Classifications

• • 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
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
• • 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
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
• • 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
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• This disclosure relates to residual marine fuels containing a blend of at least one residual fraction and at least one fraction including a fatty acid alkyl ester.
• Typical marine fuels have sulfur content above the new regulatory limits because sulfur contaminants are concentrated in the heavy fractions of crude oil (“residue”) used for marine fuel blending.
• Typical solutions for reducing sulfur in marine fuels include desulfurization and dilution of high sulfur residue with a low-sulfur blend component, referred to as a “flux,” which is often a distillate.
• Desulfurization is expensive and carbon-intensive because it requires substantial energy and hydrogen. Dilution is commonly used, but it can destabilize residual marine fuel and promote sediment and sludge formation.
• Residue contains asphaltenes that are typically kept in solution by a high concentration of aromatic molecules in the fuel. However, the distillate fuels used as flux are generally much less aromatic than residue, and dilution of a residue with a typical distillate flux can cause the asphaltenes to precipitate.
• a fuel or fuel blending composition can include 20 vol% or more of a resid-containing fraction and 5 vol% to 80 vol% of one or more fatty acid alkyl esters.
• the one or more fatty acid alkyl esters can have a BMCI of 50 or less and a SBN of 55 or more.
• Methods for forming such a fuel or fuel blending composition are also provided.
• the fuel or fuel blending composition can further include a secondary flux.
• the secondary flux can correspond to additional renewable flux or conventional distillate flux.
• the amount of renewable flux can correspond to 25 vol% or more of the fuel or fuel blending composition.
• the resulting fuel or fuel blending composition can have a BMCI - TE difference value of 15 or less.
• FIG. 1 shows compositional information and properties for various fatty acid methyl ester fractions and resid-containing fractions.
• FIG. 2 shows properties for blends formed from the fractions shown in FIG. 1.
• FIG. 3 shows properties for blends formed from the fractions show i in FIG. 1.
• FIG. 4 shows modeled properties for blends formed using a combination of fatty acid alkyl ester and conventional distillate flux.
• fatty acid alkyl esters can provide unexpected benefits when used as a blend component for forming residual marine fuels and/or fuel blending components.
• fatty acid alkyl esters have relatively low Bureau of Mines Correlation Index (BMCI) values
• BMCI Bureau of Mines Correlation Index
• fatty acid alkyl esters have unexpectedly high compatibility with residual fractions.
• addition of fatty acid alkyl ester to a vacuum resid or an atmospheric resid fraction can result in reduced or minimized sediment and/or sludge formation relative to addition of a conventional distillate flux fraction.
• distillate flux is typically used to improve the properties of a resid fraction by a sufficient amount to satisfy one or more values in a marine fuel oil specification.
• the unexpected reduction in sediment and/or sludge formation can allow fatty acid alkyl esters to be used as a flux for challenged resid fractions that otherwise would be prone to sediment formation when blended with a conventional distillate flux.
• distillate flux is effective for reducing sulfur, kinematic viscosity', and density of a vacuum resid fraction
• blending a distillate flux with vacuum resid can also pose challenges with regard to maintaining solubility of various types of aromatic species within a resid fraction. If too much distillate flux is added to a resid fraction asphaltenes and/or other multi-ring aromatic species within the resid fraction can potentially phase separate, resulting in sediment and/or sludge formation.
• BMCI Bureau of Mines Correlation Index
• BMCI values are commonly used to characterize fractions corresponding to and/or including an atmospheric resid fraction or a vacuum fraction. This is in part due to the relative ease with which BMCI values can be determined.
• a common way of evaluating the compatibility of fractions for blending is based on the difference between BMCI values and the toluene equivalence (TE) values of the fractions.
• TE toluene equivalence
• BMCI and TE also referred to as a BMCI - TE value
• a BMCI - TE value 15 or less indicates that sediment is likely to form (and/or a cleanliness rating of 3 or more will occur during a spot test according to ASTM D4740) due to precipitation of asphaltenes and/or other multi-core aromatics.
• a BMCI - TE value of 12 or more can still correspond to sample with sufficient solvation power to maintain compatibility. This would correspond to a BMCI - TE value of 12 or less being an indicator of likely precipitation of asphaltenes.
• a BMCI - TE value of 10 or less for a sample can indicate that sediment formation will occur and/or a spot rating of 3 or more will occur during a spot test according to ASTM D4740.
• the BMCI value of the resulting blend is typically similar to the weighted average of the BMCI values of the blend components.
• the TE value of the blend is typically similar to the TE value of the resid fraction.
• the TE value is an indicator of the types of multi core aromatic compounds present within a fraction. For the multi-core aromatics that lead to sediment or sludge formation, however, simply reducing the concentration to avoid sediment formation does not become effective until the concentration has been reduced to a de minimis level. Thus, the presence of even a few percent of a resid fraction in a blend can lead to incompatibility issues if the aromatic solvation power of the blend is too low.
• fatty acid alkyl esters have an unexpectedly high compatibility for blending with resid fractions.
• Fatty acid alky l esters can typically have BMCI values of around 40 or less. This is similar to the BMCI values of around 30 that are typical of various types of hydrotreated distillate fractions that are commonly used as distillate flux for blending with resid fractions to form marine fuel oils (and/or fuel blending components).
• BMCI values of around 30 that are typical of various types of hydrotreated distillate fractions that are commonly used as distillate flux for blending with resid fractions to form marine fuel oils (and/or fuel blending components).
• fatty acid alkyl esters have substantially greater compatibility for blending with resid fractions while reducing or minimizing formation of sediment and/or sludge.
• fatty acid alkyl esters for blending with resid fractions can be further seen in the unexpected difference between BMCI values and solubility blending numbers for fatty acid alkyl ester fractions. It has been discovered that fatty acid alkyl ester fractions have unexpectedly high solubility blending numbers (SBN) relative to the corresponding BMCI values. As a result, when forming a blend of a resid-containmg fraction with a fatty acid alkyl ester fraction, the resulting blend can have an unusually high SBN.
• SBN solubility blending numbers
• using a fatty acid alkyl ester fraction as a flux for a resid-containing fraction can provide the unexpected combination of reducing the density, kinematic viscosity, and optionally sulfur content of a blend while also maintaining or increasing the compatibility. This is in contrast to the expected behavior of a blend where flux is added.
• addition of flux to a resid- containing fraction can reduce one or more of density, kinematic viscosity, and sulfur, but with a corresponding reduction in compatibility.
• a blend of one or more fatty acid alkyl esters with a resid-containing fraction can be referred to as a fuel composition.
• a fuel composition is understood to refer to a fraction that can be used as a fuel; that can be used as a blending component for forming a fuel; that can be used as a fuel after adding one or more fuel additives; or a combination thereof.
• a blend of one or more fatty acid alkyl esters and a resid-containing fraction can include 5.0 vol% or more of the one or more fatty acid alkyl esters, or 10 vol% or more, or 20 vol% or more, or 30 vol% or more, or 50 vol% or more.
• the blend can include 5.0 vol% to 80 vol% of the one or more fatty acid alkyl esters, or 10 vol% to 80 vol%, or 20 vol% to 80 vol%, or 50 vol% to 80 vol%, or 5.0 vol% to 60 vol%, or 10 vol% to 60 vol%, or 20 vol% to 60 vol%.
• the blend can further include 20 vol% or more of a resid-containing fraction, or 40 vol% or more, or 50 vol% or more, such as up to 90 vol% of a resid-containing fraction.
• the blend can further include 35 vol% or less of a secondary distillate flux, or 30 vol% or less, or 20 vol% or less, such as down to including substantially no secondary distillate flux (0.1 vol% or less).
• the blend can include 5 vol% to 35 vol% of secondary flux, or 5 vol% to 25 vol%.
• Examples of a secondary flux can include conventional distillate / diesel fractions, renewable diesel fractions (such as hydrotreated vegetable oil), and/or other types of distillate boiling range fractions.
• the resid-containing fraction can be characterized based on the compatibility properties of the resid-containing fraction.
• the resid-containing fraction can have one or more of a BMCI of 30 or more, or 40 or more, or 50 or more, or 60 or more, or 70 or more, such as up to 120; a TE of 5 or more, or 20 or more, or 30 or more, or 40 or more, such as up to 80; a solubility blending number (SBN) of 60 or more, or 70 or more, such as up to 120; and/or an insolubility number (IN) of 30 or more, or 35 or more, such as up to 80.
• SBN solubility blending number
• I insolubility number
• the resid-containing fraction can also be characterized based on difference values.
• Two types of difference values are defined in this discussion.
• One difference value is a difference between BMCI and TE for a fraction (a BMCI - TE value). This difference value can be calculated by subtracting the TE value from the BMCI value.
• the BMCI - TE value can be 50 or less, or 40 or less, or 30 or less, or 20 or less, such as down to 0.
• the second difference value is a difference between SBN and IN for a fraction (a SBN - IN difference value). This difference value can be calculated by subtracting the IN value from the SBN value for a fraction.
• the SBN - IN difference value can be 40 or less, or 30 or less, such as down to 5 or possibly still lower.
• a blend corresponding to a resid- containing fraction and an elevated level of flux such as a blend including 25 vol% or more of flux, or 30 vol% or more, or 40 vol% or more, such as up to 80 vol% or possibly still higher.
• an elevated level of flux such as a blend including 25 vol% or more of flux, or 30 vol% or more, or 40 vol% or more, such as up to 80 vol% or possibly still higher.
• one option can be to have substantially all of the elevated level of flux correspond to fatty acid alkyl esters.
• Another option can be to have the elevated level of flux correspond to a combination of fatty acid alkyl esters and secondary flux.
• the amount of flux in the blend can correspond to 25 vol% to 80 vol%, or 25 vol% to 50 vol%, or 30 vol% to 80 vol%, or 30 vol% to 50 vol%, or 40 vol% to 80 vol%.
• substantially all of the flux in the blend can correspond to fatty acid alkyl esters.
• the amount of fatty acid alkyl ester in the blend can correspond to 10 vol% to 80 vol%, or 10 vol% to 50 vol%, or 15 vol% to 80 vol%, or 15 vol% to 50 vol%, or 20 vol% to 80 vol%, or 20 vol% to 50 vol%.
• the amount of renewable flux in the blend i.e., fatty acid alkyl ester plus other renewable distillate, such as hydrotreated vegetable oil
• the amount of renewable flux in the blend can correspond to 20 vol% to 80 vol%, or 20 vol% to 50 vol%, or 25 vol% to 80 vol%, or 25 vol% to 50 vol%, or 30 vol% to 80 vol%, or 30 vol% to 50 vol%.
• other properties of a resid-containing fraction can include one or more of a T90 distillation point of 550°C or more; a kinematic viscosity at 50°C of 30 cSt or more, or 100 cSt or more, or 200 cSt or more, such as up to 1000 cSt; a density at 15°C of 0.95 g/cm 3 or more, such as up to 1.06 g/cm 3 ; and/or a micro carbon residue content of 5.0 wt% to 15 wt%.
• the resid-containing fraction can have a sulfur content of 1000 wppm to 10,000 wppm.
• the resid-containing fraction can have a sulfur content of 0.5 wt% (5000 wppm) or more, or 1.0 wt%, such as up to 5.0 wt%.
• the one or more fatty acid alkyl esters can have various properties.
• the one or more fatty acid alkyl esters can have a BMCI value of 50 or less, a SBN value of 55 or more, or a combination thereof.
• the SBN value of the one or more fatty acid alkyl esters can be higher than the SBN value of the resid-containing fraction.
• a fatty acid alkyl ester can include an alkyl group containing between 1 carbon (fatty acid methyl ester) to 10 carbons (fatty acid decyl ester), or 1 to 8 carbons, or 1 to 6 carbons, or 1 to 4 carbons.
• a fatty acid alkyl ester fraction can include a blend of two or more types of fatty acid alkyl esters.
• the fatty acid alkyl esters in a blend of fatty acid alkyl esters can correspond to a blend of esters with different fatty acids, a blend of esters with different alkyl groups, or a blend of esters including both different fatty acid and different alkyl groups.
• a fatty acid alkyl ester fraction can correspond to a fatty acid methyl ester fraction that meets the requirements provided in EN 14214.
• a fatty acid alkyl ester fraction can correspond to a fraction that meets the requirements described in ASTM D6751.
• a fatty acid alkyl ester fraction can be a fraction formed at least in part by transesterification of a feedstock corresponding to canola oil; palm oil; palm oil mill effluent; rapeseed oil; com oil; soybean oil; tallow; cooking oil (such as vegetable cooking oil); used cooking oil (such as used vegetable cooking oil); or a combination thereof.
• the fuel composition (and/or fuel blending composition) formed by blending a resid- containing fraction with one or more fatty acid alkyl esters can also be characterized based on the compatibility properties of the resid-containing fraction.
• the fuel composition can have a BMCI value of 59 or less, or 55 or less, or 50 or less, such as down to 30 or possibly still lower.
• the fuel composition can have a BMCI - TE difference value of 30 or less, or 20 or less, or 15 or less, or 12 or less, or 10 or less, such as down to -20 or possibly still lower.
• a fuel composition can have a SBN - IN difference value of 20 or more, or 25 or more, or 30 or more, such as up to 60 or possibly still higher.
• a SBN - IN difference value of 20 or more generally indicates a compatible blend.
• the fuel composition can have one or more of a kinematic viscosity at 50°C of 380 cSt or less, or 180 cSt or less, or 60 cSt or less, such as down to 10 cSt or possibly still lower; a density at 15°C of 1.00 g/cm 3 or less, such as down to 0.90 g/cm 3 ; and/or a sulfur content of 10,000 wppm or less, or 5000 wppm or less (such as 4000 wppm to 5000 wppm), or 1000 wppm or less (such as 800 wppm to 1000 wppm), such as down to 10 wppm or possibly still lower.
• a kinematic viscosity at 50°C of 380 cSt or less, or 180 cSt or less, or 60 cSt or less, such as down to 10 cSt or possibly still lower such as down to 10 cSt or possibly still lower
• the fuel composition can have a sulfur content of 500 wppm or more, or 800 wppm or more, or 1000 wppm or more, or 2000 wppm or more, or 4000 wppm or more, such as up to 1000 wppm or 5000 wppm.
• the fuel composition (and/or fuel blending composition) can also have a low sediment content and/or a favorable value for the spot test cleanliness rating according to ASTM D4740.
• the fuel composition can have a sediment content of 0.1 wt% or less, or 0.07 wt% or less, or 0.05 wt% or less, such as down to having substantially no sediment (less than 0.01 wt%).
• the fuel composition can have a spot test cleanliness rating (ASTM D4740) of 1 or 2.
• the resid-containing fraction and the fatty acid alkyl ester fraction may be blended with any of the following and any combination thereof to make a fuel oil: low sulfur diesel (sulfur content of less than 500 wppm), ultra low sulfur diesel (sulfur content ⁇ 10 or ⁇ 15 ppmw), low sulfur gas oil, ultra low sulfur gasoil, 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
• fuel or fuel blending component fractions may be additized with additives such as pour point improver, cetane improver, lubricity 7 improver, antioxidant, etc. to improve properties and/or meet local specifications.
• additives such as pour point improver, cetane improver, lubricity 7 improver, antioxidant, etc. to improve properties and/or meet local specifications.
• fatty acid alkyl esters are also beneficial for use in marine residual fuels based on the reduced carbon intensity of fatty acid alkyl esters as a blend component.
• the carbon intensity of a marine residual fuel can be reduced by 10% or more, or 15% or more, or 20% or more, such as up to having a 50% reduction or possibly still more.
• the lower carbon intensity of a residual marine fuel including a fatty acid alky l ester fraction can be realized by using such a fuel in any convenient type of combustion powered device.
• a marine residual fuel containing a fatty acid alkyl ester fraction can be used as fuel for a combustion engine in a marine vessel or another convenient type of vehicle.
• Still other types of combustion devices can include generators, furnaces, and other combustion devices that are used to provide heat or power.
• BMCI Bureau of Mines Correlation Index
• VABP refers to the volume average boiling point (in degrees Kelvin) of the fraction, which can be determined based on the fractional weight boiling points for distillation of the fraction at roughly 10 vol % intervals from ' 10 vol % to ' 90 vol %.
• the dr,n value refers to the density in g/cm 3 of the fraction at ⁇ 60° F. C l 6° C.). While this definition does not directly depend on the nature of the compounds in the fraction, the BMCI index value is conventionally believed to provide an indication of the ability of a fuel oil fraction to solvate asphaltenes.
• An additional/altemative method of characterizing the solubility properties of a fuel oil (or other petroleum fraction) can correspond to the toluene equivalence (TE) of a fuel oil, based on the toluene equivalence test as described, for example, in U.S. Pat. No. 5,871,634, which is incorporated herein by reference with regard to the definitions for and descriptions of toluene equivalence, solubility number (SBN), and insolubility number (IN).
• TE toluene equivalence
• SBN solubility number
• IN insolubility number
• AMS 79-004 For the toluene equivalence test, the procedure specified in AMS 79-004 and/or as otherwise published (e.g., see Griffith, M. G. and Siegmund, C. W., “Controlling Compatibility of Residual Fuel Oils ” Marine Fuels, ASTMSTP 878, C. H. Jones, Ed., American Society for Testing and Materials, Philadelphia, 1985, pp. 227-247, which is hereby incorporated by reference herein) is defined as providing the procedure.
• a convenient volume ratio of oil to a test liquid mixture can be selected, such as about 2 grams of fuel oil (with a density of about 1 g/ml) to about 10 ml of test liquid mixture.
• test liquid mixture can be prepared by blending n-heptane and toluene in various known proportions. Each of these can be mixed with the fuel oil at the selected volume ratio of oil to test liquid mixture. A determination can then be made for each oil/test liquid mixture to determine if the asphaltenes are soluble or insoluble. Any convenient method might be used. One possibility can be to observe a drop of the blend of test liquid mixture and oil between a glass slide and a glass cover slip using transmitted light with an optical microscope at a magnification from ' 5 Ox to ' 600 *. If the asphaltenes are in solution, few, if any, dark particles will be observed.
• asphaltenes are insoluble, many dark, usually brownish, particles, usually ⁇ 0.5 microns to ' 10 microns in size, can be observed.
• Another possible method can be to put a drop of the blend of test liquid mixture and oil on a piece of filter paper and let it dry. If the asphaltenes are insoluble, a dark ring or circle will be seen about the center of the yellow-brown spot made by the oil. If the asphaltenes are soluble, the color of the spot made by the oil will be relatively uniform in color. The results of blending oil with all of the test liquid mixtures can then be ordered according to increasing percent toluene in the test liquid mixture.
• the desired TE value can be between the minimum percent toluene that dissolves asphaltenes and the maximum percent toluene that precipitates asphaltenes. Depending on the desired level of accuracy, more test liquid mixtures can be prepared with percent toluene amounts in between these limits. The additional test liquid mixtures can be blended with oil at the selected oil to test liquid mixture volume ratio, and determinations can be made whether the asphaltenes are soluble or insoluble. The process can be continued until the desired value is determined within the desired accuracy. The final desired TE value can be taken as the mean of the minimum percent toluene that dissolves asphaltenes and the maximum percent toluene that precipitates asphaltenes.
• the above test method for the toluene equivalence test can be expanded to allow for determination of a solubility number (SBN) and an insolubility number (IN) for a fuel oil sample. If it is desired to determine SBN and/or IN for a fuel oil sample, the toluene equivalence test described above can be performed to generate a first data point corresponding to a first volume ratio Ri of fuel oil to test liquid at a first percent of toluene T i in the test liquid at the TE value. After generating the TE value, one option can be to determine a second data point by a similar process but using a different oil to test liquid mixture volume ratio.
• SBN solubility number
• IN insolubility number
• a percent toluene below that determined for the first data point can be selected and that test liquid mixture can be added to a known volume of the fuel oil until asphaltenes just begin to precipitate. At that point the volume ratio of oil to test liquid mixture, R2, at the selected percent toluene in the test liquid mixture, T2, can be used the second data point. Since the accuracy of the final numbers can increase at greater distances between the data points, one option for the second test liquid mixture can be to use a test liquid containing 0% toluene or 100% n-heptane. This ty pe of test for generating the second data point can be referred to as the heptane dilution test.
• SBN and IN values were determined according to the above procedure. Other SBN and IN values were determined by calculation based on values measured according to ASTM D7157. For purposes of determining the scope of this description, the calculation described in section 4.2 of the Concawe Report No. 11/19 for determining SBN and IN should be used. As described in section 4.2 of Concawe Report No. 11/19, ASTM D7157 can be used to determine the parameters “S-value” and “S a ”. Based on those parameters, IN and SBN can be calculated according to Equations 1 and 2, where dis is the density at 15°C in kg/m 3 .
• the sediment generated by a fraction can be characterized according to ISO 10307-2, Procedure A.
• distillation points and boiling points can be determined according to ASTM D7169.
• distillation points and boiling points can be determined according to ASTM D2887, but for samples that are not susceptible to characterization using ASTM D2887, D7169 can be used.
• a distillate boiling range fraction is defined as a fraction having a T10 distillation point of 140°C or more and a T90 distillation point of 565°C or less.
• a vacuum gas oil boiling range fraction (also referred to as a heavy distillate) can have a T10 distillation point of 350°C or higher and a T90 distillation point of 535°C or less.
• a resid fraction is defined as a bottoms fraction.
• a vacuum resid is defined as a bottoms fraction having a T10 distillation point of 400°C or higher. It is noted that the definitions for distillate boiling range fraction, vacuum gas oil fraction, and resid fraction are based on boiling point only. Thus, a distillate boiling range fraction or a resid fraction can include components that did not pass through a distillation tower or other separation stage based on boiling point.
• Density of a blend at 15°C can be determined according ASTM D4052.
• Sulfur (in wppm or wt%) can be determined according to ASTM D2622, while nitrogen (in wppm or wt%) can be determined according to D5291.
• Kinematic viscosity at 40°C, 50°C, and/or 100°C can be determined according to ASTM D445. Pour point can be determined according to ASTM D97.
• Micro Carbon Residue (MCR) content can be determined according to ASTM D4530.
• the content of n-heptane insolubles can be determined according to ASTM D3279.
• CCAI is a calculated value that can be derived from other measured quantities. Flash point can be determined according to ASTM D93.
• the metals content can be determined according to IP 501.
• Aromatics content can be determined according to D5186. (It is noted that some aromatics contents reported in this discussion were alternatively determined by using 2- dimensional gas chromatography.)
• Life cycle assessment is a method of quantifying the "comprehensive" environmental impacts of manufactured products, including fuel products, from “cradle to grave".
• Environmental impacts may include greenhouse gas (GHG) emissions, freshwater impacts, or other impacts on the environment associated with the finished product.
• GFG greenhouse gas
• the general guidelines for LCA are specified in ISO 14040.
• the "carbon intensity" of a fuel product is defined as the life cycle GHG emissions associated with that product (kg C02eq) relative to the energy content of that fuel product (MJ, LHV basis).
• Life cycle GHG emissions associated with fuel products must include GHG emissions associated with crude oil production; crude oil transportation to a refinery; refining of the crude oil; transportation of the refined product to point of "fill”; and combustion of the fuel product.
• GHG emissions associated with drilling and well completion - including hydraulic fracturing shall be normalized with respect to the expected ultimate recovery of sales-quality crude oil from the well.
• All GHG emissions associated with the production of oil and associated gas including those associated with (a) operation of artificial lift devices, (b) separation of oil, gas, and water, (c) cmde oil stabilization and/or upgrading, among other GHG emissions sources shall be normalized with respect to the volume of oil transferred to sales (e.g. to crude oil pipelines or rail).
• the fractions of GHG emissions associated with production equipment to be allocated to crude oil, natural gas, and other hydrocarbon products (e.g. natural gas liquids) shall be specified accordance with ISO 14040.
• the WTR GHG emissions shall be divided by the product yield (barrels of refined product/barrels of crude), and then multiplied by the share of refinery GHG specific to that refined product.
• the allocation procedure shall be conducted in accordance with ISO 14040. This procedure yields the WTR GHG intensify of each refined product (e.g. kg C02eq/bbl gasoline).
• GHG emissions associated with rail, pipeline or other forms of transportation between the refinery and point of fueling shall be normalized with respect to the volume of each refined product sold.
• the sum of the GHG emissions associated with this step and the previous step of this procedure is denoted the "Well to tank” (WTT) GHG intensify of the refined product.
• WTT Well to tank
• GHG emissions associated with the combustion of refined products shall be assessed and normalized with respect to the volume of each refined product sold.
• the “carbon intensity” of each refined product is the sum of the combustion emissions (kg CC eq/bbl) and the "WTT" emissions (kg CC eq/bbl) relative to the energy value of the refined product during combustion. Following the convention of the EPA Renewable Fuel Standard 2, these emissions are expressed in terms of the low heating value (LHV) of the fuel, i.e. g CC eq/MJ refined product (LHV basis).
• LHV low heating value
• Table 1 shows various properties for a fuel oil (Fuel Oil 1, or FOl), three types of conventional distillate fractions, and two renewable diesel fractions.
• the conventional distillate fractions represent low sulfur diesel blending components for forming a marine fuel oil from a resid-containing fraction.
• the renewable diesel fractions correspond to diesel formed from hydrotreated vegetable oil.
• FOl represents a conventional resid fraction that could be used in a marine fuel oil, but only if blended with appropriate blend components. For example, the density and the kinematic viscosity of FOl are too high for some types of residual fuels. Conventionally, this could be corrected by blending FOl with some type of flux, such as one of the distillate or renewable diesel fractions shown in Table 1.
• Distillate 1, Distillate 2, and Distillate 3 are low sulfur distillate fractions that have BMCI values near 30, while the renewable diesel fractions have BMCI values near 0. This is in contrast to FOl, which has a BMCI value of greater than 80.
• FOl which has a BMCI value of greater than 80.
• FOl has a TE number of 73, which is roughly 10 lower than the BMCI value for FOl. None of the distillate fractions or renewable diesel fractions has a TE greater than 0.
• Table 1 also shows SBN and IN for the various fractions. As shown in Table 1, FOl has a SBN of 100 and an IN of 78. The distillate fractions have SBN values near 30, with an IN of 0. It is noted that based on both BMCI - TE and SBN - IN, FOl would be considered a challenging resid fraction for forming a marine fuel oil, as FOl is already close to the compatibility limit for avoiding sediment formation.
• FOl In order to correct the density and kinematic viscosity of FOl to levels that satisfy some residual fuel specifications, FOl would need to be blended in a roughly 80 / 20 volume ratio with a distillate boiling range flux.
• Table 2 shows calculated properties for blends formed by blending FOl with each of the distillate or renewable diesel fractions shown in Table 1 in an 80 / 20 volume ratio.
• the calculated blends including F01 and 20% of the various distillate / renewable diesel fractions all have a density and kinematic viscosity that is roughly suitable for satisfying some residual marine fuel specifications.
• the resulting blends also have BMCI - TE values near 0 or even below 0. This indicates a high likelihood of sediment formation, meaning that the resulting blend does not meet all specifications from, for example, a residual fuel oil specification in ISO 8217. It is noted that the difference between SBN and IN for the three distillate blends also indicates a blend that will result in sediment formation.
• Table 3 shows calculated blends that are similar to Table 2, but with 50 vol% of each distillate / renewable diesel fraction, rather than 20 vol%. As shown in Table 3, all of the blends including 50 vol% of distillate or renewable diesel have negative values for BMCI - TE, indicating a high likelihood of sediment formation.
• FIG. 1 shows properties for various fatty acid methyl ester (FAME) fractions and several fuel oils. It is noted that FOl in FIG. 1 is the same as FOl from Tables 1 - 3. As shown in FIG. 1, the FAME fractions have BMCI values of roughly 40 or less. This is similar to the BMCI values of roughly 30 for the distillate fractions. However, it has been discovered that fatty acid alkyl ester fractions have unexpectedly high SBN values. As shown in FIG. 1, the FAME fractions have SBN values between 65 and 85. Normally, a fraction with a BMCI of 40 or less would be expected to also have a SBN value of 50 or less.
• FAME fatty acid methyl ester
• FOl has a relatively low BMCI - TE value and low difference value between SBN and IN.
• FOl is a resid fraction that would be expected to present challenges when attempting to blend with a distillate flux.
• F03 also has low values for BMCI - TE and SBN - IN. It is noted that F03 has a spot test cleanliness rating (ASTM D4740) of 1.
• F04 is potentially more suitable for blending, but still has the potential for incompatibility when blended with larger amounts of conventional distillate.
• FIG. 2 shows a blended product made from each of the FAME fractions in FIG. 1 in combination with either FOl or F03.
• the blended products in FIG. 2 correspond to 80 vol% of FOl or F03 blended with 20 vol% of one of the FAME fractions.
• the BMCI for each blended product was calculated based on the weighted average of the BMCI values for the resid- containing fraction and the FAME fraction. The Toluene Equivalence, however, was measured for each blended product.
• each of the blended products in FIG. 2 has a BMCI - TE value of less than 15. This indicates that each of the blended products in FIG. 2 would be expected to have sediment formation. However, as shown for the blends involving F03 and FAME 1, FAME 2, and FAME 3, the measured sediment formation was less than 0.01 wt%. Additionally, the blends involving F03 and FAME 1, FAME 2, or FAME 3 all maintained a spot test cleanliness rating (ASTM D4740) of 1. This demonstrates the unexpected benefit of blending a fatty acid alkyl ester fraction with a resid-containing fraction for forming marine fuel oils. This unexpected benefit is due in part to the high SBN values for the FAME fractions. As shown in FIG.
• the solubility blending number for each of the blended fractions is equal to or greater than the corresponding solubility blending number for the resid-containing fraction used to form the blend. In fact, based on the solubility blending number values, the addition of the fatty acid alkyl ester fractions appears to stabilize the resulting blends.
• FIG. 3 shows another series of blended products based on blending F04 with FAME 1, FAME 2, and FAME 3.
• F04 was blended with 50 vol% of a FAME fraction.
• F 04 has a large value for BMCI - TE of 31.8, it would be expected conventionally that attempting to blend F04 with 50 vol% of a distillate flux would result in sediment formation.
• the most favorable distillate fraction for blending shown in Table 1 above is Distillate 1, which has a BMCI value of 32.9. Based on calculated values, a blend of 50 vol% F04 and 50 vol% Distillate 1 would be expected to have a BMCI value of 53.9.
• a blend of 50 vol% F04 and 50 vol% Distillate 1 would have a calculated BMCI - TE value of roughly 11, which is less than 15 (or less than 12) and therefore indicates a blend that would likely be incompatible.
• the calculated BMCI - TE values for the blended fractions are all less than 15, indicating a likelihood for sediment formation.
• the measured sediment formation for the blended fractions was either 0.01 wt% or less than 0.01 wt% indicating that the blended fractions would satisfy the sediment formation requirement for various types of marine fuel oils.
• fatty acid methyl esters or more generally fatty acid alkyl esters
• blending fatty acid methyl esters (or more generally fatty acid alkyl esters) with some resid- containing fractions can provide the unexpected benefit of reducing density and kinematic viscosity while also maintaining or even improving the compatibility of the resulting blend.
• This is in contrast to conventional addition of flux to a resid-containing fraction, where it would be expected that addition of flux would provide the traditional benefit of reducing density and/or kinematic viscosity, but at the cost of also reducing the compatibility of the resulting blend.
• Table 4 shows a modeled blending example of blending F03 with FAME 1 in a volume ratio of 30 vol% F03 to 70 vol% FAME 1.
• the modeled blend of 30 vol% F03 and 70 vol% FAME 1 has a predicted BMCI - TE value of 3.6. For a conventional blend, this would indicate that sediment formation was likely. However, due to the high SBN value of FAME 1, the modeled blend in Table 4 has a higher SBN value than the neat F03 fraction. As a result, even though the model blend in Table 4 shows addition of 70 vol% of FAME 1 to F03, the model blend has a SBN - IN value above 40, indicating no sediment formation.
• Blends Including Fatty Acid Alkyl Ester and Conventional Distillate [0075] Based on the ability of fatty acid alkyl esters to maintain or even improve compatibility in blends including a resid-contaimng fraction, fatty acid alkyl esters can also be used in combination with conventional distillate fractions. Using a mixture of fatty acid alkyl ester fraction(s) and conventional distillate fraction(s) as a flux for resid-containing fraction(s) can allow for greater flexibility when blending to form marine fuel products.
• FIG. 4 shows a series of model blends that were formed using a combination of F03 (from FIG. 1), FAME 1 (from FIG. 1), and Distillate 1 (from Table 1).
• the compatibility characteristics for the model blends shown in FIG. 4 were based on calculation of compatibility characteristics based on ideal blending, where BMCI and SBN values are based on weighted averages of the blend components while TE and IN values are based on the corresponding value for F03.
• the BMCI - TE values for all of the blends are substantially below 15, indicating that under conventional blending, all of the blends would be considered to have too high of a potential for sediment formation.
• adding sufficient amounts of fatty acid alkyl ester can overcome the compatibility issues that are created by adding the distillate flux.
• blends including up to 50 vol% (or more) of combined fatty acid alkyl ester and distillate flux can be added to a resid- containing fraction while still reducing or minimizing sediment formation to acceptable levels.
• Table 5 shows examples of blending an ary l ester, phenethyl octanoate, with a resid-containing fraction (F02).
• the resid-containing fraction is already prone to sediment formation. This is indicated by both the BMCI - TE value of 7.5, and confirmed by the measured sediment value of 0.49 wt%.
• the aryl ester fraction had a BMCI value of 83, which is greater than the BMCI value of 73.5 for F02.
• the aryl ester did not provide the unexpected benefits of the fatty acid alkyl ester fractions.
• the BMCI value of the aryl ester was greater than the BMCI value of F02, each of the blends shown in Table 5 has a higher measured sediment value than the measured sediment for the neat F02. This indicates that the addition of the aryl ester decreased the compatibility of the blend, as opposed to the addition of the fatty acid alkyl esters, which appeared to increase the compatibility of the blend. It is believed that the reduction in sediment amount as the amount of aryl ester is increased is due in part to dilution.
• Embodiment 1 A fuel or fuel blending composition comprising 20 vol% or more of a resid-containing fraction and 5 vol% to 80 vol% of one or more fatty acid alkyl esters, the one or more fatty acid alkyl esters comprising a BMCI of 50 or less and a SBN of 55 or more.
• Embodiment 2 The fuel or fuel blending composition of Embodiment 1, wherein the resid-containing fraction comprises a BMCI - TE difference value of 50 or less, or wherein the fuel composition comprises a BMCI - TE difference value of 15 or less, or a combination thereof.
• Embodiment 3 The fuel or fuel blending composition of any of the above embodiments, wherein the fuel composition comprises 20 vol% or more of the one or more fatty acid alkyl esters.
• Embodiment 4 The fuel or fuel blending composition of any of the above embodiments, wherein the SBN of the one or more fatty acid alky l esters is greater than a SBN of the resid-containing fraction, or wherein the one or more fatty acid alkyl esters comprise one or more fatty acid methyl esters, or a combination thereof.
• Embodiment 5. The fuel or fuel blending composition of any of the above embodiments, wherein the fuel or fuel blending composition comprises 25 vol% or more of a renewable flux, or wherein the fuel or fuel blending composition comprises 10 vol% or more of the one or more fatty acid alkyl esters, or a combination thereof.
• Embodiment 6 The fuel or fuel blending composition of any of the above embodiments, further comprising 5 vol% to 25 vol% of a secondary flux, the secondary flux comprising a BMCI of 40 or less and a SBN of 50 or less.
• Embodiment 7 The fuel or fuel blending composition of any of the above embodiments, wherein the resid-containing fraction comprises a SBN - IN difference value of 40 or less, or wherein the fuel composition comprises a SBN - IN difference value of 20 or more, or a combination thereof.
• Embodiment 8 The fuel or fuel blending composition of any of the above embodiments, wherein the resid-containing fraction comprises a kinematic viscosity at 50°C of 30 cSt or more, or wherein the resid-containing fraction comprises a density at 15°C of 0.95 g/cm 3 or more, or a combination thereof.
• Embodiment 9 The fuel or fuel blending composition of any of the above embodiments, wherein the resid-containing fraction has a T90 distillation point of 550°C or more, or wherein the resid-containing fraction comprises 5.0 wt% or more of micro carbon residue, or a combination thereof.
• Embodiment 10 The fuel or fuel blending composition of any of the above embodiments, wherein the fuel or fuel blending composition comprises a kinematic viscosity at 50°C of 380 cSt or less, or wherein the fuel or fuel blending composition comprises a kinematic viscosity at 50°C of 60 cSt or less.
• Embodiment 11 The fuel or fuel blending composition of any of the above embodiments, wherein the fuel or fuel blending composition comprises a sediment level of 0.1 wt% or less, or wherein the fuel or fuel blending composition comprises 5000 wppm or less of sulfur, or a combination thereof.
• Embodiment 12 The fuel or fuel blending composition of any of the above embodiments, wherein the fuel or fuel blending composition comprises a sulfur content of 1000 wppm or less, or a sulfur content of 800 wppm or more, or a combination thereof.
• Embodiment 13 The fuel or fuel blending composition of any of the above embodiments, wherein the one or more fatty acid alkyl esters comprise one or more fatty acid methyl esters.
• Embodiment 14 Use of a fuel comprising the fuel or fuel blending composition of any of Embodiments 1 to 13 as a fuel in a combustion device.
• Embodiment 15 A method for forming a fuel or fuel blending composition according to any of Embodiments 1 to 13, comprising blending 20 vol% or more of a resid-containing fraction and 5 vol% to 80 vol% of one or more fatty acid alkyl esters to form the fuel composition, the one or more fatty acid alkyl esters comprising a BMCI of 50 or less and a SBN of 55 or more.

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