WO2020112094A1 - Compositions de combustible marin à faible teneur en soufre - Google Patents

Compositions de combustible marin à faible teneur en soufre Download PDF

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Publication number
WO2020112094A1
WO2020112094A1 PCT/US2018/062694 US2018062694W WO2020112094A1 WO 2020112094 A1 WO2020112094 A1 WO 2020112094A1 US 2018062694 W US2018062694 W US 2018062694W WO 2020112094 A1 WO2020112094 A1 WO 2020112094A1
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Prior art keywords
gas oil
hydrotreated
composition
less
marine
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PCT/US2018/062694
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English (en)
Inventor
Erin R. Fruchey
Scott K. Berkhous
Kenneth C.H. KAR
Sheryl B. RUBIN-PITEL
Aditya S. Shetkar
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Exxonmobil Research And Engineering Company
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Priority claimed from US16/200,884 external-priority patent/US10597594B1/en
Priority claimed from US16/200,901 external-priority patent/US10781391B2/en
Priority claimed from US16/200,858 external-priority patent/US10443006B1/en
Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to CN201880021363.XA priority Critical patent/CN111492040A/zh
Priority to SG11201907793PA priority patent/SG11201907793PA/en
Priority to AU2018411477A priority patent/AU2018411477A1/en
Publication of WO2020112094A1 publication Critical patent/WO2020112094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons

Definitions

  • This invention relates generally to a hydrotreated atmospheric gas oil fraction, and methods for making low sulfur marine bunker fuels using the hydrotreated atmospheric gas oil fraction.
  • ECAs Emission Control Areas
  • the fuels used for larger ships in global shipping are typically marine bunker fuels. Bunker fuels are advantageous since they are less costly than other fuels; however, they are typically composed of cracked and/or resid fuels and hence have higher sulfur levels. Such cracked and/or resid fuels are typically not hydrotreated or only minimally hydrotreated prior to incorporation into the bunker fuel. Instead of attempting to hydrotreat the cracked and/or resid fuels to meet a desired sulfur specification, the lower sulfur specifications for marine vessels can be conventionally accomplished by blending the cracked and/or resid fuels with distillates.
  • distillate fuels While blending with distillate fuels can be effective for reducing sulfur levels, such low sulfur distillate fuels typically trade at a high cost premium for a variety of reasons, not the least of which is the utility in a variety of transport applications employing compression ignition engines.
  • distillate fuels are produced at low sulfur levels, typically significantly below the sulfur levels specified in the IMO regulations.
  • a hydrotreated atmospheric gas oil composition can include a T10 distillation point of 300°C or more, a T90 distillation point of 440°C or less, a sulfur content of 0.03 wt% to 0.6 wt%, a SBN of 40 or less, a pour point of 15°C or more, a difference between the pour point and a cloud point being 10°C or less, and a kinematic viscosity at 40°C of 10.5 cSt to 16 cSt.
  • FIG. 1 shows properties of various fuel oil blends that include a heavy hydrotreated gas oil.
  • FIG. 2 shows properties of several potential blending components for forming a marine gas oil.
  • FIG. 3 shows properties of various blended marine gas oils.
  • marine fuel oil compositions have sulfur contents of 0.5 wt% or less, where the fuel compositions include a substantial portion of a hydrotreated heavy atmospheric gas oil.
  • the hydrotreated heavy atmospheric gas oil can correspond to a gas oil with a relatively low viscosity and an elevated paraffin content in a narrow boiling range which results in a relatively high cloud point and/or pour point. This can make the hydrotreated heavy atmospheric gas oil difficult to use directly as a fuel oil, as heating the gas oil to temperatures above the cloud point can potentially reduce the viscosity to below a desirable level for use as a fuel oil in typical marine engines.
  • the viscosity and the pour point of the hydrotreated heavy atmospheric gas oil can be too high for use as a marine gas oil.
  • the hydrotreated heavy atmospheric gas oil may not meet one or more desired properties for various types of marine fuels
  • the combination of properties for the hydrotreated heavy atmospheric gas oil, in conjunction with a relatively low sulfur content can make such a gas oil beneficial for blending with a variety of other types of fractions to form low sulfur marine fuels (fuel oils or gas oils) with a sulfur content of 0.5 wt% or less, such as a sulfur content of 0.1 wt% to 0.5 wt%.
  • Such other blend fractions can include cracked and/or resid fractions, conventional marine gas oil fraction, and other distillate fractions.
  • the heavy hydrotreated atmospheric gas oil can be used in place of using an automotive diesel fuel as blend component.
  • the resulting compositions can correspond to low sulfur fuel oils under ISO 8217.
  • marine distillate fuel compositions such as marine gas oils
  • the marine distillate fuel compositions have sulfur contents of 0.5 wt% or less, such as 0.05 wt% to 0.6 wt%, or 0.1 wt% to 0.6 wt%, or 0.05 wt% to 0.5 wt%, or 0.1 wt% to 0.5 wt%.
  • the marine distillate fuel compositions can be made in part by blending the hydrotreated heavy atmospheric gas oil with other distillate fractions and/or heavy naphtha fractions.
  • the other distillate fractions and/or heavy naphtha fractions can be used to reduce the pour point and/or cloud point of the marine gas oil.
  • the resulting marine gas oil can correspond to a marine gas oil having properties that satisfy the flash point, cetane index, and kinematic viscosity at 40°C requirements of a DMA or DMB gas oil under ISO 8217, even though 60 wt% or more of the blend components in the resulting marine gas oil do not satisfy such requirements, or 70 wt% or more.
  • the resulting blend can have sufficient solubility to allow for addition of additives for cold flow improvement, such as pour point and/or cold filter plugging point additives.
  • additives for cold flow improvement such as pour point and/or cold filter plugging point additives.
  • such additives are not soluble in sufficient amount to be suitable for use in the hydrotreated heavy atmospheric gas oil alone.
  • one or more additional hydrotreated or non-hydrotreated resid or cracked fractions can also be included in the blend to form the marine fuel composition.
  • one or more additional hydrotreated distillate fractions can be included in the blend to form the marine fuel oil composition.
  • one or more hydrotreated or non-hydrotreated biofuel fractions can be included in the marine fuel oil composition.
  • one or more additives can be included in the blend to form the marine fuel oil composition.
  • marine fuel oils are formed at least in part by using residual fractions. Due to the high sulfur content of many types of residual fractions, some type of additional processing and/or blending is often required to form low sulfur fuel oils (0.5 wt% or less sulfur) or ultra low sulfur fuel oils (0.1 wt% or less sulfur). Conventionally, blending with one or more low sulfur distillate fractions (such as hydrotreated distillate fractions) is typically used to adjust the sulfur content of the resulting blended fuel. Typical distillate blending components can correspond to, for example, fractions suitable for inclusion in an ultra low sulfur diesel pool.
  • blending in a distillate fraction can also modify the viscosity, density, combustion quality (CCAI), pour point, and/or other properties of the fuel. Because having lower pour point and/or viscosity is often beneficial for improving the grade of the marine fuel oil, blending can often be preferable to performing severe hydrotreating on a resid fraction in order to meet a target sulfur level of 0.5 wt% or less.
  • CCAI combustion quality
  • a hydrotreated distillate fraction As an alternative to using a hydrotreated distillate fraction, at least a portion of such a hydrotreated distillate fraction can be replaced with a hydrotreated heavy atmospheric gas oil.
  • the boiling range of the heavy hydrotreated heavy atmospheric gas oil can be relatively narrow, such as having a T10 distillation point of roughly 300°C or more and a T90 distillation point of 440°C or less.
  • a (hydrotreated) heavy atmospheric gas oil fraction with a T10 distillation point of 300°C or more and a T90 distillation point of 440°C or less can represent a challenging fraction to handle in a refinery. This is due in part to the nature of the boiling range.
  • the preferred boiling range for a diesel fuel has a T95 distillation point and/or final boiling point around 650°F ( ⁇ 343°C). While heavier components can potentially be included in a diesel fuel fraction, including such heavier components can potentially degrade the cold flow properties and/or other properties of the diesel fuel.
  • the typical preferred boiling range for a lubricant base stock includes an initial boiling point or T5 boiling point of around 750°F ( ⁇ 399°C).
  • lower boiling components can potentially be included in a lubricant, such lower boiling components can tend to reduce the viscosity and/or increase the volatility of a lubricant base stock. Due to this gap between the end of the desired boiling range for a diesel fuel and the start of the desired boiling range for a lubricant base stock, a distillate fraction that includes a substantial portion of components in the 343°C - 399°C boiling range can be difficult to incorporate into a high value product.
  • One option could be to use a distillate fraction that includes a substantial portion of components in the 343°C - 399°C boiling range as a feed to a cracking process, such as a steam cracking process. While this can be effective for forming naphtha fractions, such additional processing can be costly, and the resulting naphtha fractions are generated by substantially shortening the chain length of the feed.
  • a cracking process such as a steam cracking process.
  • another option could be to try to upgrade such a distillate fraction to form a lubricant base stock. However, such upgrading would likely result in low yield of lubricant after additional costly processing.
  • a distillate fraction containing a substantial portion of components in the 343°C - 399°C boiling can typically have a kinematic viscosity that is too low to be desirable for use as a light neutral lubricant base stock.
  • a distillate fraction can also typically have relatively poor cold flow properties.
  • the sulfur content which can be greater than 1000 wppm versus a typical desirable sulfur content for a lubricant of less than 75 wppm.
  • a lubricant base stock from such a distillate fraction would not only require complex fractionation, but would also require significant hydrotreating for sulfur removal and/or dewaxing to achieve desirable cold flow properties.
  • the combination of fractionation and additional processing would likely result in low yields of lubricant base stock.
  • the fraction can be hydrotreated to reduce the sulfur content to between 0.05 wt% and 0.6 wt%, or 0.05 wt% to 0.5 wt%, or 0.1 wt% to 0.6 wt%, or 0.1 wt% and 0.5 wt%, or 0.3 wt% to 0.6 wt%, or 0.3 wt% to 0.5 wt%, or 0.5 wt% to 0.6 wt%.
  • this level of hydrotreatment can be similar to the type of hydrotreatment that can be performed prior to introducing a feed into a fluid catalytic cracker.
  • the hydrotreating can be performed at relatively mild conditions in the presence of a conventional hydrotreating catalyst, such as a pressure of 1.0 MPa-g to 10.3 MPa-g (or 1.5 MPa-g to 5.5 MPa-g), a weighted average bed temperature of 250°C to 380°C (or 260°C to 350°C), and a liquid hourly space velocity of 0.1 hr 1 to 5.0 hr 1 (or 0.1 hr 1 to 1.0 hr 1 ). It is noted that the temperature at the inlet to the hydrotreating stage may be somewhat cooler than the average bed temperature.
  • This mild hydrotreatment can optionally be performed using a lower purity Fk stream, such as an Fk stream containing 70 vol% to 100 vol% Fk (or 75 vol% to 95 vol%).
  • the hydrotreated effluent can then be fractionated to remove lower boiling products formed by during the hydrotreating process to produce a fraction with a T10 distillation point of 300°C or more, or 310°C or more, or 320°C or more, and a T90 distillation point of 440°C or less, or 430°C or less.
  • the hydrotreated heavy atmospheric gas oil can be characterized based on paraffin content, aromatics content pour point, cloud point, kinematic viscosity, and cetane index. Compositional values can be determined, for example, by gas chromatography, while pour point, cloud point, kinematic viscosity, and density at 15°C can be determined according to typical ASTM methods gas oil fractions. For example, T10 and T90 distillation points can be determined according to ASTM D2887.
  • paraffin content the hydrotreated heavy atmospheric gas oil can have a paraffin content 22% or more, or 25% or more, or 30 wt% or more.
  • n-paraffms can correspond to n-paraffms, or 50% or more. Depending on the aspect, this can correspond to an n-paraffm content (relative to the weight of the hydrotreated heavy atmospheric gas oil) of 12% or more, or 14 wt% or more, or 17 wt% or more. Additionally or alternately, the aromatics content of the hydrotreated heavy atmospheric gas oil can be 45% or less, or 40% or less. Additionally or alternately, the distribution of paraffins in the hydrotreated heavy atmospheric gas oil can be relatively narrow, resulting in a wax end point that is closer than usual to the cloud point. The wax end point can be determined by Differential Scanning Calorimetry.
  • the wax end point can be 42°C or less, or 40°C or less.
  • the hydrotreated heavy atmospheric gas oil can include 30 wt% to 50 wt% of aromatics, or 33 wt% to 45 wt%.
  • the high paraffin content and/or n-paraffm content in combination with a relatively narrow boiling range and/or narrow range of types of paraffins, can result in an elevated cloud point as well as having a relatively similar pour point and cloud point.
  • the hydrotreated heavy atmospheric gas oil can have pour point of 15°C or more, or 18°C or more.
  • the cloud point can be 18°C or more, or 21 °C or more, or 24°C or more.
  • the difference between the pour point and the cloud point can be 10°C or less, or 5°C or less.
  • kinematic viscosity there are several options for characterizing a hydrotreated heavy atmospheric gas oil.
  • One option can be to characterize the kinematic viscosity at temperature, such as a kinematic viscosity at 40°C (KV40), a kinematic viscosity at 50°C (KV50), or a kinematic viscosity at 100°C (KV100).
  • KV40 value can be 10.5 cSt or more, or 11.5 cSt or more, or 12.5 cSt or more, such as up to 16 cSt or possibly still higher.
  • the KV50 value can be 8.5 cSt to 11.5 cSt, or 9.0 cSt to 11.5 cSt, or 9.5 cSt to 11.5 cSt, or 8.5 cSt to 11.0 cSt, or 9.0 cSt to 11.0 cSt, or 9.5 cSt to 11.0 cSt.
  • the KV100 value can be 2.8 cSt or more, or 3.0 cSt or more, such as up to 4.0 cSt or possibly still higher. Another option can be to characterize the temperature at which the hydrotreated heavy gas oil has a kinematic viscosity of 12 cSt, or 15 cSt.
  • the hydrotreated heavy gas oil can have a kinematic viscosity of 12 cSt at 39°C - 45°C, or 41°C - 45°C.
  • the gas oil can have a kinematic viscosity of 15 cSt at a temperature of 33°C to 38°C, or 34°C to 37°C.
  • the viscosity index of the hydrotreated heavy gas oil can be 80 or more, or 90 or more, such as up to 120 or possibly still higher.
  • the density at 15°C for the hydrotreated heavy atmospheric gas oil can be 0.86 to 0.89 g/cm 3 .
  • a marine fuel oil composition as described herein may be used a blendstock for forming marine fuel oils including 0.1 wt% or less of sulfur, or 0.5 wt% or less of sulfur, or 0.1 wt% to 0.5 wt% of sulfur.
  • low sulfur diesel sulfur content of less than 500 ppmw
  • ultra low sulfur diesel sulfur content ⁇ 10 or ⁇ 15 ppmw
  • low sulfur gas oil ultra low sulfur gas oil, low sulfur kerosene, ultra low sulfur kerosene
  • hydrotreated straight run diesel hydrotreated straight run gas oil, hydrotreated straight run kerosene, hydrotreated cycle oil
  • hydrotreated thermally cracked diesel hydrotreated thermally cracked gas oil, hydrotreated thermally cracked kerosene
  • hydrotreated coker diesel hydrotreated coker gas oil, hydrotreated coker kerosene, hydrocracker diesel, hydrocracker gas oil, hydrocracker kerosene, gas-to-liquid diesel, gas-to-liquid kerosene, hydrotreated natural fats or oils such as tall oil or vegetable oil, fatty acid methyl esters, non-hydro
  • a marine distillate fuel composition as described herein may be used a blendstock for forming marine distillate fuels including 0.1 wt% or less of sulfur, or 0.5 wt% or less of sulfur, or 0.1 wt% to 0.5 wt% of sulfur.
  • low sulfur diesel sulfur content of less than 500 ppmw
  • ultra low sulfur diesel sulfur content ⁇ 10 or ⁇ 15 ppmw
  • low sulfur gas oil ultra low sulfur gas oil, low sulfur kerosene, ultra low sulfur kerosene
  • hydrotreated straight run diesel hydrotreated straight run gas oil, hydrotreated straight run gas oil, hydrotreated straight run kerosene, hydrotreated cycle oil
  • hydrotreated thermally cracked diesel hydrotreated thermally cracked gas oil, hydrotreated thermally cracked kerosene
  • hydrotreated coker diesel hydrotreated coker gas oil, hydrotreated coker kerosene, hydrocracker diesel, hydrocracker gas oil, hydrocracker kerosene, gas-to-liquid diesel, gas-to-liquid kerosene, hydrotreated natural fats or oils such as tall oil or vegetable oil, fatty acid methyl esters, non-hydr
  • a mild hydrotreating process can typically be performed on the feedstock.
  • a typical FCC feedstock can correspond to a full range atmospheric gas oil.
  • the feedstock for forming a heavy hydrotreated atmospheric gas oil can have a narrower boiling range. The narrower boiling range can be achieved, for example, by fractionating a full range atmospheric gas oil prior to hydrotreating.
  • the atmospheric gas oil feed Prior to hydrotreating, can have a T90 distillation point of 440°C or less.
  • the T10 distillation point of the atmospheric gas oil prior to hydrotreating can be 250°C or more, or 300°C or more.
  • the hydrotreated narrow atmospheric gas oil can have a T90 distillation point of 440°C or less, or 430°C or less. Additionally or alternately, the hydrotreated narrow atmospheric gas oil can have a final boiling point of 510°C or less. This is in contrast to a conventional hydrotreated feedstock, which can typically have a T90 distillation point greater than 510°C, and can often have a final boiling point above 600°C.
  • a conventional FCC feed can be based on kinematic viscosity. Due in part to the wider boiling range, a conventional FCC feed can typically have a kinematic viscosity at 50°C of 30 or more. By contrast, the hydrotreated narrow atmospheric gas oil can have a kinematic viscosity at 50°C of 8.0 cSt to 10 cSt.
  • the viscosity index of the hydrotreated narrow atmospheric gas oil can be 80 or more, or 90 or more.
  • the pour point of the hydrotreated narrow atmospheric gas oil can typically be 18 or more, or 21 or more.
  • the sulfur content of the hydrotreated narrow atmospheric gas oil can be 0.05 wt% to 0.6 wt%, or 0.1 wt% to 0.5 wt%.
  • the components in a marine fuel oil composition or a marine distillate fuel composition other than the hydrotreated heavy atmospheric gas oil can be present in an amount of 85 vol% or less individually or in total, or 75 vol% or less, or 55 vol% or less, or 35 vol% or less, such as down to 15 vol% or possibly still lower.
  • Examples of such other components can include, but are not limited to, viscosity modifiers, pour point depressants, lubricity modifiers, antioxidants, and combinations thereof.
  • Other examples of such other components can include, but are not limited to, distillate boiling range components such as straight-run atmospheric (fractionated) distillate streams, straight-run vacuum (fractionated) distillate streams, hydrocracked distillate streams, and the like, and combinations thereof.
  • distillate boiling range components can behave as viscosity modifiers, as pour point depressants, as lubricity modifiers, as some combination thereof, or even in some other functional capacity in the aforementioned low sulfur marine bunker fuel.
  • pour point depressants can include, but are not limited to, oligomers/copolymers of ethylene and one or more comonomers (such as those commercially available from Infineum, e.g., of Linden, N.J.), which may optionally be modified post polymerization to be at least partially functionalized (e.g., to exhibit oxygen-containing and/or nitrogen-containing functional groups not native to each respective comonomer).
  • comonomers such as those commercially available from Infineum, e.g., of Linden, N.J.
  • the oligomers/copolymers can have a number average molecular weight (M n ) of about 500 g/mol or greater, for example about 750 g/mol or greater, about 1000 g/mol or greater, about 1500 g/mol or greater, about 2000 g/mol or greater, about 2500 g/mol or greater, about 3000 g/mol or greater, about 4000 g/mol or greater, about 5000 g/mol or greater, about 7500 g/mol or greater, or about 10000 g/mol or greater.
  • M n number average molecular weight
  • the oligomers/copolymers can have an M n of about 25000 g/mol or less, for example about 20000 g/mol or less, about 15000 g/mol or less, about 10000 g/mol or less, about 7500 g/mol or less, about 5000 g/mol or less, about 4000 g/mol or less, about 3000 g/mol or less, about 2500 g/mol or less, about 2000 g/mol or less, about 1500 g/mol or less, or about 1000 g/mol or less.
  • the amount of pour point depressants when desired, can include any amount effective to reduce the pour point to a desired level, such as within the general ranges described hereinabove.
  • a marine fuel oil composition or marine distillate fuel composition can comprise up to 15 vol% (for example, up to 10 vol%, up to 7.5 vol%, or up to 5 vol%; additionally or alternately, at least about 1 vol%, for example at least about 3 vol%, at least about 5 vol%, at least about 7.5 vol%, or at least about 10 vol%) of slurry oil, fractionated (but otherwise untreated) crude oil, or a combination thereof.
  • a variety of blend components can be used to form marine gas oils and marine fuel oils.
  • some suitable blend components for combination with a hydrotreated heavy atmospheric gas oil can be lower boiling, lower viscosity components.
  • a suitable blend component can be a naphtha splitter bottoms stream.
  • a naphtha splitter bottoms stream can have, for example, an initial to final boiling range (or a T5 to T95 boiling range) of 150°C to 200°C.
  • This type of stream can have a sulfur content of less than 0.1 wt%, cloud point of -50°C or less, and a pour point of -60°C or less.
  • the aromatics content of the naphtha splitter bottoms can be 20 wt% or more.
  • the cetane index of such a stream can be less than 42 (or less than 40) and the kinematic viscosity at 40°C can be less than 1.0 cSt.
  • the flash point of a naphtha splitter bottoms can also be relatively low, such as a flash point of 50°C or less, or 40°C or less, such as down to 20°C or possibly still lower. Based on these properties, a naphtha splitter bottoms stream can be unsuitable for use directly as a marine gas oil. However, such properties can provide a complement to the properties of a hydrotreated narrow atmospheric gas oil.
  • Another potential blend component can be a side stream or return stream from a naphtha reformer.
  • a heavier product stream can be formed that has a T10 distillation point of 200°C or more and a T90 distillation point of 320°C or less.
  • Such a stream can primarily include aromatics that are heavier than desirable for inclusion in a gasoline pool.
  • such a stream can be a highly aromatic stream that contains 60 wt% or more aromatics, or 80 wt% or more aromatics. This can result in a low cetane index of 30 or less, or 25 or less.
  • Such a stream can also have a cloud point of -20°C or less and a pour point of -40°C or less.
  • the kinematic viscosity at 40°C for such a stream can be less than 2.0 cSt.
  • a naphtha reformer return stream is too low in cetane index and/or viscosity to be suitable as a marine gas oil
  • such a stream can be a suitable component for blending with a hydrotreated heavy atmospheric gas oil when forming a marine gas oil.
  • Still another potential blending component can be a hydrocracked gas oil.
  • a hydrocracked gas oil can correspond to a conventional blending component for forming various types of distillate fractions, including marine gas oils and/or fuel oils.
  • a hydrocracked gas oil can often have alternative, higher value uses, so the ability to replace some or all of the hydrocracked gas oil in a blend with hydrotreated heavy atmospheric gas oil can be advantageous.
  • conventional marine gas oils can also be a suitable blending component.
  • a hydrocracked gas oil can have a pour point of 0°C to 15°C and a cloud point of 3°C to 18°C.
  • a blended product By blending streams such as naphtha splitter bottoms, catalytic reformer return streams, and/or hydrocracked gas oil with the hydrotreated heavy atmospheric gas oil, a blended product can be formed with the improved flow properties of the naphtha splitter and reformer streams, but with higher viscosity, higher cetane index, and lower volatility of the heavy atmospheric gas oil.
  • three streams that are individually unsuitable as a marine gas oil can be combined to make a stream that can meet the kinematic viscosity, cetane index, and flash point specifications of a DMA or DMB marine gas oil under ISO 8217.
  • Such a blended stream can have a kinematic viscosity at 40°C of 2.0 cSt to 10.0 cSt, or 2.0 cSt to 6.0 cSt, or 6.0 cSt to 10 cSt.
  • the blended stream can have other properties suitable for a marine gas oil, such as a cetane index of 45 or more, or 50 or more, such as up to 65 or possibly still higher; and a flash point of 80°C or more, or 85°C or more.
  • hydrocracked gas oil can also be included in such a blend, so that a combined amount of hydrotreated heavy atmospheric gas oil and hydrocracked gas oil corresponds to 70 wt% or more of the marine gas oil, or 80 wt% or more.
  • cold flow additives can be soluble in the blended stream, to allow for modification of pour point, cloud point, and/or cold filter plugging point.
  • still other additional streams can also be incorporated into the marine gas oil, such as conventional marine gas oil streams, hydrotreated diesel or distillate streams, or other typical blend components that are used to form a marine gas oil.
  • a blend including a hydrotreated heavy atmospheric gas oil can correspond to a blend for forming a marine fuel oil.
  • the high cetane index of a hydrotreated heavy atmospheric gas oil can allow the hydrotreated heavy atmospheric gas oil to be used as a substitute for at least a portion of automotive diesel in a fuel oil blend. This can allow a high value blend component (automotive diesel) to be replaced with a lower value component while still forming a desired grade of fuel oil.
  • a potential blending component for forming a fuel oil can correspond to heavier products generated from a steam cracker processing train, such as a pre-cracker bottoms fraction separated from a crude feed prior to introduction into a steam cracker, or a steam cracker gas oil.
  • a mixture of the pre-cracker bottoms and steam cracker gas oil can correspond to a suitable blend component for forming a fuel oil, when combined with a hydrotreated heavy atmospheric gas oil.
  • the pre-cracker bottoms can roughly correspond to a type of vacuum resid fraction.
  • the steam cracker gas oil can be beneficial for improving the ability of the final fuel oil to maintain solubility of asphaltenes.
  • the asphaltenes in a typical resid fraction could be susceptible to precipitation when mixing the resid with a heavy hydrotreated atmospheric gas oil. This is due in part to the relatively low SBN of a heavy hydrotreated atmospheric gas oil of 40 or less, or 37 or less, or 35 or less, and/or the relatively low BMCI of 30 to 40, or 30 to 37.
  • a mixture of pre-cracker bohoms and steam cracker gas oil can be formed where at least 75 wt% of the mixture, or at least 85 wt%, corresponds to a combination of pre-cracker bohoms and steam cracker gas oil, and at least 45 wt% of the mixture corresponds to the pre-cracker bohoms, or at least 60 wt%.
  • the balance of the mixture can correspond to various types of distillate fractions, such as low sulfur distillate fractions.
  • the properties of such a mixture can vary depending on the crude used as the steam cracker feed, the relative amounts of pre-cracker bottoms and steam cracker gas oil, and the amount of additional distillate in the mixture.
  • Table 1 shows an example of ranges for properties of some types blends of pre-cracker bohoms, steam cracker gas oil, and a minor amount of various distillates. Properties for a hydrotreated heavy atmospheric gas oil (HHAGO) and a marine gas oil are also shown for comparison.
  • HHAGO hydrotreated heavy atmospheric gas oil
  • the mixture can include a) a resid component (such as pre-cracker bohoms) that includes 3.0 wt% asphaltenes or more, or 4.0 wt% or more, or 5.0 wt% or more; b) a high solubility number component (such as a steam cracker gas oil) with an asphaltene content of 0.1 wt% or less, a SBN of 80 or more, or 90 or more, or 100 or more, and a BMCI of 80 or more, or 100 or more.
  • the resulting mixture can have a BMCI of 45 or more, or 50 or more, or 55 or more.
  • the ranges for the blends including the pre-cracker bottoms and the steam cracker gas oil have a relatively low cetane number, but a relatively low pour point and a high BMCI.
  • the hydrotreated heavy gas oil has a higher pour point than a marine gas oil, for purposes of forming a fuel oil, the hydrotreated heavy gas oil can provide similar benefits to using marine gas oil or automotive diesel.
  • TSP refers to total sediment potential, according to ISO 10307-2.
  • BMCI refers to the Bureau of Mines Correlation Index.
  • a method of characterizing the solubility properties of a petroleum fraction can correspond to the toluene equivalence (TE) of a fraction, based on the toluene equivalence test as described, for example, in U.S. Patent 5,871,634 (incorporated herein by reference with regard to the definition for toluene equivalence, solubility number (SBN), and insolubility number (IN)).
  • the calculated carbon aromaticity index (CCAI) can be determined according to ISO 8217.
  • kinematic viscosity ISO 3104
  • boiling range D7169
  • the kinematic viscosity at 50°C can be 5 cSt to 300 cSt, or 5 cSt to 150 cSt, or 15 cSt to 300 cSt, or 15 cSt to 150 cSt, or 25 cSt to 300 cSt, or 25 cSt to 150 cSt.
  • the kinematic viscosity at 50°C can be at least 10 cSt, or at least 15 cSt, or at least 25 cSt. It is noted that fuel oils with a kinematic viscosity at 50°C of 15 cSt or higher can be beneficial, as such fuel oils typically do not require any cooling prior to use in order to be compatible with a marine engine. Additionally or alternately, the boiling range for the marine fuel oil can include a T50 distillation point of 320°C or more, or 340°C or more, or 360°C or more, such as up to 550°C or possibly still higher.
  • the boiling range for the marine fuel oil can include a T90 distillation point of 500°C or more, or 550°C or more, or 600°C or more, such as up to 750°C or possibly still higher.
  • the micro carbon residue of the marine fuel oil can be 5.0 wt% or less, or 4.0 wt% or less, such as down to 0.5 wt% or possibly still lower, as determined according to ISO 10370.
  • Fuel oils 1 and 2 are similar in composition, but substitute hydrotreated heavy atmospheric gas (HHAGO) oil for marine gas oil (MGO).
  • HHAGO hydrotreated heavy atmospheric gas
  • MGO marine gas oil
  • the recipe for Fuel Oils 1 and 2 is comparable to a recipe for forming a 180 cSt fuel oil.
  • Fuel Oils 3 and 4 are related in a similar manner, but with recipes designed to maximize incorporation of hydrotreated heavy atmospheric gas oil or marine gas oil, respectively. It is noted that Fuel Oils 3 and 4 include a portion of both the HHAGO and the MGO.
  • the recipes for Fuel Oils 1, 2, 3, and 4 can be viewed as“bookend” recipes that correspond to addition of roughly minimal and maximal amounts of hydrotreated heavy atmospheric gas oil / automotive diesel to the steam cracker product blends. Of course, other recipes could allow for addition of intermediate amounts.
  • Table 2 shows the fuel oil blend recipes for Fuel Oils 1, 2, 3, and 4.
  • fuel oil blends 1C, 2C, and 3C have an advantage of a higher kinematic viscosity at 50°C, based on the higher kinematic viscosity of the hydrotreated heavy atmospheric gas oil.
  • the data in FIG. 1 show that fuel oils can be formed using a variety of blend recipes that involve a hydrotreated heavy atmospheric gas oil, with amounts of the hydrotreated heavy atmospheric gas oil ranging from 10 wt% to 70 wt% of the fuel oil product.
  • FIG. 2 provides details for several potential blending components for forming a marine gas oil.
  • Column 3 corresponds to a hydrotreated heavy atmospheric gas oil (HHAGO).
  • Column 4 is a distillate fraction that corresponds to a naphtha splitter bottoms fraction (NSB).
  • Column 5 is a distillate fraction that corresponds to a return stream from a catalytic naphtha reformer (CNR).
  • CNR catalytic naphtha reformer
  • These are examples of low sulfur distillate fractions that can be beneficial for improving the cold flow properties of a marine gas oil blend that also includes a hydrotreated heavy atmospheric gas oil.
  • Column 6 corresponds to a hydrocracked gas oil (HCGO), which is a typical type of blend component for use in forming a marine gas oil.
  • Column 7 corresponds to a conventional marine gas oil (MGO).
  • the blending components shown in FIG. 2 were used to form various blends corresponding to potential marine gas oils.
  • Table 3 shows the blend recipes for six potential marine gas oils. Most of the blends in Table 3 correspond to blends where substantial amounts of hydrotreated heavy atmospheric gas oil are used in the recipe. It is noted that the blend recipe for MGO 3 corresponds to addition of small amounts of the naphtha splitter stream and the catalytic reformer return stream to a conventional marine gas oil.
  • MGO 1, MGO 2, and MGO 5 correspond to potential DMB marine gas oils
  • blends MGO 3, MGO 4, and MGO 6 correspond to potential DMA marine gas oils.
  • FIG. 3 shows additional analysis of MGO 1, MGO 2, and MGO 3.
  • FIG. 3 also shows analysis for the conventional marine gas oil used to form MGO 3. Additionally, the final column in FIG. 3 includes the specifications for a DMA marine gas oil under ISO 8217.
  • MGO 1 and MGO 2 have higher kinematic viscosities than MGO 3, based on the relatively high kinematic viscosity of the hydrotreated heavy atmospheric gas oil used to form MGO 1 and MGO 2.
  • MGO 1 and MGO 2 also have a higher pour point than MGO 3.
  • the cetane index, flash point, acid number, and carbon residue are similar to MGO 3, and comparable to the conventional marine gas oil and/or within the specifications of ISO 8217.
  • MGO 1 and MGO 2 are also comparable to the conventional marine gas oil and/or within specification under ISO 8217 with regard to a) insolubles as determined according to ASTM D4625; b) thermal stability under ASTM D6468; and filter blocking tendency under ASTM D2068.
  • FIG. 3 also provides cloud points for MGO 1 (19°C), MGO 2 (19°C), and MGO 3 (5°C). Cloud point values according to D2500 / D5771 were also obtained for the other MGO blends shown in Table 3. MGO 4 had a cloud point of 17°C, MGO 5 had a cloud point of 18°C, and MGO 6 had a cloud point of 15°C.
  • blends formed using a substantial portion of hydrotreated heavy gas oil are potentially suitable for use as marine gas oils.
  • the hydrotreated heavy gas oil is a relatively high viscosity and high boiling blend component
  • blends formed using the hydrotreated heavy atmospheric gas oil can have values within specification for cetane index while also having sufficient stability and sufficiently low values for various types of residue and insolubles.
  • improvement of cold flow properties would be beneficial. It has been unexpectedly discovered that blending hydrotreated heavy gas oil with lighter fractions, such as naphtha splitter bottoms and/or catalytic reformer return streams, can allow cold flow additives to be soluble in the resulting blend. The ability to add cold flow additives can potentially provide sufficient improvements in cold flow properties to allow use of various types of blends as marine gas oils.
  • Table 4 shows a comparison of the pour points for each MGO 1 - MGO 6, along with pour point values after addition of a commercially available cold flow additive.
  • Several different amounts of cold flow additive were investigated, as shown in Table 4.
  • the values in Table 4 were mostly determined according to ASTM D5950, with the exception of the values indicated by a Those values were determined using ASTM D97, which was believed to be comparable to ASTM D5950 for the identified values. It is noted that multiple values were obtained for some blends.
  • the blend corresponding to MGO 3 (primarily commercial marine gas oil, no hydrotreated heavy atmospheric gas oil) had a pour point of -6.0°C without the use of a pour point additive. This is in contrast to the other blends, where the presence of 30% or more of the hydrotreated heavy atmospheric gas oil resulted in a pour point of 12°C or more.
  • the MGO blends including the hydrotreated heavy atmospheric gas oil had comparable pour points to the pour point of MGO 3.
  • pour point additives and/or other cold flow improvers have poor solubility in the hydrotreated heavy atmospheric gas oil prior to blending.
  • the hydrotreated heavy atmospheric gas oil with hydrocracked gas oil, naphtha splitter bottoms, and/or catalytic naphtha return stream, the resulting blend can have sufficient solvating ability to dissolve conventional pour point additives.
  • Table 4 it was unexpectedly found that addition of pour point additives to blends including hydrotreated atmospheric gas oil resulted in pour points comparable to the pour point achieved when starting with a blend including primarily marine gas oil. This is unexpected due to the large difference in pour points between the blends including the hydrotreated heavy atmospheric gas oil and MGO 3, which primarily included a conventional marine gas oil.
  • Embodiment 1 A hydrotreated atmospheric gas oil composition comprising a T10 distillation point of 300°C or more, a T90 distillation point of 440°C or less, a sulfur content of 0.03 wt% to 0.6 wt%, a SBN of 40 or less, a pour point of 15°C or more, a difference between the pour point and a cloud point being 10°C or less, and a kinematic viscosity at 40°C of 10.5 cSt to 16 cSt.
  • Embodiment 2 The composition of Embodiment 1, wherein the composition further comprises a wax end point of 30°C to 45°C (or 32°C to 42°C).
  • Embodiment 3 The composition of any of the above embodiments, wherein the composition comprises a viscosity index of 80 or more (or 90 or more).
  • Embodiment 4 The composition of any of the above embodiments, wherein the composition comprises a cetane index of 50 or more (or 60 or more).
  • Embodiment 5 The composition of any of the above embodiments, wherein the composition comprises a sulfur content of 0.1 wt% or more; or wherein the composition comprises a sulfur content of 0.4 wt% or less; or wherein the composition comprises 0.05 wt% or less of micro carbon residue; or a combination thereof.
  • Embodiment 6 The composition of any of the above embodiments, wherein the composition comprises a paraffins content of 22 wt% or more (or 30 wt% or more); or wherein 40 wt% or more of the paraffins comprise n-paraffins; or a combination thereof.
  • Embodiment 7 The composition of any of the above embodiments, wherein the difference between the pour point and the cloud point is 5°C or less.
  • Embodiment 8 The composition of any of the above embodiments, wherein the composition comprises a kinematic viscosity at 40°C of 14 cSt or less, or wherein the composition comprises a kinematic viscosity at 50°C of 11.5 cSt or less, or a combination thereof.
  • Embodiment 9 The composition of any of the above embodiments, wherein the composition comprises a density at 15°C of 0.86 to 0.89 kg/m 3 .
  • Embodiment 10 The composition of any of the above embodiments, wherein the composition comprises a calculated carbon aromaticity index of 790 to 810, or wherein the composition comprises 30 wt% to 50 wt% aromatics (or 33 wt% to 45 wt%), or a combination thereof.
  • Embodiment 11 The composition of any of the above embodiments, wherein the composition comprises a SBN of 37 or less (or 35 or less); or wherein the composition comprises a BMCI of 40 or less (or 37 or less); or a combination thereof.
  • Embodiment 12 The composition of any of the above embodiments, wherein the composition comprises a sulfur content of 0.3 wt% to 0.5 wt%.
  • Embodiment 13 The composition of any of the above embodiments, wherein the composition comprises a low sulfur fuel oil.
  • Embodiment 14 The composition of any of Embodiments 1 - 13, wherein the composition comprises a sulfur content of 0.5 wt% to 0.6 wt%, the composition optionally comprising a low sulfur fuel oil blendstock.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des compositions de gas-oil hydrotraité lourd, ainsi que des compositions de mazout marin et des compositions de gas-oil marin qui comprennent une partie substantielle de gas-oil atmosphérique lourd hydrotraité. Le gas-oil atmosphérique lourd hydrotraité peut correspondre à un gas-oil ayant une viscosité relativement faible et une teneur élevée en paraffine dans un intervalle de distillation étroit qui résulte en un point de trouble et/ou un point d'écoulement relativement élevé(s).
PCT/US2018/062694 2018-11-27 2018-11-28 Compositions de combustible marin à faible teneur en soufre WO2020112094A1 (fr)

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CN201880021363.XA CN111492040A (zh) 2018-11-27 2018-11-28 低硫船用燃料组合物
SG11201907793PA SG11201907793PA (en) 2018-11-27 2018-11-28 Low sulfur marine fuel compositions
AU2018411477A AU2018411477A1 (en) 2018-11-27 2018-11-28 Low sulfur marine fuel compositions

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US16/200,858 2018-11-27
US16/200,884 US10597594B1 (en) 2018-11-27 2018-11-27 Low sulfur marine fuel compositions
US16/200,901 US10781391B2 (en) 2018-11-27 2018-11-27 Low sulfur marine fuel compositions
US16/200,884 2018-11-27
US16/200,858 US10443006B1 (en) 2018-11-27 2018-11-27 Low sulfur marine fuel compositions
US16/200,901 2018-11-27

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US11879105B2 (en) 2019-03-11 2024-01-23 ExxonMobil Technology and Engineering Company Marine fuel compositions with acceptable wax behavior
CA3216085A1 (fr) * 2021-04-29 2022-11-03 Timothy J. Anderson Compositions de combustible marin ayant un comportement de cire acceptable

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AU2018411477A1 (en) 2020-06-11
WO2020112096A1 (fr) 2020-06-04

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