Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
  • C10M101/02—Petroleum fractions
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
  • C10G47/16—Crystalline alumino-silicate carriers
  • C10G47/18—Crystalline alumino-silicate carriers the catalyst 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/302—Viscosity
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/104—Aromatic fractions
  • C10M2203/1045—Aromatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/106—Naphthenic fractions
  • C10M2203/1065—Naphthenic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/065—Saturated Compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/12—Gas-turbines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• This disclosure relates to base stocks, blends of base stocks, formulated lubricant compositions containing the base stocks, and uses of base stocks. This disclosure also relates to methods for improving oxidation performance and low temperature performance of formulated lubricant compositions through compositionally advantaged base stocks.
• This disclosure relates to base stocks and to formulated lubricant compositions containing the base stocks. This disclosure also relates to methods for improving oxidation performance and low temperature performance of formulated lubricant compositions through compositionally advantaged base stocks.
• This disclosure relates in part to a base stock having a kinematic viscosity at 100°C of between about 4 and about 6 cSt.
• These base stocks are also referred to as low viscosity base stocks, low viscosity lubricating oil base stocks or low viscosity products in the present disclosure.
• the base stock comprises greater than or equal to about 90 wt.
• This disclosure further relates in part to a method for improving oxidation performance of a lubricating oil as measured by a rotating pressure vessel oxidation test (RPVOT) by ASTM D2272.
• the lubricating oil comprises a base stock having a kinematic viscosity at 100°C between about 4 and about 6 cSt as a major component; and one or more additives as a minor component.
• the base stock comprises greater than or equal to about 90 wt.
• % saturates an amount and distribution of aromatics, as determined by ultra violet (UV) spectroscopy, comprising an absorptivity between 280 and 320 nm of less than about 0.020 1/gm-cm, preferably less than about 0.015 1/gm-cm; and has a cycloparaffin performance ratio greater than about 1.05.
• the method comprises controlling the cycloparaffin performance ratio to achieve a ratio greater than about 1.1; controlling monocycloparaffinic species greater than about 41 wt. %, based on the total wt. % of all saturates and aromatics; and/or controlling iso-paraffinic species greater than about 21 wt. %, based on the total wt. % of all saturates and aromatics.
• % saturates an amount and distribution of aromatics, as determined by ultra violet (UV) spectroscopy, comprising an absorptivity between 280 and 320 nm of less than about 0.020 1/gm-cm, preferably less than about 0.015 1/gm-cm; and having a cycloparaffin performance ratio greater than about 1.05 and a kinematic viscosity at 100°C between about 10 and about 14 cSt.
• UV ultra violet
• This disclosure further relates in part to a method for improving oxidation performance of a lubricating oil as measured by a rotating pressure vessel oxidation test (RPVOT) by ASTM D2272.
• the lubricating oil comprises a base stock having a kinematic viscosity at 100°C between about 10 and about 14 cSt, a viscosity index (VI) from about 80 to about 120, and a pour point less than about -12°C, as a major component; and one or more additives as a minor component.
• the base stock comprises: at least about 90 wt. % saturates, preferably great than 98 wt.
• FIG. 6 schematically shows an example of a four-stage reaction system according to an alternative embodiment of the disclosure.
• Fig. 16 shows a comparison of the amount and distribution of aromatics, as determined by ultra violet (UV) spectroscopy, in lubricating oil base stocks (i.e., a 4.5 cSt base stock of U. S. Patent application Publication No. 2013/0264246, a 4.5 cSt state of the art base stock as disclosed in U. S. Patent application Publication No. 2013/0264246, a 5 cSt base stock of this disclosure, and a 1 1+ cSt base stock of this disclosure).
• UV ultra violet
• the cycloparaffin performance ratio for base stocks having a kinematic viscosity at 100°C of greater than 8 cSt was calculated as the ratio of monocycloparaffinic (hydrogen deficiency X-class of 0) to multi-ring cycloparaffinic and naphthenoaromatic species (sum of species with hydrogen deficiency X-class of -2, -4, -6, -8 and -10) in said base stock relative to the same ratio in a heavy neutral Group II commercially available sample in 2016 or earlier with a kinematic viscosity at 100 °C within 0.3 cSt as the test sample, wherein the amounts of monocycloparaffinic to multi-ring cycloparaffinic and naphthenoaromatic species are all measured using GCMS on the same instrument at the same calibration.
• the cycloparaffin performance ratio was calculated as the ratio of monocycloparaffinic (hydrogen deficiency X-class of 0) to multi-ring cycloparaffinic and naphthenoaromatic species (sum of species with hydrogen deficiency X-class of -2, -4, -6, -8 and -10) in said base stock relative to same ratio in a light neutral Group II commercially available sample in 2016 or earlier with a kinematic viscosity at 100 °C within 0.3 cSt as the test sample, wherein the amounts of monocycloparaffinic to multi-ring cycloparaffinic and naphthenoaromatic species are all measured using GCMS on the same instrument at the same calibration.
• the absolute value of multi-ring cycloparaffins and naphthenoaromatics as shown in Figs. 9 and 10, rows 15, 16, and 17 of each, for 2+, 3+, 4+ ring cycloparaffins and naphthenoaromatics is lower in the base stocks of this disclosure as compared to commercially known base stocks across the range of viscosities.
• the example base stocks of this disclosure show less than 35.7% species with -2 X- class as shown in Fig. 8, predominantly 2+ ring cycloparaffins and naphthenoaromatics of -2 X- class, less than 11.0% species with -4 X-class as shown in Fig.
• the composition is preferably such that:
• the ratio of monocycloparaffinic (hydrogen deficiency X-class of 0) to multi-ring cycloparaffinic and naphthenoaromatic species (sum of species with hydrogen deficiency X-class of -2, -4, -6, -8 and -10) relative to the same ratio in a similar commercially available hydroprocessed base stock (cycloparaffin performance ratio) is greater than 1.05, or >1.1, or >1.2 or > 1.3 or > 1.4 as measured by GCMS; preferably greater than 1.2, more preferably greater than 1.4, and even more preferably greater than 1.6 as measured by GCMS;
• the sum of all species with hydrogen deficiency X-class of -4, -6, -8 and -10, as measured by GCMS, i.e., 3+ ring cycloparaffinic and naphthenoaromatic species constitute less than 10.5%, or ⁇ 10% or ⁇ 9% or ⁇ 8% of all species; preferably less than 10.5%, more preferably less than 9%, and even more preferably less than 8%;
• the low-viscosity base stock of the present disclosure is used in the engine or other mechanical component oil lubricant composition in an amount ranging from about 50 to about 99 weight percent, preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent, based on the total weight of the composition, or for instance as the sole base oil.
• the lubricating oil base stock composition can be determined using a combination of advanced analytical techniques including gas chromatography mass spectrometry (GCMS), supercritical fluid chromatography (SFC), carbon-13 nuclear magnetic resonance (13C NMR), proton nuclear magnetic resonance (proton-NMR), and differential scanning calorimetry (DSC).
• GCMS gas chromatography mass spectrometry
• SFC supercritical fluid chromatography
• 13C NMR carbon-13 nuclear magnetic resonance
• proton nuclear magnetic resonance proton nuclear magnetic resonance
• DSC differential scanning calorimetry
• the processed high viscosity product from the above described process can also show the unique compositional characteristics described herein. Examples of such Group II high viscosity lubricating oil base stocks having kinematic viscosity at 100°C in the range of 10-14 cSt are described in Fig. 10. For reference, the high viscosity lubricating oil base stocks of this disclosure are compared with typical Group II high viscosity base stocks having the same viscosity range.
• One option for processing a heavier feed is to use hydrocracking to convert a portion of the feed. Portions of the feed that are converted below a specified boiling point, such as a 700°F (371°C) portion that can be used for naphtha and diesel fuel products, while the remaining unconverted portions can be used as lubricant oil base stocks.
• the base stocks of the instant disclosure yield a kinematic viscosity at 100°C of greater than or equal to 2 cSt, or greater than or equal to 4 cSt, or greater than or equal to 6 cSt, or greater than or equal to 8 cSt, or greater than or equal to 10 cSt, or greater than or equal to 12 cSt, or greater than or equal to 14 cSt,.
• This permits the inventive Group II base stocks to be used in host of new lubricant applications requiring higher viscosity than what was attainable with prior art Group II base stocks.
• lower Noack volatility can be achieved over that obtained by conventional catalytic processing without having to take a narrower cut during fractionation.
• the ring opening reactions potentially have the highest selectivity increase relative to the base processing which improves some lubes quality measures (e.g., VI).
• VI lubes quality measures
• this also yields a viscosity retention advantage that is not expected to occur with ring opening.
• This viscosity increase that occurs for Group II base stocks produced by the integrated hydrocracking and dewaxing process disclosed herein is surprising and unexpected.
• the oxidative stability as measured by the RPVOT test (ASTM 11)2272 test for the time in minutes to a 25.4 psi pressure drop) of the lubricant compositions including the inventive Group II base stocks ranges from 820 to 1000, or 875 to 1000, or 875 to 950 minutes.
• the Noack volatility as measured by ASTM B3952 or D5800, Method B test of the Group II base stocks for a KVioo viscosity of at least 10 cSt is less than 4, or less than 3, or less than 2, or less than 1, or less than 0.5 wt. %.
• Typical feeds would include, for example, vacuum gas oils boiling up to about 593°C (about 1100°F) and usually in the range of about 350°C to about 500°. (about 660°F to about 935°F) and, in this case, the proportion of diesel fuel produced is correspondingly greater.
• the sulfur content of the feed can be at least 100 ppm by weight of sulfur, or at least 1000 ppm by weight of sulfur, or at least 2000 ppm by weight of sulfur, or at least 4000 ppm by weight of sulfur, or at least 40,000 ppm by weight of sulfur.
• Particularly preferable feed stock components useful in the process of this disclosure include vacuum gas oil feed stocks (e.g., medium vacuum gas oil feeds (MVGO)) having a solvent dewaxed oil feed viscosity index of from about 20 to about 45, preferably from about 25 to about 40, and more preferably from about 30 to about 35.
• vacuum gas oil feed stocks e.g., medium vacuum gas oil feeds (MVGO)
• MVGO medium vacuum gas oil feeds
• One way to facilitate having a temperature difference between a dewaxing and/or hydrocracking process and a subsequent hydrofinishing process is to house the catalyst beds in separate reactors.
• a hydrofinishing or aromatic saturation process can be included either before or after fractionation of a hydroprocessed feed.
• At least a portion of the effluent from the hydrotreating stage can be sent to a second atmospheric fractionator or separation stage for production of one or more products, such as a second naphtha product and a second jet/diesel product.
• the bottoms fraction from the second separation stage is used as input to a vacuum fractionator or separation stage for production of one or more products, such as a third diesel product, a light lube, and a heavy lube.
• a suitable feedstock 115 is introduced into first reaction stage 110 along with a hydrogen-containing stream 117.
• the feedstock is hydroprocessed in the presence of one or more catalyst beds under effective conditions.
• the effluent 119 from first reaction stage 110 is passed into separation stage 120.
• the separation stage 120 can produce at least a diesel product fraction 124, a bottoms fraction 126, and gas phase fraction 128.
• the gas phase fraction can include both contaminants such as H2S or NH3 as well as low boiling point species such as C1-C4 hydrocarbons.
• the separation stage 120 can also produce a naphtha fraction 122 and/or a kerosene fraction (not shown).
• Fig. 6 shows an example of a general reaction system that utilizes four reaction stages suitable for use in alternative embodiments of the disclosure.
• a reaction system is shown that includes a first reaction stage 310, a first fractionation stage 320, a second reaction stage 330, a second fractionation stage 340, a third reaction stage 350, and an optional fourth reaction stage 360.
• the first reaction stage 310, second reaction stage 330, a third reaction stage 350 and a fourth reaction stage 360 are represented in Fig. 6 as single reactors.
• any convenient number of reactors can be used for the first stage 310, second stage 330, third stage 350 and/or fourth stage 360.
• the second fractionator 450 may produce one or more products, such as a naphtha and LPG product 442, a fuel/diesel product 444, or a lubricant base oil product 446.
• a portion of the first fuel/diesel range material 428 from the first fractionator 420 may be recycled to the third reaction stage 440 via flow line 438 where an improvement in cold flow properties of the fuel/diesel product is desired.
• a portion or all of the first fuel/diesel range material 428 from first fractionator 420 may be recycled to the third reaction stage (see flow line 439).
• the first and second fuel/diesel range materials 439 and 444 may then be combined to form a combined fuel/diesel product 448.
• Hydrotreatment is typically used to reduce the sulfur, nitrogen, and aromatic content of a feed.
• Hydrotreating conditions can include temperatures of 200°C to 450°C, or 315°C to 425°C; pressures of 250 psig (1.8 MPa) to 5000 psig (34.6 MPa) or 300 psig (2.1 MPa) to 3000 psig (20.8 MPa); Liquid Hourly Space Velocities (LHSV) of 0.2-10 h "1 ; and hydrogen treat rates of 200 scf/B (35.6 m /m 3 ) to 10,000 scf/B (1781 m /m 3 ), or 500 (89 m /m 3 ) to 10,000 scf/B (1781 m /m 3 ).
• Preferred 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 /g, or 0.35 to 0.8 cm /g.
• the supports are preferably not promoted with a halogen such as fluorine as this generally increases the acidity of the support.
• the molybenum: tungsten ratio preferably lies in the range of 9: 1-1 :9.
• the Group VIII non-noble metal comprises nickel and/or cobalt.
• the Group VIB metal comprises a combination of molybdenum and tungsten.
• combinations of nickel/molybdenum/tungsten and cobalt/molybdenum/tungsten and nickel/cobalt/molybdenum/tungsten are used. These types of precipitates appear to be sinter-resistant. Thus, the active surface area of the precipitate is maintained during use.
• the metals are preferably present as oxidic compounds of the corresponding metals, or if the catalyst composition has been sulfided, sulfidic compounds of the corresponding metals.
• a hydrofinishing process and an aromatic saturation process can refer to a single process performed using the same catalyst.
• one type of catalyst or catalyst system can be provided to perform aromatic saturation, while a second catalyst or catalyst system can be used for hydrofinishing.
• a hydrofinishing and/or aromatic saturation process will be performed in a separate reactor from dewaxing or hydrocracking processes for practical reasons, such as facilitating use of a lower temperature for the hydrofinishing or aromatic saturation process.
• an additional hydrofinishing reactor following a hydrocracking or dewaxing process but prior to fractionation could still be considered part of a second stage of a reaction system conceptually.
• 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 about 20 weight percent for non-noble metals.
• a preferred hydrofinishing catalyst can include a crystalline material belonging to the M41S class or family of catalysts.
• the M41S 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.
• Elimination of a separation step in the first reaction stage is enabled in part by the ability of a dewaxing catalyst to maintain catalytic activity in the presence of elevated levels of nitrogen and sulfur.
• Conventional catalysts often require pre-treatment of a feedstream to reduce the sulfur content to less than a few hundred ppm.
• hydrocarbon feedstreams containing up to 4.0 wt % of sulfur or more can be effectively processed using the inventive catalysts.
• the total combined sulfur content in liquid and gas forms of the hydrogen containing gas and hydrotreated feed stock can be at least 0.1 wt %, or at least 0.2 wt %, or at least 0.4 wt %, or at least 0.5 wt %, or at least 1 wt %, or at least 2 wt %, or at least 4 wt %.
• Sulfur content may be measured by standard ASTM methods D2622.
• Hydrogen treat gas circulation loops and make-up gas can be configured and controlled in any number of ways.
• treat gas enters the hydrotreating reactor and can be once through or circulated by compressor from high pressure flash drums at the back end of the hydrocracking and/or dewaxing section of the unit.
• make-up gas can be put into the unit anywhere in the high pressure circuit preferably into the hydrocracking/dewaxing reactor zone.
• the treat gas may be scrubbed with amine, or any other suitable solution, to remove H2S and NH3.
• the treat gas can be recycled without cleaning or scrubbing.
• the liquid effluent may be combined with any hydrogen containing gas, including but not limited to H2S containing gas.
• a zeolite having the ZSM-23 structure with a silica to alumina ratio of from about 20: 1 to about 40: 1 can sometimes be referred to as SSZ-32.
• Other molecular sieves that are isostructural with the above materials include Theta-1, NU-10, EU-13, KZ-1, and NU-23.
• the dewaxing catalyst conditions can be similar to those for a sour environment.
• the conditions in a second stage can have less severe conditions than a dewaxing process in a first (sour) stage.
• the temperature in the dewaxing process can be 20°C less than the temperature for a dewaxing process in the first stage, or 30°C less, or 40°C. less.
• One method to achieve lower temperatures in the dewaxing stage is to use liquid quench.
• the catalytic dewaxing catalyst includes from 0.1 wt % to 3.33 wt % framework alumina, 0.1 wt % to 5 wt % Pt, 200: 1 to 30: 1 Si0 2 :Al 2 0 3 ratio and at least one low surface area, refractory metal oxide binder with a surface area of 100 m 2 /g or less.
• monocycloparaffinic species as measured by GCMS, constitute greater than 44% or 46 % or 48 % of all species;
• monocycloparaffinic species as measured by GCMS, constitute greater than 39% or > 39.5% or > 40% or > 41% of all species;
• cycloparaffinic and naphthenoaromatic species i.e., all species with hydrogen deficiency X-class of 0,-2,-4,-6,-8, and -10 constitute ⁇ 73% or ⁇ 72% or ⁇ 71% of all species;
• the ratio of monocycloparaffinic (hydrogen deficiency X-class of 0) to multi-ring cycloparaffinic and naphthenoaromatic species (sum of species with hydrogen deficiency X-class of -2, -4, -6, -8 and -10) relative to the same ratio in a similar commercially available hydroprocessed base stock (cycloparaffin performance ratio) is greater than 1.05, or >l. l, or >1.2, or > 1.3, or > 1.4 as measured by GCMS;
• the base stocks of this disclosure show superior low temperature performance as measured by the MRV apparent viscosity by ASTM D4684 in a 20W-50 automotive engine oil formulation. Finished lube MRV performance measured by ASTM D4684 is correlated by base stock residual wax normally measured by pour point. It has been found, surprisingly, that with base stocks at similar pour points, 25% reduction in finished lube MRV performance measured by ASTM D4684 can be achieved using the base stocks of this disclosure. An example is shown in Fig. 12. Fig.
• the base stocks of this disclosure have a lower multi-ring cycloparaffin and naphthenoaromatic content and a higher monocycloparaffin content that may be contributing to the improvement in low temperature performance. This is surprising because relatively small changes in cycloparaffin and naphthenoaromatic content would not be expected to influence low temperature performance. There is believed to be an interesting distribution of saturated species including cycloparaffins and/or branched long chain paraffins that may be contributing.
• Additional lubricating oil base stocks were produced by co-processing a feed (i.e., a vacuum gas oil feed stock (i.e., a medium vacuum gas oil feed (MVGO)) having a solvent dewaxed oil feed viscosity index of from about 20 to about 45, or a mixed feed stock having a vacuum gas oil feed (e.g., a medium vacuum gas oil feed (MVGO)) to hit conventional VI targets for the low viscosity cut which yielded the low viscosity product with unique compositional characteristics as compared with conventionally processed low viscosity base stocks.
• a feed i.e., a vacuum gas oil feed stock (i.e., a medium vacuum gas oil feed (MVGO)) having a solvent dewaxed oil feed viscosity index of from about 20 to about 45
• a mixed feed stock having a vacuum gas oil feed e.g., a medium vacuum gas oil feed (MVGO)
• the lubricating oil base stock composition was determined using a combination of advanced analytical techniques including gas chromatography mass spectrometry (GCMS), supercritical fluid chromatography (SFC), carbon- 13 nuclear magnetic resonance (13C NMR), proton nuclear magnetic resonance (proton-NMR), ultra violet spectroscopy, and differential scanning calorimetry (DSC).
• GCMS gas chromatography mass spectrometry
• SFC supercritical fluid chromatography
• 13C NMR carbon- 13 nuclear magnetic resonance
• proton nuclear magnetic resonance proton nuclear magnetic resonance
• ultra violet spectroscopy ultra violet spectroscopy
• DSC differential scanning calorimetry
• the co-processed high viscosity product from the above described process also showed the unique compositional characteristics described herein. Examples of such Group II high viscosity lubricating oil base stocks having kinematic viscosity at 100°C in the range of 10-14 cSt are also described in Fig. 15.
• the GC column was connected to the split / split-less injection port (held at 360°C and operated in split-less mode) of the GC.
• Helium in constant pressure mode ( ⁇ 7 PSI) was used for GC carrier phase.
• the outlet of the GC column was run into mass spectrometer via a transfer line held at a 350°C.
• the temperature program for the GC column is a follows: 2 minute hold at 100°C, program at 5°C per minute , 30 minute hold at 350°C.
• the mass spectrometer was operated using an electron impact ionization source (held at 250°C) and operated using standard conditions (70 eV ionization). Instrumental control and mass spectral data acquisition were obtained using the Agilent Chemstation software. Mass calibration and instrument tuning performance validated using vendor supplied standard based on instrument auto tune feature.
• GCMS retention times for samples were determined relative to a normal paraffin retention based on analysis of standard sample containing known normal paraffins. Then the mass spectrum was averaged. A group type analysis of for saturates fractions based on the characteristic fragment ions was performed. The group type analysis yielded the weight % of the following saturate and aromatic molecular types: total cycloparaffins and naphthenoaromatics, 1-6 ring cycloparaffinic species and naphthenoaromatic species, n-paraffins, monomethyl paraffins (i.e., MM paraffins), and dimethyl paraffins (i.e., DM paraffins). This procedure is similar to industry standard method ASTM D2786 - Standard Test Method for Hydrocarbon Types Analysis of Gas- Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry.
• SFC supercritical fluid chromatograph
• a commercial SFC (supercritical fluid chromatograph) system was employed for analysis of lube base stocks.
• the system was equipped with the following components: a high pressure pump for delivery of supercritical carbon dioxide mobile phase; temperature controlled column oven; auto-sampler with high pressure liquid injection valve for delivery of sample material into mobile phase; flame ionization detector; mobile phase splitter (low dead volume tee); back pressure regulator to keep the C02 in supercritical state; and a computer and data system for control of components and recording of data signal.
• a high pressure pump for delivery of supercritical carbon dioxide mobile phase
• temperature controlled column oven auto-sampler with high pressure liquid injection valve for delivery of sample material into mobile phase
• flame ionization detector flame ionization detector
• mobile phase splitter low dead volume tee
• back pressure regulator to keep the C02 in supercritical state
• a computer and data system for control of components and recording of data signal.
• approximately 75 milligrams of sample was diluted in 2 milliliter
• the SFC separation was performed using multiple commercial silica packed columns (5 micron with either 60 or 30 angstrom pores) connected in series (250 mm in length either 2 mm or 4 mm ID). Column temperature was held typically at 35 or 40°C. For analysis, the head pressure of columns was typically 250 bar. Liquid C02 flow rates were typically 0.3 ml/minute for 2 mm ID columns or 2.0 ml/minute for 4 mm ID columns. The samples run were mostly all saturate compounds which will elute before the toluene solvent.
• the SFC FID signal was integrated into paraffin and naphthenic regions.
• a SFC (supercritical fluid chromatograph) was used to analyze lube base stocks for split of total paraffins and total naphthenes. A variety of standards employing typical molecular types can be used to calibrate the paraffin/naphthene split for quantification.

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