WO2017218602A2 - Amélioration des propriétés d'huiles de base hydrotraitées - Google Patents

Amélioration des propriétés d'huiles de base hydrotraitées Download PDF

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WO2017218602A2
WO2017218602A2 PCT/US2017/037348 US2017037348W WO2017218602A2 WO 2017218602 A2 WO2017218602 A2 WO 2017218602A2 US 2017037348 W US2017037348 W US 2017037348W WO 2017218602 A2 WO2017218602 A2 WO 2017218602A2
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base oil
hydrotreated
feedstock
solvent
oil feedstock
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PCT/US2017/037348
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WO2017218602A3 (fr
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Thomas George MURRAY
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Murray Extraction Technologies Llc
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Priority to EP17734899.2A priority Critical patent/EP3469043A2/fr
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Publication of WO2017218602A3 publication Critical patent/WO2017218602A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G21/006—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents of waste oils, e.g. PCB's containing 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • the present disclosure relates to further processing of hydroprocessed base oils through subsequent solvent treatment to create improved properties, and more particularly improved low temperature properties, viscosity index, oxidation stability, and volatility properties.
  • Finished lubricants include two general components, lubricating base stocks and additives.
  • Base stocks are made by producers, which may be refiners which make base stocks from crude oil, or re-refiners which make base stocks from used lubricating oils.
  • Lubricating base stock is the major constituent in these finished lubricants and contributes significantly to the properties of the finished lubricant.
  • a few lubricating base stocks are used to manufacture a wide variety of finished lubricants by varying the mixtures of individual lubricating base stocks and individual additives.
  • finished lubricants may be used, for example, in automobiles, diesel engines, axles, transmissions, and a wide variety of industrial applications, motor oil in crankcases of cars and trucks is the largest volume single market for finished lubricants.
  • a base oil is created by blending two or more base stocks together and it is thus generally base oils (e.g. the blended base stocks) which are used to make the finished lubricants.
  • Base oils typically comprise over 70% of the finished lubricant and additives make up the balance.
  • Additives are blended with the selected base oil blend to provide a finished lubricant composition as intended to improve (or "correct") select properties of the finished lubricants.
  • Typical additives include, for example, pour point depressants, anti-wear additives, extreme pressure (EP) agents, detergents, dispersants, antioxidants, viscosity index improvers, viscosity modifiers, friction modifiers, de-emulsifiers, antifoaming agents, corrosion inhibitors, rust inhibitors, seal swell agents, emulsifiers, wetting agents, lubricity improvers, metal deactivators, gelling agents, tackiness agents, bactericides, fungicides, fluid- loss additives, colorants, and the like.
  • EP extreme pressure
  • Viscosity Index is a measure of the degree to which the viscosity of a base oil changes over changes in temperature. Less change is better, and less change correlates to a higher VI number. Viscosity Index Improvers (referred to as VI Improvers) are widely used in making motor oils, serving to maintain a higher thickness of the oil at higher temperatures than would otherwise be the case.
  • VI improvers are not only expensive but they increase lubricant viscosity, thus making it more difficult to achieve low cold cranking viscosities. It is thus advantageous to use base oils of higher Vis (before adding VI Improvers), since this both minimizes additive cost and reduces the amount of correction fluid needed to achieve the cold cranking specification, which requires thinner base oils in the 0W and 5W motor oil grades.
  • Base oils able to be blended into finished lubricants that achieve the 0W and 5W motor oil grade requirements generally require a viscosity level of no greater than 120 SUS (at 100°F) or alternatively measured 4.5 centistokes (at 100°C). At such low viscosity levels the volatility specification of 15% or 13% typically can only be achieved in Group III base oils. Thus, motor oil manufacturers seek base oils with higher Vis and excellent low temperature properties, and additionally low volatility.
  • Finished lubricants must meet the specifications for their intended application as defined typically by the concerned governing organization, although increasingly many equipment manufacturers are creating their own specifications.
  • Motor oil specifications in the United States are set by the International Lubricant Standardization and Approval Committee (ILSAC), a tri-partite group of original equipment manufacturers or OEMs (car and truck manufacturers), additive companies, and base oil producers.
  • ILSAC will periodically issue revised standards for motor oils which are termed GF (for Gasoline Fuel) and are followed by a number, that number currently being 5, and the current GF-5 standards became effective on October 1, 2011.
  • GF-5 stipulates that motor oils must meet the specifications defined in SAE J300 (established by the Society of Automotive Engineers) for 0W, 5W, 10W, and higher multi-grade oils, which include tests for cold cranking viscosity at very low temperatures.
  • the "W” in the grade designations stands for Winter and it defines the cold temperature requirements of the motor oil grade.
  • Low temperature performance is critical for engine oils because of cold temperature conditions that engines are exposed to prior to start-up in various cold climates.
  • a lube oil base stock that provides improved low temperature performance could allow inclusion of lower quality, less expensive co-base stocks or a reduction in the amount of viscosity modifier or pour point depressant in the engine oil formulation.
  • a key measure of low temperature performance is measured by the low- temperature cranking viscosity (cold crank viscosity) as is defined in test method D-5293 ("D" in the test method identifier denotes its approval as an ASTM test method).
  • This test method is abbreviated as CCS (for Cold Crank Simulator) and it is conducted at different temperatures for each grade of lube oil.
  • CCS Cold Crank Simulator
  • Column 2 in Table 1 in SAE J300 shows the Low-Temperature Cranking Viscosity (measured in mPa-s) requirements for grades of motor oil, the most restrictive of which are found on the first two rows, 0W and 5W.
  • the third column shows the Low Temperature Pumping Viscosity (often referred to as the mini-rotary viscometer test, or MRV test, and measured as per D-4684).
  • finished lubricant manufacturers also evaluate other important low temperature characteristics such as pour point (preferably measured as per D-97) and cloud point (preferably measured as per D-2500).
  • An additional low temperature test method is the Brookfield Viscometer Test which measures low temperature viscosity (preferably measured as per D-2983, or "Brookfield Viscosity") and is applied to qualify Automatic Transmission Fluids (ATF's) and hydraulic fluids.
  • Cold cranking viscosity, Brookfield Viscometer Test, MRV test, pour point, and cloud point are referred to herein as comprising "low temperature properties". In each of these instances, a lower number denotes a higher performance level.
  • a cold cranking viscosity of 3,500 is better than 4,000
  • a pour point of -15°C is better than -10°C
  • a cloud point of - 5°C is better than 0°C.
  • Oxidation stability is a further important property of base oils (and in the finished lubricants) as a major goal is to maximize useful life of the lubricant, thus delaying a need for its replacement in the application. Not only does a longer lubricant life represent cost savings from less frequent changes, but it also indicates a higher average level of performance versus time, thus providing better lubrication even while a lubricant is being degraded during use. Therefore oil stability and durability (as indicated by oxidation stability) is of particular importance in evaluation of base oils and in the finished lubricants made from base oils. Oxidation stability, and its associated elements of sludge, deposit and viscosity control, apply in making passenger car motor oil (PCMO), Heavy Duty Engine Oils (HDEOs), and many industrial lubricants.
  • PCMO passenger car motor oil
  • HDEOs Heavy Duty Engine Oils
  • Oxidation stability is defined and measured in numerous tests based on the specific market application of the lubricant. Such tests define standards in base oils or finished lubricants and may be established by equipment manufacturers or by third party organizations. In the GF-5 requirements created by ILSAC which took effect in October 2011 and are applied to PCMOs, no less than 6 (of about 21) tests are directed towards measuring different aspects of oil stability. These tests include: 1. Wear and Oil Thickening (D-7320), 2. Wear, Sludge, and Varnish Test (D-6593), 3. High Temperature Deposits, TEOST MHT (D-7097), 4. High Temperature Deposits TEOST 33C (D-6335), and 5. Aged Oil Low Temperature Viscosity, ROBO Test (D-7528) or 6. Aged Oil Temperature Low Temperature Viscosity (D-7320).
  • oxidation stability is also measured in many other tests including; Determination of Oxidation Stability of Straight Mineral Oils (IP-306), Test of Susceptibility of Ageing According to Baader (DIN 51554), Oxidation Characteristics of Inhibited Mineral Oils (D-943), Determination of the Sludging and Corrosion Tendencies of Inhibited Mineral Oils (D-4310), Oxidation Stability of Steam Turbine Oils by Rotating Pressure Vessel Oxidation Test (RPVOT), (D-2272), Determination of oxidation stability and insolubles formation of uninhibited turbine oils at 120 °C without the inclusion of water (Dry TOST Method) (D-7873), Determination of Oxidation Stability of Inhibited Mineral Turbine Oils (IP-280), 3462 Panel Coker Test (FTM 791A), Standard Test Method
  • API American Petroleum Institute
  • Group VI is a European classification
  • Group III is higher quality than Group II
  • Group II is higher quality than Group I.
  • Group II lube base stocks have much poorer CCS-volatility relationships relative to Group III and Group IV base stocks.
  • the API Base Oil Group classification system defines base oil quality by three criteria: 1) sulfur content (preferably low to reduce harmful emissions), 2) saturates (to improve oxidation stability, reduce sludge and deposit formation, and achieve better Vis and lower volatilities), and 3) viscosity index (VI) (the higher, the better).
  • VI measures the rate of change in viscosity in response to change in temperature. VI is a calculated number relative to reference base oils based on the measurement of viscosity at two temperatures, 40°C and 100°C. A higher VI indicates less viscosity change in response to temperature change, and thus higher quality base oil.
  • Saturates in general (which include both paraffinic and naphthenic compounds, which are also referred to as cyclo-paraffinic compounds) are well known to have a smaller change in viscosity in response to temperature compared with aromatics and polar compounds, and thus have higher Vis. It is thus well known that a higher level of saturates in base oil increases quality as the more saturated base oils achieve higher Vis, although there are distinctions even with the saturates category as noted next.
  • paraffinic compounds are known to have higher Vis than naphthenic components. While paraffinic components are known to have a higher VI than naphthenic compounds, naphthenic compounds are known to have better low temperature properties than paraffinic oils. Whereas VI is calculated based on viscosity measurements at 40°C and 100°C, in contrast (and as noted in Table 1 above) calculation of cold cranking viscosity is measured at -35°C, -30°C, and -25°C, for the grades of 0W, 5W and 10W, respectively. The CCS temperatures of -35°C, -30°C, and -25° C are each far below the 40 C (lowest) temperature used for determining VI.
  • hydroprocessing is used to refer to hydrocracking, hydrotreatment, hydrofinishing, catalytic de-waxing, 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 Figure 1 originates with a Fuels Hydrocracker (e.g.
  • box 160 originates 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 de-waxing-hydrofinishing processing route to base oil production shown in the upper large box. Exxon has continued to produce using its Raffinate Hydroprocessing technologies with some success as well.
  • FIGURE 2 shows the multiple pathways to creating base oils from used lubricating oils.
  • re-refining technologies most commonly apply vacuum distillation (200), thermal de-asphalting (230), or solvent de-asphalting (260), which create one or more intermediate liquids, certain of which are then further upgraded to create marketable base oil, most commonly either by clay treatment, solvent extraction, or hydrotreatment.
  • VGO vacuum gas oil
  • the de-waxing step has the beneficial effect of drastically lowering the pour point of the product by about 120°F.
  • Ashton '067 also notes how hydrotreating and dewaxing the distillate increases VI substantially over that of the feedstock with the heavier fractions increasing their VI dramatically higher than the lighter fractions (68 to 83 versus 90 to 95). It is also noted (in Table VII of Ashton) that solvent refining of the charge (which is a heavy raw wax distillate, 80% of which falls in the boiling range of 880°F to 975°F) will improve the VI from 64 to a range of 92 to 98 across the fractions.
  • solvent treatment is applied to a hydroprocessed base oil stream to create at least one higher product quality stream exhibiting improved low temperature properties.
  • Solvent treatment is preferably applied to separate the hydroprocessed base oil stream into two different streams with virtually zero loss of yield in the total (volume or mass) of the two product streams in the aggregate as compared with the volume or mass of the hydrotreated base oil feed stream (on a solvent free basis).
  • this specification describes two different products created by solvent treatment which are referred to as higher quality product or lower quality product (or stream).
  • a preferable solvent demonstrated to achieve the noted improvements is n-methyl-2-pyrollidone and the preferred process uses ranges for solvent to oil ratio, temperature, pressure and number of stages as disclosed herein.
  • a preferred mode of implementing the invention is to combine the solvent recovery distillation function with a volatility and viscosity control capability thereby extending the functionality of the distillation equipment providing the solvent recovery capability.
  • the invention is applicable to hydroprocessed base oils that have been made from crude oils (aka virgin base oils) and from used lubricating oils (aka re-refined base oils).
  • FIGURES 3 and 4 Block diagrams in which one process of the present invention is applied to hydroprocessed base oils made from crude oil and used lubricating oils are shown in FIGURES 3 and 4, respectively.
  • solvent treatment is applied to a base oil that was prior created by hydroprocessing, most commonly through hydrotreating, but which also may be produced by hydrocracking or hydrofinishing (as well as other hydrogen based technologies).
  • solvent treatment is preferably followed by a fractionation step applied for controlling volatility and enabling creation of products of specific viscosities, with such fractionation step preferably being integrated into the solvent recovery step.
  • FIGURE 1 is a block diagram illustrating each of the three different general pathways and 7 different general routes for creating base lube oils from crude oils.
  • FIGURE 2 is a block diagram illustrating each of the three different general pathways and 9 different general routes for creating base lube oils from used lubricating oils
  • FIGURE 3 is a block diagram illustrating each of the three different general pathways and 7 different general routes for creating base lube oils from crude oils where the instant invention is noted as being implemented as the last step in the processing scheme.
  • FIGURE 4 is a block diagram illustrating each of the three different general pathways and 9 different general routes for creating base lube oils from used lubricating oils where at least one embodiment of the present invention is noted as being implemented as the last step in the processing scheme and only in the instance where the base oil has first received hydrotreatment.
  • FIGURE 5 is a block diagram showing a preferred mode for implementing the solvent extraction step on a hydroprocessed base oil processed through a solvent extraction column and with raffinate and extract streams shown having removal and recovery of solvent as well as generation of the higher quality and lower quality product streams.
  • FIGURE 6 presents a chart and table showing analytical results for the higher and lower product quality streams were created when the process of at least one embodiment of the present invention was applied to a virgin hydroprocessed base oil (Purity 1003 from Holly -Frontier/PetroCanada).
  • FIGURE 7 presents a chart and table showing analytical results for the higher and lower product quality streams were created when the process of at least one embodiment of the present invention was applied to a virgin hydroprocessed base oil (HCC 150 from Heritage Crystal Clean).
  • HCC 150 virgin hydroprocessed base oil
  • FIGURE 8 is a block diagram showing how the raffinate (or extract) is passed to a first solvent recovery column with residual passed to a second solvent recovery column, which second solvent recovery column preferably also includes volatility and viscosity control functions.
  • hydroprocessing is used herein to refer to hydrocracking, hydrotreatment, hydrofinishing, catalytic de-waxing, 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. While streams and products created by other hydroprocessing technologies may also provide suitable feedstocks for the present disclosure, and the invention is thus not limited to processing only hydrotreated base oils, a preferred hydroprocessing technology for creating feedstock for at least one embodiment of the present invention is hydrotreatment (also referred to as hydrotreating).
  • Preferred process conditions for hydrotreating as contemplated in the present disclosure are preferably in the general ranges of 450°F to 700°F, and 600 psig to 1,500 psig. These process conditions preferably result in a loss of less than 10% of the lube fraction, and more preferably result in a loss of less than 5% of the lube fraction, and most preferably result in a loss of less than 2% of the lube fraction, with the lube fraction being defined as a range in which the majority of the liquid to be hydrotreated has boiling points from 550°F to 1050°F (these are atmospheric equivalent temperatures as this distillation will occur under vacuum to avoid cracking).
  • Hydrotreatment achieves improvement in color, reduction in hetero-atoms (sulfur, nitrogen, and oxygen), and conversion of unsaturated components (such as aromatics) to saturates (such as naphthenes). Many of the conversions from aromatics to saturates create naphthenic components, and hydrotreatment also may result in naphthene ring opening and isomerization, thus converting some naphthenes to paraffins, and some paraffins to iso-paraffins.
  • a preferable solvent is n-methyl-2-pyrollidone (nMP) although other solvents may be utilized.
  • Solvent to oil ratio ranges preferably include 0.3 to 10.0, more preferably include 0.5 to 5.0, and most preferably include 1.0 to 2.0, temperature ranges preferably include 25°C to the lesser of the boiling point of the solvent (under the pressure conditions being applied), more preferably include 50°C to 150°C (or the lesser of the boiling point of the solvent under the applicable pressure conditions), and most preferably include 60°C to 90°C (or the lesser of the boiling point of the solvent under the applicable pressure conditions).
  • Pressure conditions can range from vacuum (for example as may be applied in the case of extractive distillation) to ambient and beyond up to any pressure as may be applied to maintain intimate mixing of the solvent and the feedstock in a phase as best promotes the desired results of the applied process.
  • the number of theoretical stages of the extraction column preferably falls in the range of 1 to 10, more preferably in the range of 2 to 8, and most preferably in the range of 5 to 7.
  • solvent treatment is defined as applying one or more solvents which will: (a) preferentially remove naphthenic, aromatic, polar, and/or waxy compounds from a hydrotreated base oil (as in the case of a solvent applied in solvent extraction) or (b) alternatively remove paraffinic compounds from a hydrotreated base oil (as in the case of a solvent removing paraffinic compounds as applied in solvent de-asphalting), or (c) use a combination of both (a) and (b) approaches.
  • the combination of the two approaches described in (c) may be any sequence of first (a) then (b), or first (b) then (a), or both (a) and (b) may be applied together simultaneously.
  • solvent treatment will preferably include two solvents, namely a preferentially selective naphthenic/aromatic/polar/waxy solvent and a preferentially selective paraffinic solvent.
  • the solvent or solvents are preferably applied at different entry points to a contactor, extractor, centrifuge, extraction column (including a Scheibel Column), distillation column, or other device, which preferably promotes separation of material by molecular weight and gravitational or centrifugal force. Where a column is utilized then the preferred mode is to operate the solvent and oil counter currently.
  • dual solvents Under the operating conditions of the process, wherever two solvents (referred to herein as “dual solvents”) are employed such dual solvents will preferentially not be miscible with each other but will instead preferentially have increased affinity for enhancing or detracting components which each is either removing or acting as a replacement for, such as for example paraffinic components in the case of one solvent, and aromatic/polar/naphthenic/waxy components in the case of the other solvent.
  • temperature can have a particularly significant impact wherein two solvents which are substantially immiscible at one temperature are substantially miscible at another temperature.
  • all solvents are preferably recovered from the product streams and re-used in the process.
  • the terms "constituents", “compounds”, and “components” are used interchangeably.
  • FIGURE 5 the hydroprocessed base oil 500 is introduced and charged to solvent extraction column 505 at connection point 504 which preferably occurs in a lower section of solvent extraction column 505.
  • a solvent for example preferably nMP
  • connection point 503 which preferably is positioned in an upper section of solvent extraction column 505.
  • the solvent in this instance is heavier and thus it falls down through Solvent Extraction Column 505 passing counter-currently by Hydroprocessed Base Oil 500 which, being lighter, is rising up Solvent Extraction Column 505.
  • the solvent As the solvent passes by and mixes with Hydroprocessed Base Oil 500, the solvent preferentially attracts impurities out of Hydroprocessed Base Oil 500, with such impurities preferentially being aromatics, napthenes, and/or waxy components.
  • the Hydroprocessed Base Oil 500 after rising to the top of the column, has had its impurities substantially removed and then is called raffinate.
  • Raffinate 515 the solvent is distilled overhead and recovered and returned via Solvent Recycle 520 for entry into Solvent Extraction Column 505 at connection point 503.
  • the solvent after descending to the bottom of Solvent Extraction Column 505, then has collected all the impurities and is then called extract.
  • Extract 530 the solvent is distilled overhead and recovered and returned via Solvent Recycle 522 for entry into Solvent Extraction Column 505 at connection point 503. Not shown is a small makeup of solvent over time as solvent is passed out with the products. However, in a properly designed and constructed unit, solvent losses are preferably extremely low (on the order of parts per million).
  • the liquid that remains is passed as stream 540 and becomes a higher product quality base oil 550.
  • the solvent is removed from the extract, the liquid that remains is passed as stream 535 and becomes lower product quality base oil 545.
  • Raffinate 515 and Extract 530 may be one or more distillation columns in series and also are preferably capable of additional functions beyond just solvent recovery as is described in further detail below with respect to FIGURE 8.
  • the improvement in the low temperature properties was accompanied by a favorable increase in the viscosity index in the ranges of 3 to 4 VI points (higher VI increases were achieved in alternative modes of operating but this data is not reported) and without a materially negative impact on volatility.
  • the lower quality product which is about 15% yield of the feedstock
  • cold crank viscosities were increased, and thus it was degraded versus the feedstock.
  • the lower quality product remained a highly marketable base oil suitable for use in many applications.
  • surprisingly favorable effects on pour point and cloud point in certain of the higher quality and the lower quality products were generally observed as well.
  • indicatively oxidation stability in the higher product quality stream is increased by removal of the less stable aromatic and naphthenic compounds as a result of the solvent extraction process which created the higher VI product.
  • Filtration processes are readily available at commercial scale so as to achieve a similar result as was achieved with the bench scale filtration apparatus that removed the haze and cloudiness from the lower quality stream. It may be that any favorable impact on the pour point and cloud point in the lower quality product noted above was enhanced by the filtration step which removed the cloudy elements which appeared in the lower quality products after applying the solvent extraction step to the hydrotreated base oils. For example, these cloudy elements could be waxy elements that are then removed with a filtration step. The filter paper was weighed before and after filtration and it showed a minimal increase in weight relative to the amount of the filtered product. So whatever was removed was a very small portion of the lower quality product stream.
  • Table 3 shows the analytical results achieved by applying principles of the present invention to two feedstocks, the first a re-refined hydrotreated base oil feedstock available from Heritage Crystal Clean called "HCC 150", and the second a virgin hydrotreated base oil feedstock available from PetroCanada (now owned by Holly-Frontier) called "Purity 1003".
  • HCC 150 a re-refined hydrotreated base oil feedstock available from Heritage Crystal Clean
  • PetroCanada now owned by Holly-Frontier
  • Volatility is a measure of the extent of an oil to vaporize in use, with a common test method used to measure volatility being the NOACK ASTM test D-5800.
  • the NOACK test measures the amount of oil that has vaporized when a sample is heated to 242°C under a 20 mm vacuum, following a 1 hour period in which air is blown across the sample at a fixed rate.
  • the higher volatility (light ends) are removed from the starting sample and the difference in weight between the starting and ending samples is the measure of volatility.
  • an additional capability for volatility control as applied in the distillation of the solvent is preferably included, and is now disclosed, as an element of one embodiment of the present invention. This is achieved by designing in further capability into a distillation column which is used in the solvent recovery step after the extraction step is first performed. By doing this, volatility of the higher or lower quality products can be adjusted by removing a small portion of the light base oils and a small portion of the heavier portion of this same light base oil.
  • the viscosities can be adjusted by designing the distillation column not only for removal (and recovery) of solvent (and volatility control), but also for fractionation into viscosities as are suited for the specific market application. By doing this, multiple products can be created using a column that would otherwise be used solely for solvent recovery. By incorporating the ability to adjust at least one of volatility and viscosity of the products into a solvent recovery section, capital cost and operating cost savings may be achieved. For example, modifying a traditional design for a column that is used solely for solvent recovery will reduce the capital cost of adding a further column solely for product viscosity or volatility adjustment.
  • FIGURE 8 illustrates a raffinate (which could separately be an extract stream) stream 800 being charged to a distillation column 810 for purposes of recovery of some of the solvent in stream 840.
  • the material not proceeding overhead 835 (this is the raffinate stream with some of the solvent removed) is then charged to a second distillation column 820 whereupon virtually all remaining solvent is removed and recovered in stream 845.
  • the next heavier fraction depicted in the second distillation column 820 is a Spindle Oil stream 850 as a side draw, as is the next heaver fraction being a Light Base Oil 855.
  • the residual is shown as a Medium or Heavy Base oil stream 860.
  • the column is designed to remove the lighter ends from the Light Base Oil 855 (which then becomes part of the Spindle Oil 850) and to ensure the viscosity target is still met, a portion of the heavier liquid contained in Light Base Oil 855 is instead portioned into Medium or Heavy Base Oil 860 (thus increasing the yield of the Medium or Heavy Base Oil).
  • At least one process of the present invention must improve the VI of the raffinate to a sufficient degree that the volatility control and viscosity fractionation functions can then be preferentially and beneficially applied; in this way the solvent treatment and fractionation processes of at least one embodiment of the present invention are dependent upon each other.
  • the above noted fractionation step can have certain variations, some of which are described next. While the above design presents two columns in series, in some instances it may be preferable to design the process for a single column processing stream 700. In addition, the further volatility control and viscosity fractionation functions (which are in addition to solvent recovery) described above may be included for processing of either or both of the higher and lower product streams should volatility or viscosity control be desired in either of the raffinate or extract streams. Furthermore, in FIG. 8, the products presented are a spindle oil, light base oil, and medium base oil, but the creation of fewer or more products can be designed as alternate configurations to suit specific market requirements.
  • each of solvent recovery, volatility control, and viscosity targeting for specific market applications may all be afforded at reduced capital and operating costs.
  • Proper design of fractional distillation columns is well known and functional design elements needed to achieve not only solvent recovery but also volatility and viscosity control, are achievable as described above if engineered by one of ordinary skill in the art.
  • a particularly unexpected outcome of practicing at least one embodiment of the invention was achieving both a large improvement in low temperature properties of the higher quality product relative to that of the feedstock and a simultaneous improvement in the Viscosity Index (VI) in the higher quality product, also relative to that of the feedstock.
  • VI Viscosity Index
  • the result is unexpected because it is known that higher paraffinic content will result in an increased VI and it was further assumed, since the hydrotreated base oils were almost fully saturated, that the VI improvement being achieved could only occur by reducing the proportion of naphthenes in the higher quality product, there presumably being very little (if any) aromatics left in the feedstock to remove. However, it is also known that naphthenes exhibit better low temperature properties than paraffins.
  • a further item to be reconciled is that waxy compounds are known to increase VI, and so if their removal caused a better result in the cold crank viscosity in the higher quality stream that should also have been accompanied by a worst result in the VI of the higher product quality stream. But that too did not happen. Further investigation into why solvent extraction of hydrotreated base oil created both improved low temperature properties and higher VI in the higher quality products requires compositional analysis of the proportions of paraffins (including n and iso-paraffins), naphthenes (including more particularly proportional content by number of rings), residual wax components, as well as any aromatics (or non-technically described, any quasi-aromatic- naphthenes) that may be drawn into the lower quality product through the solvent treatment step applied according to principles of the present disclosure.
  • paraffins including n and iso-paraffins
  • naphthenes including more particularly proportional content by number of rings
  • residual wax components as well as any aromatics (or non-technically described, any quasi-aromatic- naphthenes)
  • a major goal of lubricant improvements is to extend and maximize the useful life of the lubricant, thus delaying a need for its replacement in the application. Not only does a longer lubricant life represent cost savings from less frequent changes, but it also indicates a higher average level of performance versus time, thus providing better lubrication even while a lubricant is being degraded during use. To achieve a longer duration of the lubricant, it must have strong oxidation stability and this is measured and is thus an additional important property of base oils.
  • compositional improvement in the higher product quality stream of one embodiment of the present invention forecast improvement in the oxidation stability of the higher product quality stream.
  • the present invention is not limited to any particular solvent in the solvent treatment process, or catalyst in the hydroprocessing steps, since feedstocks and process conditions may vary and principles of the present invention may be applied in many varied modes.
  • Solvents are also known for selectively separating aromatics, polars, and other undesirable base lube oil constituents from desirable base lube oil constituents.
  • Preferred solvents typically comprise N-methyl-2-pyrollidone, furfural, phenol, and the like. The optimum solvent may be selected based upon its effectiveness in the process as discussed above, but an alternate approach may be to utilize other solvents known for their preferential selectivity for removing paraffinic components.
  • Such preferred solvents typically comprise propane, acetone, hexane, heptane, isopropyl alcohol, and the like.
  • the optimum solvent may be selected based upon its effectiveness in the solvent treatment process as it may be applied as described according to principles of the present invention or in any alternate embodiment.

Abstract

L'extraction au solvant est appliquée à une huile de base hydrotraitée pour créer au moins un flux de produit de qualité supérieure et au moins un flux de produit de qualité inférieure, le ou les flux de produit de qualité supérieure comprenant une amélioration sur l'huile de base hydrotraitée dans au moins une propriété parmi l'indice de viscosité, les propriétés à basse température, la volatilité et la stabilité à l'oxydation par rapport à celle de la charge d'alimentation.
PCT/US2017/037348 2016-06-13 2017-06-13 Amélioration des propriétés d'huiles de base hydrotraitées WO2017218602A2 (fr)

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US3414506A (en) 1963-08-12 1968-12-03 Shell Oil Co Lubricating oil by hydrotreating pentane-alcohol-deasphalted short residue
US3617476A (en) 1969-04-10 1971-11-02 Texaco Inc Lubricating oil processing
US3691067A (en) 1970-03-04 1972-09-12 Texaco Inc Production of lubricating oils by hydrotreating and distillation
US4085036A (en) 1976-10-01 1978-04-18 Gulf Research & Development Company Process of hydrodesulfurization and separate solvent extraction of distillate and deasphalted residual lubricating oil fractions

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GB1256842A (fr) * 1969-05-22 1971-12-15
US3652448A (en) * 1969-06-30 1972-03-28 Texaco Inc Production of improved lubricating oils
US3702817A (en) * 1970-10-06 1972-11-14 Texaco Inc Production of lubricating oils including hydrofining an extract
ZA726049B (en) * 1971-09-07 1973-06-27 Sun Oil Co Pennsylvania Composition comprising stabilized hydrocracked lube and an antioxidant
JPH07116452B2 (ja) * 1986-06-23 1995-12-13 株式会社ジャパンエナジー 高芳香族基油の製造法
BR9303997A (pt) * 1993-10-01 1995-05-30 Petroleo Brasileiro Sa Processo para produção de óleos librificantes básicos de altos índices de viscosidade e óleo diesel de alto número de cetano
US5976353A (en) * 1996-06-28 1999-11-02 Exxon Research And Engineering Co Raffinate hydroconversion process (JHT-9601)
AR032930A1 (es) * 2001-03-05 2003-12-03 Shell Int Research Procedimiento para preparar un aceite de base lubricante y gas oil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414506A (en) 1963-08-12 1968-12-03 Shell Oil Co Lubricating oil by hydrotreating pentane-alcohol-deasphalted short residue
US3617476A (en) 1969-04-10 1971-11-02 Texaco Inc Lubricating oil processing
US3691067A (en) 1970-03-04 1972-09-12 Texaco Inc Production of lubricating oils by hydrotreating and distillation
US4085036A (en) 1976-10-01 1978-04-18 Gulf Research & Development Company Process of hydrodesulfurization and separate solvent extraction of distillate and deasphalted residual lubricating oil fractions

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