WO2019014681A2 - Production d'huiles de base de haute qualité - Google Patents

Production d'huiles de base de haute qualité Download PDF

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Publication number
WO2019014681A2
WO2019014681A2 PCT/US2018/042323 US2018042323W WO2019014681A2 WO 2019014681 A2 WO2019014681 A2 WO 2019014681A2 US 2018042323 W US2018042323 W US 2018042323W WO 2019014681 A2 WO2019014681 A2 WO 2019014681A2
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vgo
group
oil
processing
solvent extraction
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WO2019014681A3 (fr
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Thomas George MURRAY
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Murray Extraction Technologies LLC
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Murray Extraction Technologies LLC
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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
    • C10G67/0454—Solvent desasphalting
    • C10G67/0463—The hydrotreatment being a hydrorefining
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/003—Distillation of hydrocarbon oils distillation of lubricating oils
    • 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
    • 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

Definitions

  • the invention relates generally to base oils and, more particularly, to a process for producing high quality and low quality base oils from used lubricating oils and crude oils.
  • Viscosity Index is a measure of an oil's change in viscosity in response to a change in temperature, where a lower change is better, and which corresponds to a higher number.
  • such higher quality base oils are generally described as Group II and Group III base oils, relative to Group I which are the lowest quality base oils.
  • the divisions between Groups I, II and III are based on the levels of sulfur, saturates, and viscosity index, as noted in Table 1 below.
  • All of Groups I, II and III are derived from crude (mineral) oils as compared to Groups IV and V which are produced as petrochemicals (ultimately most being made from natural gas, or its derivatives).
  • crude oil also known as virgin base oils
  • crude oil is first distilled in an atmospheric column and then the bottoms from the atmospheric column pass to a vacuum column, in which a distillate referred to as Vacuum Gas Oil (“VGO”) is produced.
  • VGO Vacuum Gas Oil
  • CO-VGO Vacuum Gas Oil
  • Viscosity is the single most important characteristic of base oil (and lubricants in general). Viscosities of base oils are closely correlated with their boiling ranges. VGOs suited for making base oils have atmospheric equivalent boiling ranges from 550°F on the low end to 1050°F on the high end, although the majority of all base oils carry an atmospheric equivalent boiling range from 650°F on the low end to 1050°F on the high end (unless noted otherwise, all temperatures referenced herein are atmospheric equivalent boiling points).
  • VGOs may be produced which have boiling points below 550°F but, for making base oils, it is preferred that liquids that boil below 550°F be removed prior to processing, as these lighter viscosity liquids are suited for diesel, kerosene (used in making jet fuel), and gasoline versus base oils, which require thicker viscosities for their applications.
  • Base oils produced from VGO with boiling ranges from 550°F or 650°F up to 1050°F have viscosities generally ranging from about 50 to 70 and up to 700 to 750 Saybolt Universal Seconds (“SUS”) at 100°F, or alternatively measured from about 4 to 14 centistokes at 100°C. Viscosities falling in the ranges from 100 to 120 SUS and from 200 to 240 SUS are commonly used in manufacturing PCMOs and HDEOs, respectively. Heavier viscosities of 300 to 800 are most commonly used in making industrial lubricants.
  • SUS Saybolt Universal Seconds
  • FIGURE 1 shows the three general pathways by which CO-VGO is processed into Group I, II or III base oils.
  • the first pathway depicted within dashed outline 100, starts with solvent extraction and then the raffinate produced from solvent extraction is further processed by solvent de-waxing and hydrofinishing to produce Group I base oils (the lowest quality).
  • a Group I plant is thus defined as a facility which primarily processes crude oil and, with respect to the base oils that are produced, produces primarily Group I base oil.
  • Group I plants utilize process technologies including solvent extraction, dewaxing (which can be any of solvent dewaxing, catalytic dewaxing, and isodewaxing), and hydrofinishing.
  • Group I plants typically will produce valuable by-products.
  • many Group I plants also use solvent de-asphalting of vacuum column bottoms produced in processing crude oil (referred to in the present invention as CO-VCB) which produces DAO as well as an asphaltic material (DAO made from crude oil is referred to herein as CO-DAO).
  • DAO is a very thick material that, with further processing, is made into bright stock. Bright stock generally has viscosities of about 2500 SUS at 100°F or, alternatively measured, about 32 centistokes at 100°F.
  • the solvent de-waxing process shown in FIG. 1 will produce various wax products.
  • dewaxing As many Group I plants have shut down, the supply of bright stock and wax has decreased, which has served to increase the prices of bright stock and wax, and to increase the value of Group I plants still operating. Increased revenues from sale of bright stock and wax products have partially offset a decline in price and volume demanded for Group I base oils. As a result, the useful lives of many Group I plants have been extended longer than if they had been wholly dependent upon selling just Group I base oil.
  • Other dewaxing technologies include catalytic de-waxing and iso-dewaxing, neither of which typically produces wax by-products. Together, solvent de-waxing, catalytic de-waxing, and iso-dewaxing are referred to herein as "dewaxing", a “dewaxing step”, or "dewaxing technologies.”
  • hydroprocessing is used to refer to hydrocracking, hydrotreatment, hydrofinishing, catalytic dewaxing, and iso-dewaxing as well as any associated technologies which apply hydrogen and catalysts under conditions of temperature, pressure, and residence times to achieve improvement in the feedstock.
  • Box 130 in FIG. 1 begins with a Fuels Hydrocracker (e.g.
  • box 160 begins with a Lube Hydrocracker (e.g., targeted for making lube oils).
  • Lube Hydrocracker e.g., targeted for making lube oils.
  • each of these two pathways will make higher quality Group II and Group III base oils.
  • the advanced hydroprocessing technologies shown in boxes 130 and 160 are now the dominant processes used for making base oils, substantially displacing the traditional solvent extraction, solvent dewaxing, hydrofinishing processing route to Group I base oil production shown in the upper large box. Exxon has continued to produce large volumes of base oils using its raffinate hydroprocessing technologies with some success as well.
  • FIGURE 2 shows the multiple pathways for creating re-refined base oils.
  • Vacuum distillation of used lubricating oils produces an intermediate liquid which is a distillate referred to as vacuum gas oil ("VGO").
  • VGO vacuum gas oil
  • UO-VGOs produced from used lubricating oils that are PCMOs or HDEOs will have higher Vis, whereas UO-VGOs produced from used lubricating oils generated in industrial applications and railroads will have lower Vis. Since used lubricating oils may be derived from industrial uses or from PCMO or HDEO, the Vis of UO-VGO vary widely based on the type of used lubricating oil from which the UO-VGO was produced.
  • re-refining technologies most commonly apply vacuum distillation (200), thermal de-asphalting (230), or solvent de- asphalting (260), which produce one or more intermediate liquids, certain of which are then further upgraded to produce a marketable base oil, most commonly either by clay treatment, solvent extraction, or hydrotreatment.
  • Vacuum distillation (which generally occurs after atmospheric distillation) efficiently removes both lighter boiling point liquids and very heavy asphaltenes (1050 + °F boiling point) and is the most common initial step in re-refining to make UO-VGO. Thermal de-asphalting will also produce a UO-VGO, but it materially cracks the used lubricating oil which degrades the quality of the intermediate liquid, thus creating poor yields and lower quality base oils.
  • UO-VCB Solvent de-asphalting of vacuum column bottoms produced from used lubricating oils
  • DAO de-asphalted oil
  • hydrotreating and to a lesser extent solvent extraction, have become the preferred processing technologies for upgrading UO-VGO into re-refined base oils, as subsequent processing steps following vacuum distillation, thermal de-asphalting or solvent de-asphalting.
  • Hydrotreatment also referred to herein as "hydrotreating" is commonly applied in re-refining under processing severities ranging, in temperature from about 500 °F to 700°F, in pressure from about 600 to 1,500 psig, and in space velocities from about 0.5 to 2.0.
  • Hydrotreating of UO-VGO is now capable of producing re-refined base oil with Vis in excess of 110, saturates well in excess of 90%, and sulfur and nitrogen below 200 ppm, thus creating a higher quality Group II base oil.
  • Conversion of aromatics and polar compounds to saturates in hydrotreatment is primarily dictated by temperature, residence time, and pressure (leaving aside catalyst selection, hydrogen purity, and hydrogen flow rate) with implications for base oil yields and capital cost.
  • temperature there is an upper bound on temperatures above about the 650°F to 700°F range where increased residence time results in increased cracking and thus yield loss and coking of hydrotreating catalysts.
  • residence time can be increased (or alternatively stated, space velocity lowered), but there is a practical limit on results that can be achieved by increased residence time without increasing cracking.
  • Reaction dynamics limit product improvement to temperatures and residence times above which net conversion of aromatics and polars to saturates starts to reverse, thereby actually increasing aromatics and polars.
  • Group I plants are increasingly being relegated to industrial applications where VI, sulfur, and saturates are not key determinants of suitability.
  • applications where Group I base oils still dominate over Group II and Group III base oils include process oils, gear oils, general industrial oils, metalworking fluids, and the like.
  • Such markets are still substantial and in total equal about 50% of all finished lubricants sold, but a large surplus of Group I production makes it increasingly difficult to sell Group I.
  • Woodle '476 discloses a sequence involving first applying mild hydrogenation, followed by solvent refining and dewaxing.
  • the mild hydrogenation conditions include a pressure not greater than 600 psig and the patent notes a highest VI achieved of 111, thus not even achieving Group II+.
  • Such mild process hydrogenation conditions are incapable of achieving levels of de-aromatization, de-sulfurization, and de-nitrification demanded by today's higher quality finished lubricant specifications.
  • the cited advantages of this approach are creation of higher yields of base oils by upgrading the extract stream to becoming a marketable base oil, ability to source and process used lubricating oils of varied quality levels and still produce high yields of high quality products, reducing the level of capital expenditure afforded by hydrotreating only the extract stream, and finally, creating a Group III base oil.
  • MacDonald does not explain if the produced Group III base oil was derived from the raffinate (which was not hydrotreated) or the extract stream (which was hydrotreated along with the diesel), nor does MacDonald disclose the high sulfur or poor color of the raffinate stream (which is the majority of the base oil output) which is associated with solvent extraction and which will negatively and materially impact the value and marketability of such base oils.
  • a further approach that has been applied to produce higher valued products has been blending base oils of varied quality levels together to take advantage of quality disparities.
  • U.S. Patent No. 8,480,879 issued to Rosenbaum et al. in July 2013 discloses a process for blending a Fischer-Tropsch (gas-to-liquids technology) product with a base oil that does not meet Group I base oil specifications to make a product that achieves a Group I base oil and has a high viscosity index, low pour point, excellent oxidation stability, and potentially low volatility. While this approach does not involve hydrotreating or solvent extraction, it shows that combining two very different streams together can improve the quality of an otherwise off-spec and very low value material.
  • Another example of blending is U.S.
  • Patent No. 7,838,471 issued to Shirazi et al. in November 2010 which exhibits combining a Group II and Group IV base oil together to produce a base oil that meets or exceeds the criteria for SAE Grade 0W multi-grade engine oils, which represent the most challenging specifications to meet and which are currently typically met only by Groups III and IV base oils. While again not involving hydrotreating or solvent extraction, this patent shows how two relatively high end products (Groups II and IV base oils) can be combined to target the market application of a third high end product (Group III) where that third high end product is currently the most commonly used component in meeting the most challenging specification that currently exists in the PCMO lubricant market. Blending of disparate quality products thus has satisfied product specifications that would otherwise typically be addressed by process technologies such as hydro-processing or solvent extraction.
  • the present invention accordingly, provides a process for creating high yields of higher quality base oils (e.g., Group III or Group II), as well as low yields of lower quality base oils (e.g. , Group II or Group I), from used lubricating oils and crude oils.
  • Vacuum gas oils produced from used lubricating oils and from crude oils are processed via two or more process steps, including solvent extraction, solvent or catalytic or iso-dewaxing, and hydrotreating.
  • Such process enables efficient conversion and operation of refineries formerly capable only of making Group I base oils, even as their ability to make heavier base oils, waxes, and bright stocks is substantially preserved, to the same general extent as such products had been made prior to undertaking the conversion.
  • Group I base oil plants are under pressure due to an increase in demand for higher quality Group II and Group III base oils in many finished lubricant applications, including most notably automobile (PCMO) and truck (HDEO) lubricants as two very large applications where engines have been improved markedly in recent years.
  • PCMO automobile
  • HDEO truck
  • the existing solvent extraction, solvent de-asphalting, dewaxing, and hydrofinishing technologies which make Group I base oils from crude oils cannot make Group II and III base oils from crude oils.
  • fundamental changes in how a Group I plant is designed, constructed, and operated are needed to upgrade its capabilities to making Group II and III base oils.
  • the UO-VGO produced from the used lubricating oil may achieve a VI of 90 or more (a VI in the range of 90 to 100 is most typical of Group I base oils).
  • the UO-VGO feedstock be derived from used oils made from PCMO and HDEO as much as possible. This is preferably measured by measuring the VI of the UO-VGO derived from the gathered used lubricating oil.
  • sourcing used lubricating oils whose UO-VGOs achieve Vis of 90 or above. If used oils can be sourced where the Vis of their associated UO-VGOs are 95, 100, 105, 110, or even 115 or more, then this is progressively more preferable.
  • UO-VGOs generally have lower viscosities (i.e. , they are thinner) compared with the average CO-VGO made from crude oils. The reason is that UO-VGOs tend to reflect the lower viscosities common to PCMOs and HDEOs, in the range of 100 to 250 SUS (at 100°F), whereas CO-VGOs on average may have higher viscosities when processing heavier crude oils as are common crude oil sources for many refineries.
  • hydrofinishing as used in Group I base oil plants, applies milder process severities in the range of 600 to 800 psi or even 1,000 psi, and less than 600°F to 700°F.
  • Such pressures and temperatures are typically not able to achieve the levels of hydro- desulfurization (HDS), hydro-denitrification (HDN), and hydro-dearomatization (HDA) as are demanded for applications requiring Group II and Group III base oils, even with UO- VGO Vis of 90 and above.
  • HDS hydro- desulfurization
  • HDN hydro-denitrification
  • HDA hydro-dearomatization
  • sulfur levels preferably less than 300 ppm, more preferably less than 150 ppm, and most preferably less than 10 ppm, and,
  • nitrogen levels preferably less than 300 ppm, more preferably less than 150 ppm, and most preferably less than 10 ppm, and,
  • c. saturates levels of preferably greater than 90%, more preferably greater than 95%, and most preferably greater than 99%
  • viscosity indexes preferably greater than 105, more preferably greater than 110, and most preferably greater than 115.
  • the levels of aromatics and polar compounds in UO-VGO is lower than in CO-VGO and more particularly when the solvent extraction step is applied to processing a UO-VGO that has first been hydrotreated, the levels of aromatics and polars are even lower still, often being under 5% or even under 1%. Accordingly, in processing UO-VGO that has first been hydrotreated, it is preferable that lower solvent-to-oil ratios ranging from 0.8 to 3. Ox be applied, more preferable that solvent-to-oil ratios of l.Ox to 2. Ox be applied, and most preferable that solvent-to-oil ratios of 1.3x to 1.8x be applied in order to achieve the optimum combination of yields and product quality.
  • balancing processing severities in solvent extraction unit and hydrotreating may be expressly controlled so as to achieve an optimum or desired product quality and yield result, but such a balancing can only occur when the VGO is being processed by means of both hydrotreating and solvent extraction (but in either sequence).
  • This capability is particularly important as it can enable hydrotreatment severities to be reduced to take advantage of the positive benefits of solvent extraction, which will then result in less cracking and creation of lower valued by-products (such as fuels and non-condensable gases, which are of low or no value).
  • the processing sequence generally applied is first solvent extraction followed by dewaxing and then hydrotreating.
  • the processing sequence will preferably not include dewaxing at all.
  • the sequence is preferably hydrotreating first followed by solvent extraction, but the sequence may be reversed. It is preferable to first hydrotreat and then utilize solvent extraction as this maximizes the product quality that will be passed to the solvent extraction unit with the result that both the raffinate and extract streams from the solvent unit will then preferably become highly marketable base oils.
  • this configuration allows hydrotreatment of only one stream (such as either UO-VGO or CO-VGO) versus two streams (such as raffinate and extract). This also serves to increase total yield of higher quality product since most of the lower quality molecules that are passed to the solvent extraction unit have already been substantially upgraded during hydrotreating.
  • the effluent from hydrotreating UO-VGO (before solvent extraction) that falls in the base oil boiling range (that then passes to solvent extraction) is preferably in excess of 80%, more preferably in excess of 85%, and most preferably in excess of 90%.
  • the base oils in the raffinate stream are preferably in excess of 65%, more preferably in excess of 75%, and most preferably in excess of 85%, of the hydrotreated effluent that falls in the base oil boiling range.
  • the vast majority of these raffinate base oils are preferably then processed to become Group III, with only a small minority of these thus becoming Group II (the Group II portions are generally the most low viscosity base oils falling in the range of 50 to 80 SUS).
  • the majority (if not all) of this preferably becomes a Group II base oil, which itself is of a very high quality.
  • the extract stream in Group I base oil plants processing CO-VGO by means of solvent extraction (which occurs before dewaxing and hydrofinishing), will generally not even be Group I (instead typically being a lower valued fuel stream or a hydrogen deficit feed to make gasoline, diesel, and jet fuels), and it can be up to 40% of the CO-VGO.
  • the present invention allows the full range of selection as to the proportions of CO-VGO and UO-VGO processed through the plant at any given point in time.
  • the preferred design for the plant offers the flexibility to run either all CO-VGO, all UO-VGO, or some portions of CO-VGO and UO-VGO blended together (e.g., Blended VGO), as a key element of the present invention. Since processing CO-VGO as before will enable creation of bright stock and wax products, there is thus no impairment of capability to produce these valuable products while the CO-VGO is being run, even after the conversion of the Group I base oil plant as described herein.
  • the present invention provides a number of advantages over conventional technology, including the following:
  • FIGURE 1 is a schematic diagram of multiple pathways to produce base oils from crude oils in accordance with the prior art.
  • FIGURE 2 is a schematic diagram of multiple pathways to produce base oils from using lubricating oils in accordance with the prior art.
  • FIGURE 3 is a schematic diagram exemplifying a preferred embodiment of the invention where CO-VGO is processed in a substantially similar way as per the traditional sequence in making Group I base oils, and UO-VGO is processed in a preferred sequence of hydrotreating before solvent extraction in making Group III base oils.
  • FIGURE 4 is a schematic diagram exemplifying a first alternative embodiment of the invention where CO-VGO and UO-VGO may be blended together and processing occurs in which hydrotreating precedes solvent extraction.
  • FIGURE 5 is a schematic diagram exemplifying a second alternative embodiment of the invention where CO-VGO and UO-VGO may be blended together and the processing occurs where solvent extraction precedes hydrotreating, thus necessitating a blocked out configuration which requires storage of intermediate raffinate and extract liquids.
  • FIGURES 6A, 6B, and 6C exemplify three distinct modes in which CO- VGO and UO-VGO may be processed either singly, or in blended form as achieved by gate valves, a blending (proportional) valve, or check valves.
  • FIGURE 3 presents a preferred configuration in which CO-VGO is processed using the traditional solvent extraction, solvent dewaxing (which could be catalytic dewaxing), and hydrofinishing sequence.
  • solvent dewaxing which could be catalytic dewaxing
  • hydrofinishing sequence When UO-VGO is being run, the assumption in FIG. 3 is that the hydrofinishing has preferably been upgraded to hydrotreating, if and as needed the solvent extraction unit has also been upgraded, and that an additional fractionation capability may optionally be added so as to provide continuous fractionation of both the higher valued (primarily Group III) stream and the lower valued Group II stream.
  • FIG. 3 thus assumes that CO-VGO and UO-VGO will each be run separately through the plant at different times (i.e., blocked out).
  • the solid lines represent processing of CO-VGO and the dotted lines represent processing of UO-VGO.
  • CO-VGO 300 is charged first to solvent extraction unit 311, and the extract (which is a low value stream) is then generated as stream 313. Also charged to solvent extraction unit 311 is CO-DAO 307 generated by solvent de-asphalting unit 305, which has been generated from the vacuum column bottoms CO-VCB 303. The separate or blended processing of UO-VCB 304 is presented as a further option from which is then generated UO-DAO 308 which is passed to solvent extraction unit 311. Also generated in solvent de-asphalting unit 305 are one or more asphalt-like products shown as CO- Asphalt 309 and UO- Asphalt 310.
  • hydrotreating unit 317 are produced by removal of these wax compounds from the raffinate (or converted by catalytic dewaxing or iso-dewaxing). Thereafter the raffinate after removal (or conversion) of the waxy compounds becomes dewaxed oil which is passed to hydrotreating unit 319.
  • hydrotreating 319 a small volume of naphtha, kerosene, and diesel (along with sulfur in the form of H2S) is generated.
  • the majority of the product is passed to fractionation unit 323 where the stream is fractionated in the proper viscosities which are denoted as stream Group II 325. Included in Group II 325 will thus be base oils of different viscosities along with bright stock which has primarily been recovered through the stream called CO- DAO 307 (and prospectively UO-DAO 308), generated by solvent de-asphalting unit 305.
  • UO-VGO is first passed to hydrotreater 319 (upgraded from hydrofinishing).
  • the hydrotreated UO-VGO is then passed as stream 359 to solvent extraction unit 311, thus bypassing solvent dewaxing step 316.
  • the dewaxing step is preferably not applied because the UO-VGO has been made from used lubricating oils which have already been dewaxed).
  • an alternative embodiment is processing CO-VGO in solvent dewaxing unit 516 and generating wax products and dewaxed oil, with such dewaxed oil being available for processing in other units as have available capacity.
  • Solvent extraction unit 311 then produces two streams, the first of which is unfractionated Groups III and II 367 generated from the raffinate and the second of which is unfractionated Group II 363 generated from the extract.
  • hydrotreating 319 a small volume of naphtha, kerosene, and diesel (along with sulfur in the form of H2S) is also generated as stream 370.
  • Each of the two unfractionated base oil streams 367 and 363 are then passed to their respective fractionation columns 323 and 373.
  • fractionation column 323 leads to creation of Group III and Group II base oils labeled as stream 376 and fractionation column 373 leads to creation of Group II base oils 379.
  • FIGURE 4 presents an alternate configuration in which CO-VGO and UO- VGO may either be run separately or blended in varied proportions (e.g. Blended VGO) and then processed together under a hydrotr eating, solvent dewaxing (which could instead be catalytic dewaxing or iso-dewaxing), solvent extraction processing sequence.
  • Running a Blended VGO is depicted by means of a proportional valve (425 in FIG. 4).
  • the function of a proportional valve is to allow either of two alternative feedstocks to be run through the plant individually and exclusively, or to allow for any proportions of the two alternative feedstocks to be combined together and then run through the plant as a blend.
  • FIG. 4 assumes that hydrofinishing is preferably upgraded to hydrotr eating, if and as needed the solvent extraction unit has also been upgraded, and an additional fractionation capability may optionally be added so as to provide continuous fractionation of both the higher valued (primarily Group III) stream and the lower valued (Group II) stream.
  • FIG. 4 thus assumes that CO-VGO and UO-VGO will be run through the plant at the same time, but in varied proportions as desired.
  • the solid lines represent processing of CO-VGO and the dotted lines represent additional processing associated with the addition of UO-VGO.
  • FIG. 4 depicts processing each of the CO-VGO and UO-VGO, or Blended VGO, through the dewaxing unit.
  • CO-VGO 400 and UO-VGO 450 are charged via proportional valve 425 to hydrotreating unit 419.
  • CO-DAO 407 generated by solvent de-asphalting unit 405, which has been generated from vacuum column bottoms CO-VCB 403.
  • UO-DAO 408 generated from solvent extraction unit 411.
  • Also generated in solvent de-asphalting unit 405 are one or more asphalt-like products shown as CO-Asphalt 409 and UO-Asphalt 410.
  • hydrotreating 419 a small volume of naphtha, kerosene, and diesel (along with sulfur in the form of H2S) is also generated as stream 470. Because most CO-VGOs contain waxy compounds, after hydrotreating in hydrotreating unit 419, the hydrotreated oil is then passed to solvent dewaxing (which may instead be catalytic dewaxing or iso-dewaxing), whereupon wax products 417 are produced by removal of these wax compounds from the hydrotreated oil (or converted by catalytic dewaxing or iso-dewaxing).
  • solvent dewaxing which may instead be catalytic dewaxing or iso-dewaxing
  • the dewaxed (and already hydrotreated oil) is then passed to solvent extraction unit 411.
  • the raffinate stream 467 from solvent unit 411 is then passed to fractionation unit 423 where raffinate stream 467 is fractionated in the proper viscosities which are denoted as Groups III and II base oils 476.
  • the extract stream 463 from solvent extraction unit 411 is then passed to fractionation unit 473 where extract stream 463 is fractionated in the proper viscosities which are denoted as Group II base oils 479.
  • fractionation units 423 and 473 Included in either of the heavier streams produced by fractionation units 423 and 473 will be the bright stock which has primarily been recovered through the stream called CO-DAO 407, generated by solvent de-asphalting unit 405. Also included in products produced by fractionation units 423 and 473 will be heavier viscosity base oils which are inherent within CO-VGO which tend to be higher viscosity than the base oils found in most UO-VGOs.
  • FIGURE 5 presents an alternate configuration in which CO-VGO and UO- VGO may either be run separately, or blended in varied proportions and run as Blended VGO processed together under a solvent extraction, solvent dewaxing (which could instead be catalytic dewaxing or iso-dewaxing), hydrotreating processing sequence.
  • solvent dewaxing which could instead be catalytic dewaxing or iso-dewaxing
  • hydrotreating processing sequence is preferably upgraded to hydrotreating, and, if and as needed, the solvent extraction unit has also been upgraded. Because each of the CO-VGO and the raffinate and extract streams may be run blocked out, additional fractionation capability may not be required (and FIG. 5 does not show any additional fractionation).
  • FIG. 5 allows for Blended VGO to be run through the plant at the same time, but in varied proportions as desired.
  • the solid lines represent processing of CO-VGO and the dotted lines represent additional processing associated with the addition of UO-VGO.
  • An explanation of processing for the CO-VGO and UO-VGO streams as shown in FIG. 5 follows under three different scenarios. The first scenario is where only CO- VGO is processed. The second scenario is where only UO-VGO is processed. The third scenario is where both CO-VGO and UO-VGO are blended and then processed in some proportions (referred to herein as "blended VGO"). As noted previously, such flexibility is presented in the present invention by means of a proportional valve.
  • CO-VGO 500 is charged via proportional valve 525 to solvent extraction unit 511, and the extract (which is a low value stream) is then generated as stream 513.
  • CO-DAO 507 generated by solvent de-asphalting unit 505, which has been generated from vacuum column bottoms CO-VCB 503.
  • UO-DAO 508 generated from solvent extraction unit 511.
  • One or more asphalt-like products are also generated in solvent de-asphalting unit 505 shown as CO-Asphalt 509 and UO-Asphalt 510.
  • the raffinate from solvent unit 511 is then passed to solvent dewaxing step
  • hydrotreating unit 517 are produced by removal of these wax compounds from the raffinate (or converted by catalytic dewaxing or iso-dewaxing). Thereafter the raffinate after removal (or conversion) of the waxy compounds becomes dewaxed oil which is passed to hydrotreating unit 519.
  • hydrotreating 519 a small volume of naphtha, kerosene, and diesel (along with sulfur in the form of H2S) is generated.
  • the majority of the product is passed to fractionation unit 523 where the stream is fractionated in the proper viscosities which are denoted as stream Group II 579. Included in Group II 579 will thus be base oils of different viscosities along with bright stock which has primarily been recovered through the stream called CO- DAO 507 (and prospectively UO-DAO 508), generated by solvent de-asphalting unit 505.
  • raffinate stream 541 is passed directly from solvent extraction unit 511 (or raffinate is passed from Intermediate Raffinate Storage 545), it is then processed in hydrotreater 519 whereupon it becomes Unfractionated Groups III and II 567. Unfractionated Groups III and II 567 is then passed to fractionation unit 523 whereupon it is fractionated into its products by viscosity and becomes Groups III and II Products 576.
  • extract stream 553 is passed directly from solvent extraction unit 511 (or extract is passed from Intermediate Extract Storage 555), it is then processed in hydrotreater 519 whereupon it becomes Unfractionated Group II 563.
  • Unfractionated Group II 563 is then passed to fractionation unit 523 whereupon it is fractionated into its products by viscosity and becomes Group II Products 579.
  • a small volume of naphtha, kerosene, and diesel (along with sulfur in the form of H2S) is also generated as stream 570.
  • the Group II products in stream 576 will most likely be higher VI than the Group II products in stream 579, even though each will be processed in fractionation column 523 (preferably run blocked out so as not to commingle the higher VI and lower VI base oils together).
  • solvent dewaxing unit 516 processes CO-VGO and generates wax products and dewaxed oil, with such dewaxed oil being available for processing in other units as have available capacity.
  • scenario 3 in FIG. 5 (Blended VGO) is illustrated by assuming the starting feedstock mix is 100% UO-VGO, but that CO-VGO is increased as a % of the feedstock, and then viewing the preferred mode of operating the invention.
  • the sequence of the solvent extraction unit 511 prior to hydrotreater 519 necessitates the utilization of intermediate storage 545 and 555 as the raffinate and extract must be processed in separate blocks.
  • FIGURES 6A, 6B, and 6C depict several means of valve assemblies which enable the two feedstocks to be processed individually or in blended mode through a blending valve (FIG. 6A), gate valves (FIG. 6B), or check valves (FIG. 6C).
  • a blending valve FIG. 6A
  • gate valves FIG. 6B
  • check valves FIG. 6C
  • the blending valve 605 FIG. 6A
  • either of the CO-VGO 600 or UO-VGO 601, or some blend of the two may be processed passing through to gate valve assembly manifold 607 in which the material may then be passed along any of three different pathways.
  • gate valves 625 and 610 allow either of the CO-VGO 620 or UO-VGO 621, respectively, or some blend of the two, to be processed passing through to gate valve assembly manifold 627 in which the material may then be passed along any of three different pathways.
  • centrifugal pumps 635 and 645 allow either of the CO-VGO 630 or UO-VGO 631, respectively, or some blend of the two, to be processed passing through check valves 640 and 650, respectively, to gate valve assembly manifold 637 in which the material may then be passed along any of three different pathways.
  • a preferred mode of the present invention may be to run CO- VGO and UO-VGO separately and further to run processing of each in the sequence of hydrotreating and then solvent extraction, followed by fractionation, using dewaxing when CO-VGO is being processed in sufficient quantities to generate material amounts of wax products. It is thus also a preferred mode of the current invention that when most or all feedstock being processed is UO-VGO, or CO-VGO which has minimal wax compounds, that the dewaxing unit is bypassed as this will save operating cost and is not expected to result in a material loss of wax product creation. In such times, the dewaxing unit can alternatively be used for processing CO-VGO.
  • processing CO-VGO through the hydrotreater 519 first before dewaxing and solvent extraction may produce benefits in product quality or yield (or reduced operating) cost.
  • this configuration where hydrotreating precedes solvent extraction, along with the addition of a fractionation column, avoids block treating the raffinate and extract streams separately.
  • FIGS. 3 and 4 would then be the preferred mode for processing CO-VGO (but this is not depicted).
  • Many such variations may be considered obvious and desirable by those skilled in the art based upon a review of the foregoing description of the preferred embodiments that are described in this specification.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un processus de création d'huiles de base de meilleure qualité supérieure et de qualité inférieure à partir d'huiles lubrifiantes et d'huiles brutes usagées, les huiles de base de qualité supérieure pouvant être des huiles de base de groupe III ou de groupe II et les huiles de base de qualité inférieure pouvant être des huiles de groupe II ou de groupe I. Des gazoles sous vides produits à partir d'huiles lubrifiantes usagées et à partir d'huiles brutes sont traités par le biais de deux étapes de traitement ou plus, comprenant l'extraction de solvant, le déparaffinage de solvant ou catalytique ou iso, et l'hydrotraitement. Un tel processus permet une conversion et un fonctionnement efficaces de raffineries qui ne pouvaient auparavant que fabriquer des huiles de base de groupe I, même si leur capacité à fabriquer des huiles de base plus lourdes, des cires, et des bright stocks est conservée, sensiblement dans la même mesure où de tels produits ont été réalisés avant l'entreprise de la conversion.
PCT/US2018/042323 2017-07-14 2018-07-16 Production d'huiles de base de haute qualité Ceased WO2019014681A2 (fr)

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US62/532,935 2017-07-14
US16/036,120 2018-07-16
US16/036,120 US20190016973A1 (en) 2017-07-14 2018-07-16 Production of High Quality Base Oils

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EP4495213A1 (fr) * 2023-07-18 2025-01-22 SK Innovation Co., Ltd. Procédé de production d'une huile de base lubrifiante comprenant une fraction d'huile usée raffinée, et huile de base lubrifiante ainsi produite

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US10421916B2 (en) * 2017-11-30 2019-09-24 Vertex Energy System for producing an American Petroleum Institute Standards Group III Base Stock from vacuum gas oil
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
KR102442618B1 (ko) 2021-08-17 2022-09-14 에스케이이노베이션 주식회사 폐윤활유 정제 유분을 활용한 고품질 윤활기유 제조 공정
EP4689011A1 (fr) * 2023-04-04 2026-02-11 ExxonMobil Technology and Engineering Company Élimination de composés aromatiques et polaires dans des charges d'alimentation de lubrifiant par extraction liquide-liquide à contre-courant à l'aide de dihydrolévoglucosénone en tant que solvant
KR20250012981A (ko) 2023-07-18 2025-01-31 에스케이이노베이션 주식회사 폐윤활유 정제 유분을 활용한 윤활기유 제조 공정 및 이에 의해 제조되는 윤활기유
KR20250012982A (ko) * 2023-07-18 2025-01-31 에스케이이노베이션 주식회사 폐윤활유를 재활용하는 방법
WO2026039209A1 (fr) * 2024-08-16 2026-02-19 ExxonMobil Technology and Engineering Company Co-traitement d'huile lubrifiante usagée pour produire des huiles de base du groupe ii/iii
WO2026039184A1 (fr) * 2024-08-16 2026-02-19 ExxonMobil Technology and Engineering Company Co-traitement d'huile lubrifiante usagée pour augmenter la production d'huile de base ii/iii du groupe ii/iii

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BR0215816B1 (pt) * 2002-07-15 2012-11-27 processo para a refinação de óleos de petróleo usados por extração com solventes alifáticos.
US8366912B1 (en) * 2005-03-08 2013-02-05 Ari Technologies, Llc Method for producing base lubricating oil from waste oil

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Publication number Priority date Publication date Assignee Title
EP4495213A1 (fr) * 2023-07-18 2025-01-22 SK Innovation Co., Ltd. Procédé de production d'une huile de base lubrifiante comprenant une fraction d'huile usée raffinée, et huile de base lubrifiante ainsi produite
US12606755B2 (en) 2023-07-18 2026-04-21 Sk Innovation Co., Ltd. Method of producing lube base oil and lube base oil produced thereby

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