluorescence), as described, for example, in ASTM standard D2622.
- Nitrogen may be measured by syringe/inlet oxidative combustion with chemiluminescence detection, for example, by the method described in ASTM standard D4629. Aromatics may be measured as described below. As taught by the specification, olefins may be measured by using a Bromine index determined by coulimetric analysis, for example, by using ASTM standard D2710. The weight percent of total oxygen may be measured by neutron activation in combination with high-resolution ⁇ H-NMR. If necessary, the total oxygen content may be placed on a water-free basis by measuring water content.
- samples having a water content known to be less than about 200 ppm by weight may use known derivitization methods (e.g., by using calcium carbide to form acetylene) followed by GC-MS.
- samples having a water content known to be greater than about 200 ppm by weight one may use the Karl-Fischer method, for example, by the method described in ASTM standard D4928.
- the total alcohol content may be determined by high-resolution iH-NMR, and the percentage present primarily as C ⁇ 2-C24 primary alcohols may be determined by GC-MS. Cetane number may be determined by using, for example, ASTM standard D613.
- the level of aromatics may be determined by using high-resolution ⁇ H-NMR, for example, by using ASTM standard D5292. Dioxygenates are measured by using infrared (IR) absorbance spectroscopy. Branching characteristics of iso-paraffins may be measured by a combination of high-resolution l ⁇ C-NMR and GC with high- resolution MS.
- IR infrared
- a cascaded two-bed catalyst system consisting of a first stage Pt/ZSM-48 catalyst immediately followed by a second stage of Pt/Beta catalyst is shown to be highly active and selective for hydroisomerization and dewaxing of waxes with high molecular weight components.
- TBP x% indicates temperature below which x wt% of hydrocarbon samples boils.
- Time on stream (TOS) is the time during which the feed contacts the catalyst. IBP is initial boiling point. TBP is terminal boiling point.
- SCF/bbl standard cubic feed of hydrogen per barrel of feed
- n.1.1 "1 . or n.L.L "1 or n.L (gas) / L (feed) LHSV is defined as liquid hourly space velocity.
- WHSV is defined as weight hourly space velocity.
- a mild (e.g., 500-630°F (260-332°C)) Pt/Beta temperature should be employed during lube hydroprocessing.
- the mild Pt/Beta temperature should be employed with varying Pt/ZSM-48 temperature to achieve a target lube pour point.
- low operating pressure ⁇ 2,000 psi (272 arm) hydrogen pressure
- Stand-alone Pt/ZSM-48 was also evaluated for isomerizing and dewaxing C80 wax to 700°F+ (371°C+) lube basestocks (Tables 2). Comparison of lube yields for the two catalyst systems is illustrated in Figure 1. Figure 1 shows that the cascaded Pt/ZSM-48 followed by Pt/Beta gave essentially identical lube yields compared to Pt/ZSM-48 alone. The addition of Pt/Beta had minimal effects on the range of Pt/ZSM-48 operating temperature , (Tables '1 and 2).
- Figure 3 shows high viscosity indices observed for the Pt/ZSM-48- Pt/Beta wax isomerates, although they are slightly lower than those of Pt/ZSM-48 isomerates.
- a viscosity index of at least 150 at a -20°C lube pour point and a viscosity index of at least 130 at a pour point of no more than -50°C is preferred.
- the hydrotreated SASOLTM PARAFLINTTM C80 wax (C80) feed was obtained from Moore and Munger, Inc., (Shelton, CT) and used as received without additional pretreatment.
- the C80 wax was a mixture of predominantly linear paraffins with very low content of olefins and oxygenates.
- SASOLTM has been marketing three commercial grades of waxes: PARAFLINTTM HI, a 700°F+ (371°C+) full range wax; PARAFLINTTM C80 and C105, 700-1100°F (371-593°C) and 1100°F+ (593°C+) distillate fractions, respectiyely.
- the molecular weight distribution (in terms of boiling point) of the waxes is illustrated briefly in Table 3.
- Pt/Beta Catalyst Preparation of Pt/Beta Catalyst.
- Pt/Beta catalyst was prepared by extruding a water-containing mull mix or paste containing 65 parts of Zeolite Beta with 35 parts of alumina (dry basis). After drying, the Zeolite Beta containing catalyst was calcined under nitrogen at 900°F (482°C) and exchanged at ambient temperature with a sufficient quantity of ammonium nitrate to remove residual sodium in the zeolite channels. The extrudate was then washed with de-ionized water and calcined in air at 1000°F (538°C).
- the 65% Zeolite Beta/35% Alumina extrudate was steamed at 1020°F (549°C) to reduce the Alpha value of the calcined catalyst to less than 10.
- the steamed, 65% low acidity Beta/35% Alumina catalyst was ion exchanged with a tetraammine platinum chloride solution under ion exchange conditions to uniformly produce a catalyst containing 0.6% Pt. After washing with de-ionized water to remove residual chlorides, the catalyst was dried at 250°F (121°C) followed by final air calcination at 680°F (360°C).
- Pt/ZSM-48 catalyst was prepared by extruding a water-containing mull mix or paste containing 65 parts of ZSM-48 with 35 parts of alumina (dry basis). After drying, the ZSM-48 containing catalyst was calcined under nitrogen at 900°F (482°C) and exchanged at ambient temperature with a sufficient quantity of ammonium nitrate to remove residual sodium in the zeolite channels. The extrudate was then washed with deionized water and calcined in air at 1000°F (538°C).
- Wax Hydroprocessing The wax hydroisomerization experiments were performed using a micro-unit equipped with two three-zone furnaces and two down-flow trickle-bed tubular reactors (1/2" ID) in cascade (with option to bypass the second reactor). The unit was carefully heat-traced to avoid freezing of the high melting point C80 wax. To reduce feed bypassing and lower zeolite pore diffusion resistance, the catalysts extrudates were crushed and sized to 60-80 mesh. The reactors 1 -and 2 were then loaded with 15 cc of the 60-80 mesh Pt/ZSM-48 catalyst and the 60-80 mesh Pt/Beta catalyst, respectively.
- the pour point and cloud point of 700°F+ (371°C+) lubes were measured by D97 and D2500 methods, and their viscosities were determined at both 40°C and 100°C according to D445-3 and D445-5 methods, respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US41694902P | 2002-10-08 | 2002-10-08 | |
US416949P | 2002-10-08 | ||
PCT/US2003/032098 WO2004033592A1 (en) | 2002-10-08 | 2003-10-07 | Lube hydroisomerization system |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1556463A1 true EP1556463A1 (en) | 2005-07-27 |
Family
ID=32093932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03770719A Withdrawn EP1556463A1 (en) | 2002-10-08 | 2003-10-07 | Lube hydroisomerization system |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040108245A1 (en) |
EP (1) | EP1556463A1 (en) |
JP (1) | JP2006502295A (en) |
CN (1) | CN1703491A (en) |
AU (1) | AU2003279227B2 (en) |
CA (1) | CA2499352A1 (en) |
WO (1) | WO2004033592A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2009084B1 (en) * | 2006-03-31 | 2013-08-28 | Nippon Oil Corporation | Lube base oil, process for production thereof, and lubricating oil composition |
JP2007270062A (en) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | Lubricant base oil, lubricating oil composition and method for producing lubricant base oil |
JP5137314B2 (en) | 2006-03-31 | 2013-02-06 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
JP5290912B2 (en) * | 2009-08-18 | 2013-09-18 | Jx日鉱日石エネルギー株式会社 | Method for producing lubricating base oil |
JP5552139B2 (en) * | 2012-05-23 | 2014-07-16 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil, lubricating oil composition, and method for producing lubricating base oil |
US9587180B2 (en) * | 2012-12-18 | 2017-03-07 | Exxonmobil Research And Engineering Company | Process for making lube base stocks from renewable feeds |
CN105778993B (en) * | 2014-12-23 | 2018-07-17 | 神华集团有限责任公司 | The lube base oil product that the system and method for production lube base oil and production obtain |
KR101692547B1 (en) | 2016-04-26 | 2017-01-03 | 에스케이이노베이션 주식회사 | Process for reducing haze in heavy base oil and hydroisomerization catalyst system having reduced haze |
WO2018109015A1 (en) | 2016-12-16 | 2018-06-21 | Shell Internationale Research Maatschappij B.V. | Catalyst system for dewaxing |
US11351528B2 (en) | 2018-04-17 | 2022-06-07 | Shell Usa, Inc. | Catalyst system for dewaxing |
Family Cites Families (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2250410A (en) * | 1938-05-21 | 1941-07-22 | Shell Dev | Catalytic treatment of hydrocarbons |
US3711399A (en) * | 1970-12-24 | 1973-01-16 | Texaco Inc | Selective hydrocracking and isomerization of paraffin hydrocarbons |
US4097364A (en) * | 1975-06-13 | 1978-06-27 | Chevron Research Company | Hydrocracking in the presence of water and a low hydrogen partial pressure |
US4181597A (en) * | 1977-01-26 | 1980-01-01 | Mobil Oil Corporation | Method of stabilizing lube oils |
US4388177A (en) * | 1981-01-13 | 1983-06-14 | Mobil Oil Corporation | Preparation of natural ferrierite hydrocracking catalyst and hydrocarbon conversion with catalyst |
US4335019A (en) * | 1981-01-13 | 1982-06-15 | Mobil Oil Corporation | Preparation of natural ferrierite hydrocracking catalyst and hydrocarbon conversion with catalyst |
US4490242A (en) * | 1981-08-07 | 1984-12-25 | Mobil Oil Corporation | Two-stage hydrocarbon dewaxing hydrotreating process |
US4377469A (en) * | 1981-09-30 | 1983-03-22 | Mobil Oil Corporation | Maintaining catalytic activity of sodium aluminosilicates |
US4431517A (en) * | 1981-11-13 | 1984-02-14 | Standard Oil Company (Indiana) | Process for mild hydrocracking of hydrocarbon feeds |
US4431527A (en) * | 1981-11-13 | 1984-02-14 | Standard Oil Company (Indiana) | Process for hydrogen treating high nitrogen content hydrocarbon feeds |
US4483764A (en) * | 1981-11-13 | 1984-11-20 | Standard Oil Company (Indiana) | Hydrocarbon conversion process |
US4431516A (en) * | 1981-11-13 | 1984-02-14 | Standard Oil Company (Indiana) | Hydrocracking process |
US4460698A (en) * | 1981-11-13 | 1984-07-17 | Standard Oil Company (Indiana) | Hydrocarbon conversion catalyst |
US4402866A (en) * | 1981-12-16 | 1983-09-06 | Mobil Oil Corporation | Aging resistance shape selective catalyst with enhanced activity |
US4784747A (en) * | 1982-03-22 | 1988-11-15 | Mobil Oil Corporation | Catalysts over steam activated zeolite catalyst |
US4510045A (en) * | 1982-05-28 | 1985-04-09 | Mobil Oil Corporation | Hydrocarbon dewaxing process using steam-activated alkali metal zeolite catalyst |
US4568449A (en) * | 1982-08-16 | 1986-02-04 | Union Oil Company Of California | Hydrotreating catalyst and process |
US4436614A (en) * | 1982-10-08 | 1984-03-13 | Chevron Research Company | Process for dewaxing and desulfurizing oils |
US4431519A (en) * | 1982-10-13 | 1984-02-14 | Mobil Oil Corporation | Method for catalytically dewaxing oils |
US4610778A (en) * | 1983-04-01 | 1986-09-09 | Mobil Oil Corporation | Two-stage hydrocarbon dewaxing process |
US4594146A (en) * | 1983-10-06 | 1986-06-10 | Mobil Oil Corporation | Conversion with zeolite catalysts prepared by steam treatment |
DE3587895T2 (en) * | 1984-05-03 | 1994-12-01 | Mobil Oil Corp | Catalytic dewaxing of light and heavy oils in two parallel reactors. |
US4601993A (en) * | 1984-05-25 | 1986-07-22 | Mobil Oil Corporation | Catalyst composition dewaxing of lubricating oils |
US4767522A (en) * | 1984-11-28 | 1988-08-30 | Mobil Oil Corporation | Distillate dewaxing process with mixed zeolites |
US4919788A (en) * | 1984-12-21 | 1990-04-24 | Mobil Oil Corporation | Lubricant production process |
US4599162A (en) * | 1984-12-21 | 1986-07-08 | Mobil Oil Corporation | Cascade hydrodewaxing process |
US4636299A (en) * | 1984-12-24 | 1987-01-13 | Standard Oil Company (Indiana) | Process for the manufacture of lubricating oils |
AU603344B2 (en) * | 1985-11-01 | 1990-11-15 | Mobil Oil Corporation | Two stage lubricant dewaxing process |
US4975177A (en) * | 1985-11-01 | 1990-12-04 | Mobil Oil Corporation | High viscosity index lubricants |
US5037528A (en) * | 1985-11-01 | 1991-08-06 | Mobil Oil Corporation | Lubricant production process with product viscosity control |
US4622130A (en) * | 1985-12-09 | 1986-11-11 | Shell Oil Company | Economic combinative solvent and catalytic dewaxing process employing methylisopropyl ketone as the solvent and a silicate-based catalyst |
US4684756A (en) * | 1986-05-01 | 1987-08-04 | Mobil Oil Corporation | Process for upgrading wax from Fischer-Tropsch synthesis |
US5059299A (en) * | 1987-12-18 | 1991-10-22 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils |
US5075269A (en) * | 1988-12-15 | 1991-12-24 | Mobil Oil Corp. | Production of high viscosity index lubricating oil stock |
US5246566A (en) * | 1989-02-17 | 1993-09-21 | Chevron Research And Technology Company | Wax isomerization using catalyst of specific pore geometry |
DK0458895T3 (en) * | 1989-02-17 | 1995-11-06 | Chevron Usa Inc | Isomerization of waxy lubricating oils and petroleum wax using a silicoaluminophosphate molsi catalyst |
EP0460300A1 (en) * | 1990-06-20 | 1991-12-11 | Akzo Nobel N.V. | Process for the preparation of a presulphided catalyst; Process for the preparation of a sulphided catalyst, and use of said catalyst |
US5358628A (en) * | 1990-07-05 | 1994-10-25 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US5146022A (en) * | 1990-08-23 | 1992-09-08 | Mobil Oil Corporation | High VI synthetic lubricants from cracked slack wax |
US5232579A (en) * | 1991-06-14 | 1993-08-03 | Mobil Oil Corporation | Catalytic cracking process utilizing a zeolite beta catalyst synthesized with a chelating agent |
US5288395A (en) * | 1991-07-24 | 1994-02-22 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US5208403A (en) * | 1992-01-09 | 1993-05-04 | Mobil Oil Corporation | High VI lubricant blends from slack wax |
US5516736A (en) * | 1992-03-12 | 1996-05-14 | Mobil Oil Corp. | Selectivating zeolites with organosiliceous agents |
US5275719A (en) * | 1992-06-08 | 1994-01-04 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US5643440A (en) * | 1993-02-12 | 1997-07-01 | Mobil Oil Corporation | Production of high viscosity index lubricants |
BR9303997A (en) * | 1993-10-01 | 1995-05-30 | Petroleo Brasileiro Sa | Process for the production of basic librifying oils with high viscosity indexes and high cetane diesel oil |
US5498821A (en) * | 1994-10-13 | 1996-03-12 | Exxon Research And Engineering Company | Carbon dioxide addition in hydrocracking/hydroisomerization processes to control methane production |
US5689031A (en) * | 1995-10-17 | 1997-11-18 | Exxon Research & Engineering Company | Synthetic diesel fuel and process for its production |
US5976351A (en) * | 1996-03-28 | 1999-11-02 | Mobil Oil Corporation | Wax hydroisomerization process employing a boron-free catalyst |
GB2311789B (en) * | 1996-04-01 | 1998-11-04 | Fina Research | Process for converting wax-containing hydrocarbon feedstocks into high-grade middle distillate products |
US5911874A (en) * | 1996-06-28 | 1999-06-15 | Exxon Research And Engineering Co. | Raffinate hydroconversion process |
EP0912243B1 (en) * | 1996-07-15 | 2001-12-05 | Chevron U.S.A. Inc. | Sulfur resistant hydroconversion catalyst and hydroprocessing of sulfur-containing lube feedstock |
WO1998002502A1 (en) * | 1996-07-16 | 1998-01-22 | Chevron U.S.A. Inc. | Base stock lube oil manufacturing process |
ES2236796T3 (en) * | 1996-10-31 | 2005-07-16 | Exxonmobil Oil Corporation | HIGHLY SELECTIVE DEPARAFINED PROCESS IN THE FORM THAT DELAYS THE AGING OF THE CATALYST. |
US6322692B1 (en) * | 1996-12-17 | 2001-11-27 | Exxonmobil Research And Engineering Company | Hydroconversion process for making lubricating oil basestocks |
US6096189A (en) * | 1996-12-17 | 2000-08-01 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
US5935417A (en) * | 1996-12-17 | 1999-08-10 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
US6099719A (en) * | 1996-12-17 | 2000-08-08 | Exxon Research And Engineering Company | Hydroconversion process for making lubicating oil basestocks |
US6090989A (en) * | 1997-10-20 | 2000-07-18 | Mobil Oil Corporation | Isoparaffinic lube basestock compositions |
US6013171A (en) * | 1998-02-03 | 2000-01-11 | Exxon Research And Engineering Co. | Catalytic dewaxing with trivalent rare earth metal ion exchanged ferrierite |
US6663768B1 (en) * | 1998-03-06 | 2003-12-16 | Chevron U.S.A. Inc. | Preparing a HGH viscosity index, low branch index dewaxed |
US6231749B1 (en) * | 1998-05-15 | 2001-05-15 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US6190532B1 (en) * | 1998-07-13 | 2001-02-20 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US6051129A (en) * | 1998-07-24 | 2000-04-18 | Chevron U.S.A. Inc. | Process for reducing haze point in bright stock |
US6080301A (en) * | 1998-09-04 | 2000-06-27 | Exxonmobil Research And Engineering Company | Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins |
US6179994B1 (en) * | 1998-09-04 | 2001-01-30 | Exxon Research And Engineering Company | Isoparaffinic base stocks by dewaxing fischer-tropsch wax hydroisomerate over Pt/H-mordenite |
US6337010B1 (en) * | 1999-08-02 | 2002-01-08 | Chevron U.S.A. Inc. | Process scheme for producing lubricating base oil with low pressure dewaxing and high pressure hydrofinishing |
US6310265B1 (en) * | 1999-11-01 | 2001-10-30 | Exxonmobil Chemical Patents Inc. | Isomerization of paraffins |
US6398946B1 (en) * | 1999-12-22 | 2002-06-04 | Chevron U.S.A., Inc. | Process for making a lube base stock from a lower molecular weight feedstock |
US6294077B1 (en) * | 2000-02-02 | 2001-09-25 | Mobil Oil Corporation | Production of high viscosity lubricating oil stock with improved ZSM-5 catalyst |
US6652735B2 (en) * | 2001-04-26 | 2003-11-25 | Exxonmobil Research And Engineering Company | Process for isomerization dewaxing of hydrocarbon streams |
-
2003
- 2003-10-03 US US10/678,434 patent/US20040108245A1/en not_active Abandoned
- 2003-10-07 AU AU2003279227A patent/AU2003279227B2/en not_active Ceased
- 2003-10-07 EP EP03770719A patent/EP1556463A1/en not_active Withdrawn
- 2003-10-07 CA CA002499352A patent/CA2499352A1/en not_active Abandoned
- 2003-10-07 WO PCT/US2003/032098 patent/WO2004033592A1/en active Application Filing
- 2003-10-07 JP JP2004543636A patent/JP2006502295A/en active Pending
- 2003-10-07 CN CN200380101105.6A patent/CN1703491A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO2004033592A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2006502295A (en) | 2006-01-19 |
US20040108245A1 (en) | 2004-06-10 |
CN1703491A (en) | 2005-11-30 |
CA2499352A1 (en) | 2004-04-22 |
AU2003279227A1 (en) | 2004-05-04 |
WO2004033592A1 (en) | 2004-04-22 |
AU2003279227B2 (en) | 2008-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2003300330B2 (en) | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax | |
EP0783470B1 (en) | Upgrading of fischer-tropsch heavy end products | |
Taylor et al. | Selective hydroisomerization of long chain normal paraffins | |
JP5042622B2 (en) | Fischer-Tropsch Premium Diesel and Method for Producing Lubricating Base Oil | |
AU2004252511B2 (en) | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including Fischer-Tropsch wax | |
NL1026460C2 (en) | Stable, moderately unsaturated distillate fuel blending materials prepared by hydroprocessing Fischer-Tropsch products under low pressure. | |
US7198710B2 (en) | Isomerization/dehazing process for base oils from Fischer-Tropsch wax | |
US6962651B2 (en) | Method for producing a plurality of lubricant base oils from paraffinic feedstock | |
JP2002503755A (en) | Base oil for lubrication excellent in low temperature characteristics and method for producing the same | |
AU2004250190A1 (en) | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including Fischer-Tropsch wax, plus solvent dewaxing | |
US6700027B1 (en) | Process for the oligomerization of olefins in Fischer-Tropsch condensate using chromium catalyst and high temperature | |
AU2003279227B2 (en) | Lube hydroisomerization system | |
JP2002503751A (en) | A method for improving the quality of a waxy raw material using a catalyst containing a mixture of a powder deflow catalyst and a powder isomerization catalyst formed in separated particles | |
JPH0715103B2 (en) | Hydrocracking and catalytic dewaxing methods | |
CN115698230A (en) | Process for the preparation of fischer-tropsch derived middle distillates and base oils | |
CA2029999A1 (en) | Catalytic process for manufacture of low pour lubricating oils | |
JPH0867883A (en) | Method and catalyst for dewaxing hydrocarbon feedstock |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20050414 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1080104 Country of ref document: HK |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1080104 Country of ref document: HK |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20120501 |