EP3635076A1 - Production of diesel and base stocks from crude oil - Google Patents
Production of diesel and base stocks from crude oilInfo
- Publication number
- EP3635076A1 EP3635076A1 EP18730909.1A EP18730909A EP3635076A1 EP 3635076 A1 EP3635076 A1 EP 3635076A1 EP 18730909 A EP18730909 A EP 18730909A EP 3635076 A1 EP3635076 A1 EP 3635076A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- product
- lubricant base
- base oil
- viscosity
- 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.)
- Pending
Links
Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0418—The hydrotreatment being a hydrorefining
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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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
- 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
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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
- 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
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
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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
- 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
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
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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
- 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
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0436—The hydrotreatment being an aromatic saturation
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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
- 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
- C10G69/08—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 reforming naphtha
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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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/003—Distillation of hydrocarbon oils distillation of lubricating oils
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1025—Natural gas
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- Crude petroleum may be distilled and fractionated into many products such as gasoline, kerosene, jet fuel, asphaltenes, and the like.
- One portion of the crude petroleum form the base of lubricating base oils used in, inter alia, the lubricating of internal combustion engines.
- Lube oil users are demanding ever increasing base oil quality, and refiners are finding that their available equipment is becoming less and less able to produce base oils that meet these higher quality specifications.
- New processes are required to provide refiners with the tools for preparing high quality modern base oils, particularly using existing equipment at lower cost and with safer operation.
- Finished lubricants used for such things as automobiles, diesel engines, and industrial applications generally are comprised of a lube base oil and additives.
- a few lube base oils are used to produce a wide variety of finished lubricants by varying the mixtures of individual lube base oils and individual additives.
- lube base oils are simply
- Lube base oils are normally used
- the cut points are set to control the final viscosity and flash point of the lube base oil.
- Group I base oils those with greater than 300 ppm sulfur and 10 wt% aromatics, are generally produced by first extracting a vacuum gas oil (or waxy distillate) with a polar solvent, such as N-methyl-pyyrolidone, furfural, or phenol. The resulting waxy raffinates produced from solvent extraction processes are then dewaxed, either catalytically with the use of a dewaxing catalyst such as ZSM-5, or by solvent dewaxing. The resultant base oil may be hydrofinished to improve color and other lubricant properties.
- a vacuum gas oil or waxy distillate
- a polar solvent such as N-methyl-pyyrolidone, furfural, or phenol.
- the resulting waxy raffinates produced from solvent extraction processes are then dewaxed, either catalytically with the use of a dewaxing catalyst such as ZSM-5, or by solvent dewaxing.
- the resultant base oil may be hydrofinished to improve color and
- Group II base oils those with less than 300 ppm sulfur and 10 wt% aromatics, and with a viscosity index range of 8-120, are typically produced by hydrocracking followed by selective catalytic dewaxing and hydrofinishing.
- Hydrocracking upgrades the viscosity index of the entrained oil in the feedstock by ring cracking and aromatics saturation. The degree of aromatics saturation is limited by the high temperature (300-450°C) of the hydrocracking stage.
- the hydrocracked oil is dewaxed, either by solvent dewaxing or by catalytic dewaxing, with catalytic dewaxing typically being the preferred method.
- the dewaxed oil is then preferably hydrofinished at mild temperatures (150-300°C) to remove polynuclear aromatics (PNAs) which were not converted in the first stage and the dewaxing stage and which have a strongly detrimental impact on lube base oil quality.
- PNAs polynuclear aromatics
- Group III base oils have the same sulfur and aromatics specifications as Group II base stocks but have viscosity indices above 120. These materials are manufactured with the same type of catalytic technology employed to produce Group II base oils but with either the hydrocracker being operated at higher severity, or with the use of feedstocks with higher wax content.
- a typical lube hydroprocessing plant consists of two primary processing stages.
- a feedstock typically a vacuum gas oil, deasphalted oil, processed gas oils, or any combination of these materials
- hydrocracked oil is dearomatized, preferably with an aromatic saturation catalyst, and dewaxed, preferably with the use of a highly shape-selective catalyst capable of wax conversion by isomerization.
- the dewaxed, dearomatized oil can be subsequently hydrofinished to remove PNA impurities.
- Operation of the final hydrofinishing step is optimized to convert PNA impurities since significant conversion of one ring and two ring aromatics cannot be accomplished in the final hydrofinishing step because of its low operating temperature.
- the claimed invention provides a process of producing Group III base oils, along with a naphtha product and diesel product, from whole waxy crude oil without the typical vacuum distillation stage and separations to form the typical cuts off of the vacuum tower.
- the crude oil may be hydroprocessed, dearomatized, dewaxed, and hydrofinished to produce a Group III base oil.
- the dewaxing catalyst will isomerize the naphtha range molecules to increase the octane value to a suitable level for blending into gasoline and the diesel range molecules to reduce the diesel cloud point.
- a method for producing lubricant base oils from a whole petroleum crude oil is provided.
- a whole petroleum crude oil feedstock comprising less than about 2 wt% of heptane asphaltenes, less than about 2 wt% of Conradson carbon residue (CCR), and less than about 50 ppm of metals is hydrotreated over at least one bed of a hydrotreating catalyst under effective hydrotreating conditions to produce a hydrotreated effluent having less sulfur, nitrogen and aromatics than the whole petroleum crude oil.
- CCR Conradson carbon residue
- the hydrotreated effluent is then dewaxed in the presence of a dewaxing catalyst to produce a naphtha product having an octane value greater than 60, a diesel product having a cloud point less than 0°C, and a lubricant base oil product, which is fractionated into at least a low viscosity lubricant base oil product having a viscosity of 2-8 cSt at 100°C and a high viscosity lubricant base oil product having a viscosity of 6-30 cSt at 100°C.
- a naphtha product, a diesel product, and a lubricant base oil product is produced from a whole petroleum crude oil.
- a whole petroleum crude oil feedstock, containing less than about 2 wt% of heptane asphaltenes, less than about 2 wt% of Conradson carbon residue (CCR), and less than about 50 ppm of metals, is provided, without separation or pretreatment, to a hydrotreating unit, where it is hydrotreated over at least one bed of a hydrotreating catalyst under effective hydrotreating conditions to produce a hydrotreated effluent having less than 15 ppm sulfur, less than 5 ppm nitrogen, less than 2 wt% C3- paraffins, and less than 25 wt% of aromatics.
- the hydrotreated effluent is dewaxed in the presence of a dewaxing catalyst to produce a dewaxed effluent, which is separated into at least a naphtha product having an octane value greater than 60, a diesel product having a cloud point less than 0°C, and a base stock product.
- the base stock product is subjected to hydrofinishing and/or aromatic saturation to remove polynuclear aromatic compounds and produce a hydrofinished base stock, which is then fractionated into at least a low viscosity lubricant base oil product having a viscosity of 2-8 cSt at 100°C and a high viscosity lubricant base oil product having a viscosity of 6-30 cSt at 100°C.
- FIG. 1 schematically shows an example of a configuration suitable for processing a whole waxy crude oil feed to form lubricant base oils.
- methods are provided for producing lubricant base oils from crude oil.
- crude oil is subjected to atmospheric distillation to obtain a distillate cut and an atmospheric residual cut.
- the atmospheric residual cut is then sent to vacuum distillation where at least volatile distillate, light neutral distillate, heavy neutral distillate, and vacuum residual cuts are obtained.
- Deasphalting is then performed on the vacuum residual cut to remove asphaltenes, and the deasphalted oil is then subjected, along with the light neutral and heavy neutral cuts, to solvent extraction to remove aromatics.
- the raffinate from solvent extraction may then be hydroprocessed and dewaxed to produce base oils.
- FIG. 1 shows an example reactor system 100 for the inventive process.
- a feedstock 102 that meets certain specifications is subjected in a first stage to hydrotreatment in a hydroprocessing unit 110 to remove sulfur, nitrogen and saturate aromatics.
- the hydrotreated effluent 112 is then processed in a second stage 120 over a stacked bed of noble metal catalysts.
- the top bed of noble metal hydrogenation catalyst further saturates the aromatics in the hydrotreated effluent 112.
- the bottom bed contains a catalytic dewaxing catalyst which isomerizes the C4-Cs n-paraffins (naphtha range molecules) to high octane iso-paraffins to bring the naphtha product octane number to greater than 70 so it can be directly blended into gasoline.
- the catalytic dewaxing catalyst also isomerizes the C9 to 650°F- (343°C-) boiling point n-paraffins (diesel range molecules) to low pour point iso-paraffins to reduce diesel cloud point, and the 650°F+ (343°C+) range n-paraffins into low pour point Group III lube base stocks.
- the dewaxed effluent 122 is separated by distillation in column 130 into a naphtha cut 132, a diesel cut 134 and base stock cut 136, and the base stock cut 136 is hydrofinished in hydrofinishing unit 140 to remove trace polynuclear aromatics.
- the hydrofinished base stock 142 is then stripped to remove light hydrocarbons and separated in column 150 into two fractions - a light neutral base stock 152 having a low viscosity, 3-5 cSt (at 100°C), and a heavy neutral base stock 154 having a high viscosity, 8-15 cSt (at 100°C).
- Both Group III base stock fractions have a viscosity index of greater than 120 and pour point of -15°C and the cloud point-pour point spread is less than 30°C.
- Suitable feedstocks for the present invention include whole petroleum crude oils that are low in metals and heptane asphaltenes. These whole petroleum crude oils often contain a high volume of waxy hydrocarbons. Ideally, the feedstock will be suitable for processing without separation.
- One way of defining a feedstock is based on the boiling range of the feed.
- One option for defining a boiling range is to use an initial boiling point for a feed and/or a final boiling point for a feed.
- Another option, which in some instances may provide a more representative description of a feed is to characterize a feed based on the amount of the feed that boils at one or more temperatures. For example, a "T5" boiling point for a feed is defined as the temperature at which 5 wt% of the feed will boil off.
- a "T50" boiling point is a temperature at 50 wt% of the feed will boil. The percentage of a feed that will boil at a given temperature can be determined by the method specified in ASTM D2887.
- Whole waxy crudes suitable for the claimed process include, for example, feeds with an initial boiling point of at least 70°F (21°C), or at least 100°F (37°C), or at least 125°F (51°C).
- the content of heptane asphaltenes in the whole crude feedstock can be less than 2.0 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.25 wt%, based on the total weight of the feedstock.
- the content of heptane asphaltenes in the 1050°F+ (565°C+) fraction of the feedstock is less than 5.0 wt%.
- the feedstock may have a metals content of less than 50 ppm, or less than 20 ppm, or less than 15 ppm, or less than 10 ppm, or less than 5 ppm, and a content of carbonaceous residue of less than 2.0 wt%, or less thanl .5 wt%, or less than 1.0 wt%, or less than 0.5 wt%, as measured by the micro carbon residue test defined in ASTM D4530.
- the feedstock 102 is hydrotreated in a first stage of the reactor system by a hydroprocessing unit 110. Hydrotreatment is typically used to reduce the sulfur, nitrogen, and aromatic content of a feed.
- the catalysts used for hydrotreatment of the crude oil can include conventional hydroprocessing catalysts, such as those that comprise at least one Group VIII non- noble metal (Columns 8-10 of IUPAC periodic table), preferably Fe, Co, and/or Ni, such as Co and/or Ni; and at least one Group VI metal (Column 6 of IUPAC periodic table), preferably Mo and/or W.
- Such hydroprocessing catalysts optionally include transition metal sulfides that are impregnated or dispersed on a refractory support or carrier such as alumina and/or silica.
- the support or carrier itself typically has no significant/measurable catalytic activity.
- Substantially carrier- or support-free catalysts commonly referred to as bulk catalysts, generally have higher volumetric activities than their supported counterparts.
- the catalysts can either be in bulk form or in supported form.
- other suitable support/carrier materials can include, but are not limited to, zeolites, titania, silica-titania, and titania-alumina.
- Suitable aluminas are porous aluminas such as gamma or eta having average pore sizes from 50 to 200 A, or 75 to 150 A; a surface area from 100 to 300 m 2 /g, or 150 to 250 m 2 /g; and a pore volume of from 0.25 to 1.0 cm 3 /g, or 0.35 to 0.8 cm 3 /g. More generally, any convenient size, shape, and/or pore size distribution for a catalyst suitable for hydrotreatment of a distillate (including lubricant base oil) boiling range feed in a
- the at least one Group VIII non-noble metal, in oxide form can typically be present in an amount ranging from 2 wt% to 40 wt%, preferably from 4 wt% to 15 wt%.
- the at least one Group VI metal, in oxide form can typically be present in an amount ranging from 2 wt% to 70 wt%, preferably for supported catalysts from 6 wt% to 40 wt% or from 10 wt% to 30 wt%. These weight percents are based on the total weight of the catalyst.
- Suitable metal catalysts include cobalt/molybdenum (1-10% Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide, 10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W as oxide) on alumina, silica, silica-alumina, or titania.
- the hydrotreatment is carried out in the presence of hydrogen.
- a hydrogen stream is, therefore, fed or injected into a vessel or reaction zone or hydroprocessing zone in which the hydroprocessing catalyst is located.
- Hydrogen which is contained in a hydrogen "treat gas,” is provided to the reaction zone.
- Treat gas can be either pure hydrogen or a hydrogen-containing gas, which is a gas stream containing hydrogen in an amount that is sufficient for the intended reaction(s), optionally including one or more other gasses (e.g., nitrogen and light hydrocarbons such as methane), and which will not adversely interfere with or affect either the reactions or the products.
- the treat gas stream introduced into a reaction stage will preferably contain at least 50 vol. % and more preferably at least 75 vol% hydrogen.
- Hydrogen can be supplied at a rate of from 100 SCF/B (standard cubic feet of hydrogen per barrel of feed) (17 Nm 3 /m 3 ) to 1500 SCF/B (253 Nm 3 /m 3 ).
- the hydrogen is provided in a range of from 200 SCF/B (34 Nm 3 /m 3 ) to 1200 SCF/B (202 Nm 3 /m 3 ).
- Hydrogen can be supplied co-currently with the input feed to the hydrotreatment reactor and/or reaction zone or separately via a separate gas conduit to the hydrotreatment zone.
- Hydrotreating conditions can include temperatures of 200°C to 450°C, or 315°C to 425°C, preferably 340°C to 420°C; pressures of 250 psig (1.8 MPag) to 5000 psig (34.6 MPag) or 300 psig (2.1 MPag) to 3000 psig (20.8 MPag), preferably 1500 psig (10.3 MPag) to 2500 psig (13.8 MPag), more preferably 1750 psig (12.1 MPag) to 2250 psig (13.1 MPag); liquid hourly space velocities (LHSV) of 0.1 hr "1 to 10 hr "1 , preferably 0.1 hr "1 to 2 hr “1 , more preferably 0.3 hr " 1 to 0.7 hr “1 ; and hydrogen treat rates of 200 SCF/B (35.6 m3/m3) to 10,000 SCF/B (1781 m 3 /m 3 ), or 500 (89 m 3 /m 3
- the hydrotreatment may be carried out in one or more catalyst beds.
- the hydroprocessing unit 110 contains more than one hydrotreatment catalyst beds, in some embodiments, two catalyst beds, and in some embodiments, three catalyst beds.
- the hydrotreated effluent 112 contains less sulfur, nitrogen, and aromatics than the feedstock 102. In some embodiments, the hydrotreated effluent 112 will contain less than 15 ppm of sulfur, less than 5 ppm of nitrogen, less than 2 wt% of C 3 - paraffins, and less than 25 wt% of aromatics.
- the petrolatum can be exposed to one or more beds of hydrocracking catalyst.
- the hydrocracking conditions can be selected so that the total conversion from all hydrotreating and/or hydrocracking stages is 15 wt% or less, or 10 wt% or less, or 8 wt% or less, as described above.
- Hydrocracking catalysts typically contain sulfided base metals on acidic supports, such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. Often these acidic supports are mixed or bound with other metal oxides such as alumina, titania or silica.
- acidic supports such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. Often these acidic supports are mixed or bound with other metal oxides such as alumina, titania or silica.
- metals for hydrocracking catalysts include nickel, nickel-cobalt- molybdenum, cobalt-molybdenum, nickel-tungsten, nickel- molybdenum, and/or nickel- molybdenum-tungsten. Additionally or alternately, hydrocracking catalysts with noble metals can also be used.
- noble metal catalysts include those based on platinum and/or palladium.
- Support materials which may be used for both the noble and non-noble metal catalysts can comprise a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, alumina-silica being the most common (and preferred, in one embodiment).
- a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, zirconia, or combinations thereof, with alumina, silica, alumina-silica being the most common (and preferred, in one embodiment).
- the conditions selected for hydrocracking can depend on the desired level of conversion, the level of contaminants in the input feed to the hydrocracking stage, and potentially other factors.
- a hydrocracking process can be carried out at temperatures of 550°F (288°C) to 840°F (449°C), hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05 h "1 to 10 h "1 , and hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B).
- temperatures of 550°F (288°C) to 840°F (449°C) hydrogen partial pressures of from 250 psig to 5000 psig (1.8 MPag to 34.6 MPag)
- liquid hourly space velocities from 0.05 h "1 to 10 h "1
- hydrogen treat gas rates of from 35.6 m 3 /m 3 to 1781
- the conditions can include temperatures in the range of 600°F (343°C) to 815°F (435oC), hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag to 20.9 MPag), and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
- the LHSV relative to only the hydrocracking catalyst can be from 0.25 h "1 to 50 h "1 , such as from 0.5 h _1 to 20 h "1 , and preferably from 1.0 h _1 to 4.0 h "1 .
- a high pressure stripper (or another type of separator) can then be used in between the hydrotreatment stage 110 and catalytic dewaxing stage 120 of the reaction system to remove gas phase sulfur and nitrogen contaminants.
- a separator allows contaminant gases formed during hydrotreatment (such as FhS and NH 3 ) to be removed from the reaction system prior to passing the hydrotreated effluent 112 into a later stage of the reaction system.
- One option for the separator is to simply perform a gas-liquid separation to remove contaminants.
- Another option is to use a separator such as a flash separator that can perform a separation at a higher temperature.
- the hydrotreated effluent 112 is then processed over one or more catalyst beds containing a dewaxing catalyst in a catalytic dewaxing unit 120.
- a dewaxing catalyst is located in a bed downstream from any hydrotreatment catalyst stages and/or any
- hydrotreatment catalyst present in a stage. This can allow the dewaxing to occur on molecules that have already been hydrotreated to remove a significant fraction of organic sulfur- and nitrogen-containing species.
- Suitable dewaxing catalysts can include molecular sieves such as crystalline aluminosilicates (zeolites).
- the molecular sieve can comprise, consist essentially of, or be a molecular sieve having a structure with 10-m ember rings or smaller, such as ZSM-22, ZSM-23, ZSM-35 (or ferrierite), ZSM-48, or a combination thereof, for example ZSM-23 and/or ZSM-48, or ZSM-48 and/or zeolite Beta.
- molecular sieves that are selective for dewaxing by isomerization as opposed to cracking can be used, such as ZSM-48, ZSM-23, or a combination thereof.
- the molecular sieve can comprise, consist essentially of, or be a 10-member ring 1-D molecular sieve.
- Examples include EU-1, ZSM-35 (or ferrierite), ZSM-11, ZSM-57, NU-87, SAPO-11, ZSM-48, ZSM-23, and ZSM-22.
- Preferred materials are EU-2, EU-11, ZBM-30, ZSM-48, or ZSM-23.
- ZSM-48 is most preferred.
- a zeolite having the ZSM-23 structure with a silica to alumina ratio of from 20: 1 to 40: 1 can sometimes be referred to as SSZ-32.
- the dewaxing catalyst can include a binder for the molecular sieve, such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
- a binder for the molecular sieve such as alumina, titania, silica, silica-alumina, zirconia, or a combination thereof, for example alumina and/or titania or silica and/or zirconia and/or titania.
- the dewaxing catalysts used in processes according to the disclosure are catalysts with a low ratio of silica to alumina.
- the ratio of silica to alumina in the zeolite can be less than 200: 1, such as less than 110: 1, or less than 100: 1, or less than 90: 1, or less than 75: 1.
- the ratio of silica to alumina can be from 50: 1 to 200: 1, such as 60: 1 to 160: 1, or 70: 1 to 100: 1.
- the catalysts according to the disclosure further include a metal hydrogenation component.
- the metal hydrogenation component is typically a Group VI and/or a Group VIII metal.
- the metal hydrogenation component is a Group VIII noble metal.
- the metal hydrogenation component is Pt, Pd, or a mixture thereof.
- the metal hydrogenation component can be a combination of a non-noble Group VIII metal with a Group VI metal. Suitable combinations can include Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.
- the metal hydrogenation component may be added to the catalyst in any convenient manner.
- One technique for adding the metal hydrogenation component is by incipient wetness. For example, after combining a zeolite and a binder, the combined zeolite and binder can be extruded into catalyst particles. These catalyst particles can then be exposed to a solution containing a suitable metal precursor.
- metal can be added to the catalyst by ion exchange, where a metal precursor is added to a mixture of zeolite (or zeolite and binder) prior to extrusion.
- the amount of metal in the catalyst can be at least 0.1 wt% based on catalyst, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25 wt%, or at least 0.3 wt%, or at least 0.5 wt% based on catalyst.
- the amount of metal in the catalyst can be 20 wt% or less based on catalyst, or 10 wt% or less, or 5 wt% or less, or 2.5 wt% or less, or 1 wt% or less.
- the amount of metal can be from 0.1 to 5 wt%, preferably from 0.1 to 2 wt%, or 0.25 to 1.8 wt%, or 0.4 to 1.5 wt%.
- the metal is a combination of a non-noble Group VIII metal with a Group VI metal
- the combined amount of metal can be from 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2.5 wt% to 10 wt%.
- the dewaxing catalysts useful in processes according to the disclosure can also include a binder.
- the dewaxing catalysts used in process according to the disclosure are formulated using a low surface area binder, where a low surface area binder represents a binder with a surface area of 100 m 2 /g or less, or 80 m 2 /g or less, or 70 m 2 /g or less.
- the amount of zeolite in a catalyst formulated using a binder can be from 30 wt% zeolite to 90 wt% zeolite relative to the combined weight of binder and zeolite.
- the amount of zeolite is at least 50 wt% of the combined weight of zeolite and binder, such as at least 60 wt% or from 65 wt% to 80 wt%.
- a zeolite can be combined with binder in any convenient manner.
- a bound catalyst can be produced by starting with powders of both the zeolite and binder, combining and mulling the powders with added water to form a mixture, and then extruding the mixture to produce a bound catalyst of a desired size.
- Extrusion aids can also be used to modify the extrusion flow properties of the zeolite and binder mixture.
- the amount of framework alumina in the catalyst may range from 0.1 to 3.33 wt%, or 0.1 to 2.7 wt%, or 0.2 to 2 wt%, or 0.3 to 1 wt%.
- Process conditions in a catalytic dewaxing zone can include a temperature of from 200 to 450°C, preferably 270 to 400°C, a hydrogen partial pressure of from 1.8 MPag to 34.6 MPag (250 psig to 5000 psig), preferably 4.8 MPag to 20.8 MPag, and a hydrogen circulation rate of from 35.6 m 3 /m 3 (200 SCF/B) to 1781 m 3 /m 3 (10,000 SCF/B), preferably 178 m 3 /m 3 (1000 SCF/B) to 890.6 m 3 /m 3 (5000 SCF/B).
- the conditions can include temperatures in the range of 600°F (343°C) to 815°F (435°C), hydrogen partial pressures of from 500 psig to 3000 psig (3.5 MPag-20.9 MPag), and hydrogen treat gas rates of from 213 m 3 /m 3 to 1068 m 3 /m 3 (1200 SCF/B to 6000 SCF/B).
- the liquid hourly space velocity (LHSV) can be from 0.2 h "1 to 10 h "1 , such as from 0.5 h "1 to 5 h "1 and/or from 1 h "1 to 4 h "1 .
- the dewaxed effluent 122 is separated by distillation in column 130 into a naphtha product 132 having a boiling point range of less than about 350°F (176°C), a diesel product 134 having a boiling point range of about 350°F (176°C) to about 700°F (371°C), and a Group III lube base stock product 136 having a boiling point of greater than about 700°F (371°C).
- the naphtha product 132 has an octane value greater than 60, preferably greater than 65, more preferably greater than 70, and ideally greater than 75, allowing it to be directly blended into gasoline.
- the diesel product 134 has a T90 of between 650°F (343°C) and 700°F (371°C), a cloud point of less than 0°C, preferably less than -10°C, and more preferably less than -15°C, and qualifies as an ultra-low sulfur diesel product.
- the base stock product 136 is of Group III quality, having a viscosity index of more than 120, less than 300 ppm sulfur, and 10 wt% aromatics.
- the base stock product 136 is processed through a hydrofinishing and/or aromatic saturation stage 140.
- Hydrofinishing and/or aromatic saturation catalysts can include catalysts containing Group VI metals, Group VIII metals, and mixtures thereof.
- preferred metals include at least one metal sulfide having a strong hydrogenation function.
- the hydrofinishing catalyst can include a Group VIII noble metal, such as Pt, Pd, or a combination thereof.
- the mixture of metals may also be present as bulk metal catalysts wherein the amount of metal is 30 wt% or greater based on catalyst.
- Suitable metal oxide supports include low acidic oxides such as silica, alumina, silica-aluminas or titania, preferably alumina.
- the preferred hydrofinishing catalysts for aromatic saturation will comprise at least one metal having relatively strong hydrogenation function on a porous support.
- Typical support materials include amorphous or crystalline oxide materials such as alumina, silica, and silica-alumina.
- the support materials may also be modified, such as by halogenation, or in particular fluorination.
- the metal content of the catalyst is often as high as 20 weight percent for non-noble metals.
- a preferred hydrofinishing catalyst can include a crystalline material belonging to the M41 S class or family of catalysts.
- the M41 S family of catalysts are mesoporous materials having high silica content. Examples include MCM-41, MCM-48 and MCM-50. A preferred member of this class is MCM-41.
- an aromatic saturation catalyst can be selected based on activity and/or selectivity for aromatic saturation, while a hydrofinishing catalyst can be selected based on activity for improving product specifications, such as product color and polynuclear aromatic reduction.
- Hydrofinishing conditions can include temperatures from 125°C to 425°C, preferably 180°C to 280°C, a hydrogen partial pressure from 500 psig (3.4 MPa) to 3000 psig (20.7 MPa), preferably 1500 psig (10.3 MPa) to 2500 psig (17.2 MPa), and liquid hourly space velocity from 0.1 hr "1 to 5 hr "1 LHSV, preferably 0.5 hr "1 to 1.5 hr "1 . Additionally, a hydrogen treat gas rate of from 35.6 m 3 /m 3 to 1781 m 3 /m 3 (200 SCF/B to 10,000 SCF/B) can be used.
- the hydrofinished base stock 142 is then stripped to remove light hydrocarbons and separated in column 150 into two fractions - a light neutral base stock 152 having a low viscosity of 2-8 cSt (at 100°C), preferably 3-5 cSt (at 100°C), and a heavy neutral base stock 154 having a high viscosity of 6-30 cSt (at 100°C), preferably 8-15 cSt (at 100°C).
- Both Group III base stock fractions have a viscosity index of greater than 120 and pour point of -15°C and the cloud point- pour point spread is less than 30°C.
- the inventive process provides several advantages over the typical base oil production process.
- Whole petroleum crude with a high concentration of waxy hydrocarbons can be efficiently upgraded to finished products without the difficulties waxy hydrocarbons generally present in processing. Because the waxy hydrocarbons are never concentrated, the need for heated tanks and transport lines in the process is eliminated.
- the finished products can be obtained in essentially two stages - hydroprocessing and catalytic dewaxing. In the two stages, the 350°F- (176°C-) molecules are upgraded by octane enhancement to a product high enough in octane to directly blend into gasoline.
- the 350°F-650°F (176-343°C) distillate molecules are dewaxed, desulfurized, and hydrogenated into ultra-low sulfur diesel, and the 650°F+ (343°C+) molecules are hydroisomerized and hydrogenated into Group III base stock. Further, the process minimizes distillation as no molecules are vaporized more than once and the high viscosity Group III base stock product is produced without vaporization.
- the 650°F- (343°C-) components of the feedstock reduce mass transport limitations in the dewaxing catalyst and keep the yield of C 3 - paraffin molecules to less than 2 wt%. Less than 25 wt%, preferably less than 20 wt%, more preferably less than 15 wt%, and ideally 10 wt% of the 650°F+ lubricant range molecules are converted into 650°F- (343°C-) fuel range molecules.
- the waxy crude oil is processed over a stacked bed of three commercially available nickel-molybdenum sulfided hydroprocessing catalysts at about 1800 psig, about 0.4 hr "1 LHSV, and about 340°C start of cycle temperature.
- the yield of 650°F+ (343°C+) product is about 28 wt%.
- the total liquid product has a sulfur content of ⁇ 1 ppm and a nitrogen content of ⁇ 1 ppm.
- the hydroprocessed effluent is subjected to dewaxing over an alumina-bound ZSM-48 having a silica to alumina ratio of about 70: 1 with 0.6 wt% of platinum at about 0.675 hr "1 LHSV, about 340°C, and 1800 psig.
- the dewaxed effluent is distilled to produce a 1 wt% yield of C 3 - paraffins, 44 wt% C 4 - 350°F+ (176°C+) gasoline with 73 octane, 30 wt% yield of ULSD with a cetane of 60 and a cloud point of -20°C, and a 25% yield of 650°F+ (343°C+) base stocks.
- the 650°F+ (343°C+) base stocks is processed over an alumina bound MCM-41 catalyst with 0.3 wt% of palladium and 0.9 wt% of platinum at about 1.0 hr "1 LHSV, about 220°C, and 1800 psig, which produces negligible 650°F- (343°C-) products.
- the hydrofinished 650°F+ (343°C+) base stocks is distilled into two fractions - 66 wt% of a 4 cSt (at 100°C) light neutral Group III base stock with a viscosity index of 122 and a pour point of -40°F, and 34 wt% of a 8 cSt (at 100°C) heavy neutral Group III base stock with a viscosity index of 128 and a pour point of -20°F.
- the inventive process yields 25 wt% of 650°F+ (343°C+) Group III base stock product - meaning 83% of the 650°F+ (343°C+) molecules from the crude oil feedstock are retained. More than half of the 17% conversion of the 650°F+ (343°C+) molecules to 650°F- (343°C-) molecules is caused by the boiling point lowering effect of paraffin isomerization (n- C20 molecules converting to tri-methyl C17 molecules) and aromatics saturation (naphthalenes with a C 6 to C 8 side-chain hydrogenating to decalins with no change in side-chain structure).
- the 350°F- (176°C-) fraction (naphtha) is also sulfur free.
- the 350°F-650°F (176-343°C) distillate fraction is upgraded by reducing the pour point from +15°C to -30°C and the sulfur content from 100 ppm to less than 1 ppm, producing a premium quality ultra-low sulfur diesel blendstock.
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Abstract
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DE102019124731A1 (en) * | 2019-09-13 | 2021-03-18 | Clariant International Ltd | IMPROVED PROCESS FOR CATALYZED HYDROISOMERIZATION OF HYDROCARBONS |
US11034895B1 (en) * | 2020-01-22 | 2021-06-15 | Axens SA | Process for production of on specification group III/III+ base oils while preserving base oil yield |
US11566189B2 (en) | 2020-05-22 | 2023-01-31 | ExxonMobil Technology and Engineering Company | Process to produce high paraffinic diesel |
US11597885B2 (en) * | 2020-07-21 | 2023-03-07 | ExxonMobil Technology and Engineering Company | Methods of whole crude and whole crude wide cut hydrotreating and dewaxing low hetroatom content petroleum |
CN112593905B (en) * | 2020-11-16 | 2021-12-07 | 中国石油大学(北京) | High-viscosity oil exploitation method |
BR112023014398A2 (en) * | 2021-01-19 | 2023-09-26 | Chevron Usa Inc | Method for producing high quality base oils using two-stage hydrofinishing |
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US5993644A (en) * | 1996-07-16 | 1999-11-30 | Chevron U.S.A. Inc. | Base stock lube oil manufacturing process |
FR2808028B1 (en) | 2000-04-21 | 2003-09-05 | Inst Francais Du Petrole | FLEXIBLE PROCESS FOR PRODUCING OIL BASES WITH A ZSM-48 ZEOLITE |
CN1208437C (en) * | 2001-04-28 | 2005-06-29 | 中国石油化工股份有限公司 | Process for preparing light fuel oil and basic oil of lubricant at same time |
EP1456327A1 (en) * | 2001-12-20 | 2004-09-15 | Uop Llc | A method to produce lube basestock |
US7282137B2 (en) | 2002-10-08 | 2007-10-16 | Exxonmobil Research And Engineering Company | Process for preparing basestocks having high VI |
US7077947B2 (en) * | 2002-10-08 | 2006-07-18 | Exxonmobil Research And Engineering Company | Process for preparing basestocks having high VI using oxygenated dewaxing catalyst |
CN100537719C (en) * | 2005-07-15 | 2009-09-09 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of producing high hexadecane value, low-coagulation diesel oil |
CN101376838B (en) * | 2007-08-27 | 2012-09-12 | 中国石油化工股份有限公司 | Production method of lubricating oil basic oil |
AU2008318836B2 (en) | 2007-10-31 | 2013-04-04 | Chevron U.S.A. Inc. | Hydroconversion processes employing multi-metallic catalysts and method for making thereof |
US8394255B2 (en) * | 2008-12-31 | 2013-03-12 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
CN101921621B (en) * | 2009-06-09 | 2013-05-01 | 中国石油化工股份有限公司 | Method for manufacturing isoparaffin solvent oil |
US8617383B2 (en) * | 2010-06-29 | 2013-12-31 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
US8992764B2 (en) * | 2010-06-29 | 2015-03-31 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
CN102911720B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Hydrogenation method for producing lubricating base oil |
WO2013039998A1 (en) * | 2011-09-13 | 2013-03-21 | Exxonmobil Research And Engineering Company | Process for the production of diesel fuel and lubricant base oil |
WO2014082985A1 (en) * | 2012-11-28 | 2014-06-05 | Shell Internationale Research Maatschappij B.V. | Hydrotreating and dewaxing process |
WO2014177424A2 (en) * | 2013-05-02 | 2014-11-06 | Shell Internationale Research Maatschappij B.V. | Process for preparing a heavy base oil |
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US10160923B2 (en) * | 2014-11-05 | 2018-12-25 | Uop Llc | Processes for maximizing high quality distillate |
CN106566589A (en) * | 2016-11-13 | 2017-04-19 | 中国海洋石油总公司 | Method for processing high-wax-content lubricant base oil |
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