Fuel oil blends with cashew nut shell liquid for improved compatibility

Abstract

Methods are provided for blending challenged fractions into a fuel oil while improving compatibility. Corresponding fuel oil blends formed using such a method are also provided. The methods include blending cashew nut shell oil with the challenged fraction or the fuel oil (or other conventional fraction) first, prior to blending the challenged fraction with the fuel oil. It has been discovered that using a desirable blend order can reduce the TSP of the resulting blended product. Additionally, use of cashew nut shell liquid as a blend component can allow an unexpectedly large amount of a challenged fraction, such as steam cracker tar, to be incorporated into a marine fuel oil while still producing a marine fuel blend with a TSP of less than 0.1 wt%.

Description

FUEL OIL BLENDS WITH CASHEW NUT SHELL LIQUID FOR IMPROVED COMPATIBILITY FIELD OF THE INVENTION

[0001] Methods for blending challenged fractions into fuel oils while reducing or minimizing compatibility issues by incorporating cashew nut shell liquid are provided. Corresponding fuel oils having improved compatibility are also provided.BACKGROUND OF THE INVENTION

[0002] Steam cracked tar (SOT) is a type of pyrolysis tar that is a relatively low-value stream from a steam cracking process. Steam cracked tar is a challenging fuel oil blending component, as it contains a relatively high content of high-severity asphaltenes derived from the steam cracking process. In practice, only a small amount of steam cracked tar can be blended into fuel oil before negatively affecting fuel compatibility. However, blending steam cracked tar into fuel oil is a relatively high value disposition for steam cracked tar. It would be desirable to have additional methods for allowing more steam cracked tar to be blended into fuel oils while maintaining acceptable fuel compatibility.

[0003] Cashew nut shell liquid (CNSL) is a non-edible oil derived from the shell of cashew nuts. The oil is considered waste based and is listed on the European Renewable Energy Directive Annex 9 A list of advanced feedstocks.

[0004] When originally extracted / recovered from the cashew nut shells, the cashew nut shell liquid primarily contains anacardic acid, with a smaller proportion of cardol and methyl derivatives of cardol. This initial version of cashew nut shell liquid can be converted into “technical grade” cashew nut shell liquid, such as by heat treatment, degumming, distillation, and / or other convenient process that can convert and / or remove carboxylic acids and allow for separation to form a desired product. The resulting technical grade cashew nut shell liquid is primarily composed of caradanol, with some cardol as well as other components. Technical grade cashew nut shell liquid is a commercially available product from a variety of sources.

[0005] U.S. Patent Application Publication 2024 / 0368488 describes marine fuel blends that include a cashew nut shell liquid that contains 50 wt% or more of cardanol.

[0006] U.S. Patent 8,609,599 describes use of cashew nut shell liquid in marine lubricants.

[0007] U.S. Patent Application Publication 2016 / 0200995 describes use of cashew nut shell liquid as a blend component for reducing the viscosity of heavy oils.

[0008] U.S. Patent 7,906,010 describes incorporation of steam cracked tar into a fuel oil.

[0009] U.S. Patent 8,987,537 describes fuel oil blends corresponding to a mix of atmospheric tower bottoms (also referred to as long residue) with various non-hydroprocessed fractions. A large number of examples are provided, but the highest content of pyrolysis tar or thermal tar shown in a blend in any of the examples is 1 wt%.SUMMARY OF THE INVENTION

[0010] In an aspect, a method for improving the stability of a fuel oil blend or blend component is provided. The method includes providing a challenged fraction and a conventional fraction, the challenged fraction having at least one of an insolubility number of 30 or more and a toluene equivalence of 30 or more. The method further includes mixing a cashew nut shell liquid fraction with at least one of the challenged fraction and the conventional fraction. Additionally, the method includes forming a blended fraction containing at least a portion of the mixture, the blended fraction containing at least a portion of the cashew nut shell liquid fraction, at least a portion of the challenged fraction, and at least a portion of the conventional fraction, wherein the blended fraction comprises 5.0 vol% or more of the at least a portion of the cashew nut shell liquid fraction and 2.0 vol% or more of the at least a portion of the challenged fraction, relative to a volume of the blended fraction.

[0011] In another aspect, a fuel oil or fuel oil blend component is provided. The fuel oil or fuel oil blend component includes 1.0 wt% to 20 wt% of a challenged fraction, relative to a weight of the fuel oil or fuel oil blend component, the challenged fraction having at least one of a toluene equivalence of 30 or more and an insolubility number of 30 or more, the challenged fraction optionally having a TSP of 0.10 wt% or less. The fuel oil or fuel oil blend component further includes 5.0 wt% to 80 wt% of a cashew nut shell liquid fraction, a volume ratio of the cashew nut shell liquid fraction to the challenged fraction being 3.0 or higher, optionally but preferably 4.5 or higher. Additionally, the fuel oil or fuel oil blend component includes 20 wt% to 94 wt% of a conventional fraction having a TSP of 0.10 wt% or less, wherein the fuel oil or fuel oil blend component comprises a TSP of 0.10 wt% or less.BRIEF DESCRIPTION OF THE DRAWING

[0012] FIG. 1 shows compositional data and properties for fractions used to make various blends.DETAILED DESCRIPTION OF THE INVENTION

[0013] In various aspects, methods are provided for blending challenged fractions into a fuel oil while improving compatibility. Corresponding fuel oil blends formed using such a method are also provided. The methods include blending cashew nut shell oil with the challenged fraction or the fuel oil (or other conventional fraction) first, prior to blending the challenged fraction with the fuel oil. It has been discovered that using a desirable blend order can reduce the total sediment potential (TSP) of the resulting blended product. Additionally, use of cashew nut shell liquid as a blend component can allow an unexpectedly large amount of a challenged fraction, such as steam cracker tar, to be incorporated into a marine fuel oil while still producing a marine fuel blend with a TSP of less than 0.1 wt%. Pyrolysis tar (such as steam cracker tar) and / or other thermally cracked tars are examples of challenged fractions. More generally, challenged fractions correspond to fractions that have at least one of an insolubility number greater than 30 and a toluene equivalence number greater than 30. Other examples of challenged fractions include main column bottoms from fluid catalytic cracking (FCC main column bottoms) and vis-breaker tars, as well as resid fractions from specific types of crude oils that have higher toluene equivalence / insolubility numbers.

[0014] Pyrolysis tar, such as steam cracker tar, is a challenged fraction formed during hydrocarbon pyrolysis. Due to the nature of the pyrolysis reaction environment, pyrolysis tar corresponds to a high boiling range fraction with a substantial asphaltene content. Generally, pyrolysis tar is self-compatible, so that the total sediment potential (TSP) for a pyrolysis tar is below 0.10 wt%. This is typically true even after addition of flux to the pyrolysis tar to reduce the viscosity of the pyrolysis tar to a value that facilitates pipeline transport and / or other types of transport.

[0015] Unfortunately, due to the nature of pyrolysis tar, the options for incorporating pyrolysis tar into an economically viable product are limited. It is possible to upgrade pyrolysis tar via hydroprocessing, but this consumes a substantial amount of hydrogen relative to the volume of upgraded pyrolysis tar that is generated. It would be desirable to be able to incorporate pyrolysis tar into a residual fuel, such as a marine residual fuel, without having to perform prior hydroprocessing on the pyrolysis tar. However, due to the high insolubility number of pyrolysis tars (indicating the presence of components that can potentially precipitate), it is difficult to add more than 2.0 wt% of pyrolysis tar to a typical marine fuel blend, relative to the weight of the marine fuel blend, while still maintaining a TSP value of less than 0.10 wt% for the blended fuel.

[0016] Cashew nut shell liquid (CNSL) can be used as renewable blending component. In addition to being approximately half the cost of biodiesel, CNSL is formed from plant matter that cannot be used as a food source, which is an advantage for a renewable fuel as it means the renewable fuel is not competing with edible food consumption. Because of the dark color and compositional properties, CNSL is not considered a viable option for production of onroad diesel and / or sustainable aviation fuels. However, vessels that operate on residual fuel oil or very low sulfur fuel oil (VLSFO) can handle a wider range of qualities of fuel, making CNSL a potential candidate as a blend component. Unlike fatty acid methyl esters / biodiesel, CNSL contains phenolic compounds with potential to stabilize highly aromatic asphaltenes contained in pyrolysis tar.

[0017] It has been unexpectedly discovered that the order of blending impacts the ability of cashew nut shell liquid for improving compatibility in fuel oil blends that include cashew nut shell liquid, at least one challenged fraction, and at least one conventional fraction (such as a very low sulfur fuel oil). If the cashew shell nut liquid is one of the first two components introduced into the blend, improved compatibility is achieved. However, if a challenged fraction is combined first with a conventional fraction, and then the cashew nut shell liquid is added, the compatibility benefit is reduced.

[0018] It has further been discovered that cashew nut shell oil can provide compatibility benefits when blending fractions that are individually self-compatible, but which can result in sediment formation when blended. As an example, one type of challenged fraction is pyrolysis tar, such as steam cracker tar. Although steam cracked tar has a high asphaltene content, it is also typically self-compatible, with a total sediment potential (TSP) value below 0.10 wt%. It would be desirable to be able to blend steam cracker tar in larger amounts with a conventional fuel oil, such as a very low sulfur fuel oil. Depending on the source of the fuel oil, such a very low sulfur fuel oil can also be self-compatible, with a TSP value below 0.10 wt%, or below 0.05 wt%. Although these fractions separately arc self-compatible, when blended, sediment can form. Conventionally, addition of even 2.0 wt% or more of steam cracker tar to a fuel oil blend can result in a TSP value for the resulting blend of well over 0.20 wt%. It has been discovered, that cashew shell nut oil, if blended in a sufficient amount with one of the individual components prior to blending the challenged and conventional component together, can reduce or minimize the TSP value of the resulting blend.

[0019] It is noted that in this discussion, the term “conventional fraction” is used to refer to both conventional mineral fractions other than challenged fractions, as well as conventional bio-derived fractions different than cashew nut shell liquid.Feedstocks - Challenged Fractions

[0020] In various aspects, cashew nut shell liquid is used to improve the compatibility of a fuel oil formed by blending a challenged fraction with a conventional fuel oil fraction. A challenged fraction generally corresponds to a fraction that has an elevated value for insolubility number (IN), an elevated value for toluene equivalence (TE), or a combination thereof. When insolubility number is characterized for a challenged fraction, the challenged fraction can have an insolubility number (IN) of 30 or more, such as up to 200 or possibly still higher. When toluene equivalence is characterized for a challenged fraction, the challenged fraction can have a toluene equivalence (TE) of 30 or more, such as up to 150 or possibly still higher. In aspects where both insolubility number and toluene equivalence are characterized for a challenged fraction, at least one of the insolubility number and the toluene equivalence can be 30 or more.

[0021] Table 1 shows insolubility number values and toluene equivalence values for some representative types of conventional and challenged fractions.Table 1 - TE and IN Values< >< >< >< > < >

[0022] Some examples of challenged fractions are pyrolysis tar fractions, such as fluxed pyrolysis tar fractions. Generally, a pyrolysis tar corresponds to a bottoms fraction from apyrolysis process, such as a steam cracking process. Generally, in order to provide pyrolysis tar in a form that can be moved and / or transported within a reaction system, the pyrolysis tar will correspond to a fluxed pyrolysis tar. Depending on the aspect, a pyrolysis tar without flux can have a T10 distillation point of 270°C or higher, or a T5 distillation point of 250°C or higher, or an initial boiling point of 250°C or higher. If a fluxed pyrolysis tar is used, the pyrolysis tar (including flux) can have a T10 distillation point of 180°C or higher. The T10, T5, or initial boiling point can be determined according to ASTM D2887. If the sample is not suitable for characterization using ASTM D2887, then ASTM D7169 can be used instead.

[0023] It is noted that many crude oils have TE and / or IN values that are less than 30. However, some select types of crude oils can have TE and / or IN values of 30 or more, and therefore can qualify as challenged fractions. It is further noted that thermal cracking of a conventional resid tends to increase the TE and / or IN value of the resulting cracked fraction, while hydroprocessing tends to reduce the TE and / or IN value of a fraction.

[0024] In some aspects, the challenged fraction, such as a pyrolysis tar fraction, can be self-compatible. In such aspects, the total sediment potential (TSP) value for the challenged fraction can be 0.10 wt% or less, or 0.05 wt% or less, such as down to substantially no sediment (detection limit). In this discussion, TSP is measured according to ISO 10307-2. It is noted that for some fractions, the “total sediment existent” (TSE) or “total sediment accelerated” (TSA) may be reported instead. Total sediment existent and / or total sediment accelerated can also be 0.10 wt% or less, or 0.05 wt% or less, such as down to substantially no sediment (detection limit). In this discussion, TSE is measured according to ISO 10307-1 while TSA is measured according to ISO 10307-2.

[0025] In this discussion, the kinematic viscosity of a fraction can be characterized according to D7042. A challenged fraction can have a kinematic viscosity at 50°C (KV50) of 50 cSt or higher, or 75 cSt or higher, or 100 cSt or higher, or 300 cSt or higher, such as up to 1000 cSt or possibly still higher. It is noted that when originally formed as a bottoms fraction, pyrolysis tar often has a kinematic viscosity at 50°C that is relatively high, such as a KV50 of 150 cSt or higher, or 300 cSt or higher. For practical reasons, it is often difficult to transport pyrolysis tar at the original viscosity it is formed at. Thus, pyrolysis tar can be fluxed to reduce the KV50 to less than 100 cSt to facilitate transport (such as pipeline transport). Any convenient type of flux can be used that is miscible with the pyrolysis tar that provides a reduction in viscosity. Examples of suitable fluxes include, but are not limited to, steam cracker gas oil, diesel boiling range fractions, and atmospheric gas oils. It is noted that for a fluxed pyrolysistar, the properties of a challenged fraction as described herein correspond to the pyrolysis tar including any flux that has been added to the pyrolysis tar.

[0026] The Bureau of Mines Correlation Index (BMCI) provides a method for characterizing the ability of a fuel oil fraction to maintain solubility of compounds such as asphaltenes. The BMCI index can be calculated based on Equation (1):

[0027] 456.8

[0028] In Equation (1), 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 “d6o” value refers to the density in g / cm3of the fraction at ~60° F. (~16° C.). While this definition does not directly depend on the nature of the compounds in the fraction, the BMCI value is conventionally believed to provide an indication of the ability of a fuel oil fraction to solvate asphaltenes.

[0029] 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).

[0030] 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, ASTM STP 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. Generally, 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. Then, various mixtures of the 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 ~50x to ~600x. If the asphaltenes are in solution, few, if any, dark particles will be observed. If the 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.

[0031] 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 Ti 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. Alternatively, 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 as 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 type of test for generating the second data point can be referred to as the heptane dilution test.

[0032] Based on the toluene equivalence test and heptane dilution test (or other test so that Ri, R2, Ti, and T2 are all defined), the insolubility number (IN) and solubility number (SBN) for a sample can be calculated based on Equations (2) and (3).

[0035] As noted in U.S. Pat. No. 5,871,634, alternative methods are available for determining the solubility number of a fuel oil that has an insolubility number of zero.

[0036] The presence of asphaltenes can also be an indicator of a challenged fraction. In some aspects, the asphaltene content of a challenged fraction can be 5.0 wt% or more, or 7.5 wt% or more, or 10 wt% or more, or 12.5 wt% or more, or 15 wt% or more, such as up to 25 wt% or possibly still higher. In this discussion, asphaltene content is determined according to method IP 143.Feedstocks - Conventional Fuel Oil Blend Components

[0037] In various aspects, a fuel oil blend can correspond to a blend of at least one challenged fraction, at least one conventional fuel oil fraction, and cashew nut shell liquid. The conventional fuel oil fraction(s) can include at least one mineral fraction. Optionally, the conventional fuel oil fraction(s) can further include one or more bio-derived fractions different from cashew nut shell liquid. More generally, the “conventional” fuel oil fractions described herein correspond to any fractions that are different from the challenged fraction and the cashew nut shell liquid. Thus, the conventional fuel oil fractions include mineral fractions, bioderived fractions, and any other fractions that do not qualify as challenged fractions. It is noted that hydrotreated mineral fractions are included within the definition of a mineral fraction.

[0038] Relative to the volume of the one or more conventional fuel oil fractions, the mineral fraction can correspond to 60 vol% or more of the one or more conventional fractions, or 75 vol% or more, or 90 vol% or more, such as up to being substantially all of the one or more conventional fractions. The amount of the one or more bio-derived fractions different from cashew nut shell liquid can correspond to 35 vol% or less of the one or more conventional fractions, or 25 vol% or less, or 15 vol% or less, or 5.0 vol% or less, such as down to having substantially no content corresponding to additional bio-derived fractions. In some aspects the amount of bio-derived fractions in the one or more conventional fractions can correspond to 10 vol% to 35 vol% of the one or more conventional fractions, or 20 vol% to 30 vol%.

[0039] One way of characterizing the one or more conventional fractions is based on the BMCI of the conventional fraction(s). The BMCI value of a fraction roughly correlates with aromaticity, and provides an indication of the solvation power of the fraction. For conventional fractions, typical fractions have a BMCI of 50 to 70. Paraffinic conventional fractions have aBMCI of 40 to 50. Highly aromatic conventional fractions have a BMCI of 70 or higher, or 80 or higher. As noted above, the TE and IN values for a conventional fraction are 30 or less. In some aspects, a convention fuel oil fraction can have a TE of 20 or less (such as down to 0), an IN of 20 or less (such as down to 0), or a combination thereof.

[0040] In some aspects, a conventional fraction can have a TSP value of 0.10 wt% or less, or 0.05 wt% or less, such as down to having substantially no TSP (less than 0.01 wt%). Additionally or alternately, a conventional fraction can have an asphaltenes content of 5.0 wt% or less, or 2.0 wt% or less, or 1.0 wt% or less, such as down to having substantially no asphaltene content.

[0041] In some aspects, other properties of a conventional fraction can include one or more of a T90 distillation point of 450°C or more, or 500°C or more, or 55O°C or more, such as up to 750°C; 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 / cm3or more, such as up to 1.06 g / cm3; and / or a micro carbon residue content of 1.0 wt% to 15 wt%. In some aspects, the conventional fraction can have a sulfur content of 1,000 wppm to 10,000 wppm. In some aspects, the conventional fraction can have a sulfur content of 0.5 wt% (5,000 wppm) or more, or 1.0 wt%, such as up to 5.0 wt%.

[0042] When forming a marine fuel oil, in addition to a conventional fraction, cashew nut shell liquid, and a challenged fraction, any other convenient type of blend component can also be included. Thus, the conventional fraction, the cashew nut shell liquid, and the challenged 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, gas-to-liquid diesel, gas-to-liquid kerosene, hydrotreated vegetable oil, fatty acid methyl esters, non-hydrotreated straight-run diesel, non-hydrotreated straight-run kerosene, non-hydrotreated straight-run gas oil and any distillates derived from low sulfur crude slates, gas-to-liquid wax, and other gas-to-liquid hydrocarbons, non-hydrotreated cycle oil, non-hydrotreated fluid catalytic cracking slurry oil, non-hydrotreated pyrolysis gas oil, non-hydrotreated cracked light gas oil, non-hydrotreatedcracked heavy gas oil, non-hydrotreated pyrolysis light gas oil, non-hydrotreated pyrolysis heavy gas oil, non-hydrotreated thermally cracked residue, non-hydrotreated thermally cracked heavy distillate, non-hydrotreated coker heavy distillates, non-hydrotreated vacuum gas oil, non-hydrotreated coker diesel, non-hydrotreated coker gasoil, non-hydrotreated coker vacuum gas oil, non-hydrotreated thermally cracked vacuum gas oil, non-hydrotreated thermally cracked diesel, non-hydrotreated thermally cracked gas oil, hydrotreated fats or oils such as hydrotreated vegetable oil, hydrotreated tall oil, etc., fatty acid methyl ester, Group 1 slack waxes, lube oil aromatic extracts, deasphalted oil, atmospheric tower bottoms, vacuum tower bottoms, any residue materials derived from low sulfur crude slates, LSFO, RSFO, other LSFO / RSFO blend stocks.

[0043] As needed, fuel or fuel blending component fractions may be additized with additives such as pour point improver, cetane improver, lubricity improver, antioxidant, etc. to improve properties and / or meet local specifications.Blending of Challenged Fraction, Conventional Fraction, and Cashew Nut Shell Liquid

[0044] In various aspects, a blended fuel is formed by blending cashew nut shell liquid with at least one challenged fraction and at least one conventional fraction. Relative to the weight of the blended fuel, the weight of the cashew nut shell liquid in the blended fuel is 5.0 vol% to 80 vol%, or 5.0 vol% to 70 vol%, or 5.0 vol% to 60 vol%, or 5.0 vol% to 50 vol%, or 5.0 vol% to 30 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 10 vol% to 80 vol%, or 10 vol% to 70 vol%, or 10 vol% to 60 vol%, or 10 vol% to 50 vol%, or 10 vol% to 30 vol%, or 15 vol% to 80 vol%, or 15 vol% to 70 vol%, or 15 vol% to 60 vol%, or 15 vol% to 50 vol%, or 15 vol% to 30 vol%, or 20 vol% to 80 vol%, or 20 vol% to 70 vol%, or 20 vol% to 60 vol%, or 20 vol% to 50 vol%, or 30 vol% to 70 vol%, or 30 vol% to 50 vol%.

[0045] The amount of the challenged fraction, such as pyrolysis tar, in the blended fuel is typically relatively low. Conventionally, pyrolysis tar is limited to 2.0 vol% or less of a blended fuel composition when forming a fraction with a TSP of 0.10 wt% or less by blending with a typical conventional fraction. However, by incorporating cashew nut shell liquid along with a challenged fraction, the amount of the challenged fraction can be increased while still maintaining a reduced or minimized TSP, such as a TSP of 0.10 wt% or less.

[0046] The amount of the challenged fraction that can be added when incorporating cashew nut shell liquid, while still maintaining a reduced or minimized TSP, depends in part on the nature of the conventional fraction. For example, when a typical conventional fraction is present in the blend (BMCI of 50 to 70), the amount of the challenged fraction that can beadded is 1.5 vol% to 20 vol%, or 1.5 vol% to 15 vol%, or 1.5 vol% to 10 vol%, or 1.5 vol% to 7.5 vol%, or 1.5 vol% to 5.0 vol%, or 2.0 vol% to 20 vol%, or 2.0 vol% to 15 vol%, or 2.0 vol% to 10 vol%, or 2.0 vol% to 7.5 vol%, or 2.0 vol% to 5.0 vol%, or 2.5 vol% to 20 vol%, or 2.5 vol% to 15 vol%, or 2.5 vol% to 10 vol%, or 2.5 vol% to 7.5 vol%, or 2.5 vol% to 5.0 vol%, or 3.0 vol% to 20 vol%, or 3.0 vol% to 15 vol%, or 3.0 vol% to 10 vol%, or 3.0 vol% to 7.5 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 5.0 vol% to 10 vol%, or 5.0 vol% to 7.5 vol%, or 7.0 vol% to 20 vol%, or 7.0 vol% to 15 vol%, or 7.0 vol% to 10 vol%. When the conventional fraction is a highly paraffinic fraction (BMCI of 40 to 50), the amount of the challenged fraction that can be added may be reduced, due to the initially lower ability of paraffinic conventional fraction to contribute to maintaining a reduced or minimized TSP. In such aspects where the conventional fraction has a BMCI of 40 to 50, the amount of challenged fraction that can be added is 1.0 vol% to 20 vol%, or 1.0 vol% to 15 vol%, or 1.0 vol% to 10 vol%, or 1.0 vol% to 7.5 vol%, or 1.0 vol% to 5.0 vol%, or 1.5 vol% to 20 vol%, or 1.5 vol% to 15 vol%, or 1.5 vol% to 10 vol%, or 1.5 vol% to 7.5 vol%, or 1.5 vol% to 5.0 vol%, or 2.0 vol% to 20 vol%, or 2.0 vol% to 15 vol% or 2.0 vol% to 10 vol%, or 2.0 vol% to 7.5 vol%, or 2.0 vol% to 5.0 vol%, or 3.0 vol% to 20 vol%, or 3.0 vol% to 15 vol%, or 3.0 vol% to 10 vol%, or 3.0 vol% to 7.5 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 5.0 vol% to 10 vol%, or 5.0 vol% to 7.5 vol%, or 7.0 vol% to 20 vol%, or 7.0 vol% to 15 vol%, or 7.0 vol% to 10 vol%. When the conventional fraction is a highly aromatic fraction (BMCI of 70 or higher, or 80 or higher), the amount of the challenged fraction that can be added is 2.0 vol% to 20 vol%, or 2.0 vol% to 15 vol%, or 2.0 vol% to 10 vol%, or 2.0 vol% to 7.5 vol%, or 2.0 vol% to 5.0 vol%, or 2.5 vol% to 20 vol%, or 2.5 vol% to 15 vol% or 2.5 vol% to 10 vol%, or 2.5 vol% to 7.5 vol%, or 2.5 vol% to 5.0 vol%, or 3.0 vol% to 20 vol%, or 3.0 vol% to 15 vol%, or 3.0 vol% to 10 vol%, or 3.0 vol% to 7.5 vol%, or 5.0 vol% to 20 vol%, or 5.0 vol% to 15 vol%, or 5.0 vol% to 10 vol%, or 5.0 vol% to 7.5 vol%, or 7.0 vol% to 20 vol%, or 7.0 vol% to 15 vol%, or 7.0 vol% to 10 vol%.

[0047] The balance of the blended fuel can correspond to the at least one conventional fraction. For example, in some aspects the blended fuel can contain 28 vol% to 94 vol% of the conventional fraction, or 28 vol% to 89 vol%, or 28 vol% to 80 vol%, or 28 vol% to 70 vol%, or 40 vol% to 94 vol%, or 40 vol% to 89 vol%, or 40 vol% to 80 vol%, or 40 vol% to 70 vol%, or 60 vol% to 94 vol%, or 60 vol% to 89 vol%, or 60 vol% to 80 vol%, or 75 vol% to 94 vol%.

[0048] In some aspects, a minimum volume ratio of cashew nut shell liquid to challenged fraction can be present in the blended fuel, in order to maintain a TSP value of 0.10 wt% orless for the blended fuel. In such aspects, the volume ratio of cashew nut shell liquid to challenged fraction can be 3.0 (3.0 to 1) or more, or 4.0 or more, or preferably 4.5 or more, or 5.0 or more, or 6.0 or more, or 7.0 or more, such as up to 25 or possibly still higher.

[0049] It has been discovered that the order of combining the blend components can have an impact on the amount of TSP in the resulting blend. In particular, at intermediate levels of cashew nut shell liquid in a blend, if the cashew nut liquid is added prior to addition of at least one of the challenged fraction and the conventional fraction, a lower TSP value is obtained. By contrast, if the challenged fraction and the conventional fraction are blended first, and then the cashew nut shell liquid is added, a higher TSP value is observed. Without being bound by any particular theory, it is believed that addition of the cashew nut shell liquid at an earlier stage in the blend process allows the cashew nut shell liquid to prevent formation of precursors that result in increased TSP. By contrast, if the cashew nut shell liquid is added after combining the challenged fraction and the conventional fraction, it is believed that the precursors for TSP are able to form, and the cashew nut shell liquid will have a reduced ability to prevent the precursors from forming TSP. It is noted that at higher concentrations of cashew nut shell liquid, the cashew nut shell liquid does appear to be able to re-dissolve the TSP.

[0050] After forming a blend containing a challenged fraction, a conventional fraction, and cashew nut shell liquid, the resulting blend can be characterized. In some aspects, the resulting blend can have a TSP value of 0.10 wt% or less, or 0.08 wt% or less, or 0.05 wt% or less, such as down to 0.01 wt% or possibly still lower. In other aspects, the cashew nut shell liquid can reduce the TSP of a resulting blend for a blend that potentially has a TSP value of greater than 0.10 wt%. In such aspects, the TSP value of the resulting blend can be 0.20 wt% or less, or 0.15 wt% or less, or 0.10 wt% or less, or 0.08 wt% or less, or 0.05 wt% or less, such as down to 0.01 wt% or possibly still lower.

[0051] The resulting blend can also have other properties. Depending on the aspect, the resulting blend can have one or more of the following properties: a derived cetane number of 5 or higher as determined according to ASTM D7668; a density at 15°C of 0.89 to 1.05 g / ml according to ASTM D7042; a kinematic viscosity at 50°C of 25 cSt to 500 cSt according to ASTM D7042; a micro carbon residue content of 0.1 wt% to 5.0 wt% according to ASTM D4530; and / or a potassium content of 100 wppm or less. The sulfur content of the blend can vary depending on the conventional component used for forming the blend, and the target type of fuel oil. For example, if the goal is to make a blend incorporating a very low sulfur fuel oiland / or to make a blend usable as a very low sulfur fuel oil, then the resulting blend can have a sulfur content of 0.01 wt% to 0.5 wt%.Examples

[0052] Several blends were evaluated to determine the benefit of cashew nut shell liquid for improving steam cracker tar and fuel oil compatibility. Steam cracker tar is a pyrolysis tar formed during a steam cracking process. Samples of a very low sulfur fuel oil (VLSFO), steam cracker tar (SCT), and cashew nut shell liquid (CNSL) were obtained commercially. It is noted that the cashew nut shell liquid sample was a degummed cashew nut shell liquid to remove excess potassium. The properties of the neat samples are summarized in FIG. 1. All the neat samples are self-compatible with TSE / TSP values of less than 0.10 wt%.

[0053] The composition of cashew nut shell liquid can be determined according to any convenient method that is commercially used. Various grades of technical cashew nut shell liquid are commercially available, such as grades having at least 50 wt% cardanol, at least 60 wt% cardanol, and at least 70 wt% cardanol. Table 2 shows an example of a composition of a commercially available technical grade cashew nut shell liquid.Table 2 - Composition of Technical Grade Cashew Nut Shell LiquidExample 1 - Cashew Nut Shell Liquid and Steam Cracker Tar

[0054] As an initial test, blends were made of the cashew shell nut liquid (CNSL) and the steam cracker tar (SCT) fractions shown in FIG. 1. Table 3 shows an example of this type of blend.Table 3 - Two Component Blend CNSL and SCT

[0055] As shown in Table 3, compatibility improvement was observed with such 2-component blends of CNSL and SCT. In the blend shown in Table 3, the TSP of SCT alone was 0.08 wt%. After addition of CNSL, the TSP was improved to 0.04 wt% and 0.03 wt% at 10 vol% and 30 vol% of CNSL, respectively. The addition of CNSL not only did not introduce additional sediment in SCT, but it was also able to solubilize the asphaltenes that had been dropped out of solution. The result suggests that there is some improvement in compatibility due to the addition of CNSL. It is noted that the TSP reduction effect shown in Table 3 is larger than what would be predicted by simple dilution. The fact that the TSP reduction is not simply a dilution effect is further illustrated in the next example.Example 2 - Blend of SCT, CNSL, and VLSFO

[0056] In this example, steam cracker tar (SCT) and cashew nut shell liquid (CNSL) were blended together first, and then very low sulfur fuel oil (VLSFO) was added to form the final blended product. By adding the CNSL to the SCT, followed by addition of the VLSFO, the TSP of the resulting blend was reduced or minimized. The CNSL, SCT, and VLSFO fractions correspond to the fractions shown in FIG. 1.

[0057] Table 4 and Table 5 show the TSP reduction due to CNSL. For the blends shown in Table 4 and Table 5, mixtures of SC Tar and CNSL were mixed for one hour, followed by the addition of VLSFO. SC Tar concentrations were kept constant at 4 vol% in Table 4 and 8 vol% in Table 5, respectively, relative to the total volume of the final blended product. CNSL was varied from 0-30 vol% and VLSFO was used to balance.Table 4 - Blends with 4 vol% SCT

[0058] For the 30 vol% blend of CNSL in Table 4, the volume ratio of CNSL to SCT in the blend is roughly 7.0 (7.0 to 1). This is well above the volume ratio of 4.5 or higher that is believed to be needed to reduce the TSP to 0.10 wt% or less.Table 5 - Blends with 8 vol% SCT

[0059] In the results shown in both Table 4 and Table 5, the TSP showed an increase at 1 vol% CNSL but started to decrease at 5 vol% CNSL. The TSP values for the 0-5% CNSL data points are within repeatability of the test method. (0.089*SQRT(TSP)) The result suggests that minimum of 5 vol% CNSL is needed to start observing asphaltene stabilization. Further addition of CNSL at 30% showed more reduction in TSP. It is noted that the volume ratio of CNSL to SCT for the 30 vol% blend is less than 4.0, and therefore the resulting TSP for the blend is greater than 0.10 wt%.

[0060] The results in Table 4 and Table 5 also more clearly illustrate that the benefit of addition of CNSL is substantially greater than what would be expected by mere dilution. For example, in Table 4, the TSP of the SCT and VLSFO alone is 0.29 wt%. Based on addition of 30 vol% of CNSL, a reduction in TSP to roughly 0.20 wt% might be expected just based on dilution. However, the TSP for the 30 vol% CNSL blend in Table 4 is 0.04 wt%. Similarly, in Table 5, the TSP of the blend of SCT and VLSFO alone is 0.65 wt%. By dilution, addition of 30 vol% CSNL might result in a TSP as low as roughly 0.40 wt%. As shown in Table 5, however, the blend with 30 vol% CNSL has a TSP of only 0.15 wt%.Example 3 - Blends with CNSL Added After Blending SCT and VLSFO

[0061] In this example, the CNSL is not added to the blend until after the SCT and VLSFO are mixed together. It is noted that the VLSFO used in this example is not necessarily the same as the VLSFO used in Example 2. Without being bound by any particular theory, this is believed to allow TSP precursors to form, thereby resulting in blends with increased TSP. This increased TSP due to blend order can be mitigated when sufficiently large amounts of CNSL are added to a blend.

[0062] 'fable 6 shows the results from the blends formed in this example. SCT and a VLSFO were mixed followed by the addition of CNSL.Table 6 - Addition of CNSL After Mixing of SCT and VLSFO

[0063] As shown in Table 6, at 5 vol% CNSL concentration, both the sample containing 7 vol% SCT and the sample containing 10 vol% SCT experienced an increase in TSP, suggesting more asphaltene precipitation. This was in contrast with the results in Table 4 and Table 5 where TSP decreased at 5 vol% CNSL. Further addition of CNSL to 20 vol% resulted in a net decrease in TSP in the 7 vol% SCT sample. This indicates that with sufficient addition of CNSL, the formation of TSP precursor can be reversed. For the 10 vol% SCT sample, addition of 20 vol% CNSL resulted in a decrease in TSP relative to the 5 vol% CNSL sample, but was still an increase relative to the blend containing only 10 vol% SCT in VLSFO. This is believed to be due to the fact that the volume ratio of CNSL to SCT was still a relatively low 2.0. This indicates that weight ratios of CNSL to SCT of 2.5 or more may be needed to fully reverse TSP precursor formation when adding CNSL after a challenged fraction is already blended with a conventional fraction.Additional Embodiments

[0064] Embodiment 1. A method for improving the stability of a fuel oil blend or blend component, comprising: providing a challenged fraction and a conventional fraction, the challenged fraction having at least one of an insolubility number of 30 or more and a toluene equivalence of 30 or more; mixing a cashew nut shell liquid fraction with at least one of the challenged fraction and the conventional fraction; and forming a blended fraction comprising at least a portion of the mixture, the blended fraction comprising at least a portion of the cashew nut shell liquid fraction, at least a portion of the challenged fraction, and at least a portion of the conventional fraction, wherein the blended fraction comprises 5.0 vol% or more of the at least a portion of the cashew nut shell liquid fraction and 2.0 vol% or more of the at least a portion of the challenged fraction, relative to a volume of the blended fraction.

[0065] Embodiment 2. The method of Embodiment 1, wherein the blended fraction comprises 5.0 vol% to 15 vol% of the at least a portion of the cashew nut shell liquid fraction,or wherein the blended fraction comprises 5.0 vol% to 30 vol% of the at least a portion of the cashew nut shell liquid fraction.

[0066] Embodiment 3. The method of any of the above embodiments, wherein the challenged fraction comprises a TSP of 0.10 wt% or less, or wherein the conventional fraction comprises a TSP of 0.10 wt% or less, or wherein the blended fraction has a TSP of 0.10 wt% or less, or a combination thereof.

[0067] Embodiment 4. The method of any of the above embodiments, wherein the at least a portion of the conventional fraction comprises 60 wt% or more of a mineral fraction, relative to a weight of the at least a portion of the conventional fraction, or wherein the conventional fraction comprises 5.0 wt% or less of asphaltenes, or wherein the conventional fraction comprises a T90 distillation point of 450°C or higher, or a combination thereof.

[0068] Embodiment 5. The method of any of the above embodiments, wherein a volume ratio of the at least a portion of the cashew nut shell liquid fraction to the at least a portion of the challenged fraction is 3.0 or more, and preferably 4.5 or more.

[0069] Embodiment 6. The method of any of the above embodiments, wherein the conventional fraction comprises an insolubility number of 20 or less and a toluene equivalence of 20 or less.

[0070] Embodiment 7. The method of any of the above embodiments, wherein the challenged fraction comprises an unfluxed pyrolysis tar having a T10 distillation point of 270°C or higher, or wherein the challenged fraction comprises a fluxed pyrolysis tar having a T10 distillation point of 180°C or higher.

[0071] Embodiment 8. The method of any of the above embodiments, wherein the blended fraction comprises 3.0 vol% or more of the challenged fraction, or wherein the blended fraction comprises 5.0 vol% or more of the challenged fraction.

[0072] Embodiment 9. A fuel oil or fuel oil blend component, comprising: 1.0 vol% to 20 vol% of a challenged fraction, relative to a volume of the fuel oil or fuel oil blend component, the challenged fraction comprising at least one of a toluene equivalence of 30 or more and an insolubility number of 30 or more, the challenged fraction optionally having a TSP of 0.10 wt% or less; 5.0 vol% to 80 vol% of a cashew nut shell liquid fraction, a volume ratio of the cashew nut shell liquid fraction to the challenged fraction being 3.0 or higher, optionally 4.5 or higher; and 20 vol% to 94 vol% of a conventional fraction having a TSP of 0.10 wt% or less, wherein the fuel oil or fuel oil blend component comprises a TSP of 0.10 wt% or less.

[0073] Embodiment 10. The fuel oil or fuel oil blend component of Embodiment 9, wherein the conventional fraction comprises an insolubility number of 20 or less and a toluene equivalence of 20 or less.

[0074] Embodiment 11. The fuel oil or fuel oil blend component of any of Embodiments 9 to 10, wherein the conventional fraction comprises 60 wt% or more of a mineral fraction, relative to a weight of the conventional fraction, or wherein the conventional fraction comprises a T90 distillation point of 450°C or higher, or a combination thereof.

[0075] Embodiment 12. The fuel oil or fuel oil blend component of any of Embodiments 9 to 11, wherein the conventional fraction has a BMCI of 50 or less.

[0076] Embodiment 13. The fuel oil or fuel oil blend component of any of Embodiments 9 to 11, wherein the conventional fraction has a BMCI of 50 to 70, and wherein the fuel oil or fuel oil blend component comprises 1.5 vol% or more of the challenged fraction.

[0077] Embodiment 14. The fuel oil or fuel oil blend component of any of Embodiments 9 to 11, wherein the conventional fraction has a BMCI of 70 or higher, and wherein the fuel oil or fuel oil blend component comprises 2.0 vol% or more of the challenged fraction.

[0078] Embodiment 15. The fuel oil or fuel oil blend component of any of Embodiments 9 to 14, wherein the blended fraction comprises 3.0 vol% or more of the challenged fraction, or wherein the blended fraction comprises 5.0 vol% or more of the challenged fraction.

[0079] Additional Embodiment A. The fuel oil or fuel oil blend component of any of Embodiments 9 to 15, wherein the challenged fraction comprises an unfluxed pyrolysis tar having a T10 distillation point of 270°C or higher, or wherein the challenged fraction comprises a fluxed pyrolysis tar having a T10 distillation point of 180°C or higher.

[0080] All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0081] While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims

CLAIMSWHAT IS CLAIMED IS:

1. A method for improving the stability of a fuel oil blend or blend component, comprising: providing a challenged fraction and a conventional fraction, the challenged fraction having at least one of an insolubility number of 30 or more and a toluene equivalence of 30 or more; mixing a cashew nut shell liquid fraction with at least one of the challenged fraction and the conventional fraction; and forming a blended fraction comprising at least a portion of the mixture, the blended fraction comprising at least a portion of the cashew nut shell liquid fraction, at least a portion of the challenged fraction, and at least a portion of the conventional fraction, wherein the blended fraction comprises 5.0 vol% or more of the at least a portion of the cashew nut shell liquid fraction and 2.0 vol% or more of the at least a portion of the challenged fraction, relative to a volume of the blended fraction.

2. The method of claim 1 , wherein the blended fraction comprises 5.0 vol% to 15 vol% of the at least a portion of the cashew nut shell liquid fraction, or wherein the blended fraction comprises 5.0 vol% to 30 vol% of the at least a portion of the cashew nut shell liquid fraction.

3. The method of any of the above claims, wherein the challenged fraction comprises a TSP of 0.10 wt% or less, or wherein the conventional fraction comprises a TSP of 0.10 wt% or less, or wherein the blended fraction has a TSP of 0.10 wt% or less, or a combination thereof.

4. The method of any of the above claims, wherein the at least a portion of the conventional fraction comprises 60 wt% or more of a mineral fraction, relative to a weight of the at least a portion of the conventional fraction, or wherein the conventional fraction comprises 5.0 wt% or less of asphaltenes, or wherein the conventional fraction comprises a T90 distillation point of 450°C or higher, or a combination thereof.

5. The method of any of the above claims, wherein a volume ratio of the at least a portion of the cashew nut shell liquid fraction to the at least a portion of the challenged fraction is 3.0 or more, and preferably 4.5 or more.

6. The method of any of the above claims, wherein the conventional fraction comprises an insolubility number of 20 or less and a toluene equivalence of 20 or less.

7. The method of any of the above claims, wherein the challenged fraction comprises an unfluxed pyrolysis tar having a T10 distillation point of 270°C or higher, or wherein the challenged fraction comprises a fluxed pyrolysis tar having a T10 distillation point of 180°C or higher.

8. The method of any of the above claims, wherein the blended fraction comprises 3.0 vol% or more of the challenged fraction, or wherein the blended fraction comprises 5.0 vol% or more of the challenged fraction.

9. A fuel oil or fuel oil blend component, comprising: 1.0 vol% to 20 vol% of a challenged fraction, relative to a volume of the fuel oil or fuel oil blend component, the challenged fraction comprising at least one of a toluene equivalence of 30 or more and an insolubility number of 30 or more, the challenged fraction optionally having a TSP of 0.10 wt% or less; 5.0 vol% to 80 vol% of a cashew nut shell liquid fraction, a volume ratio of the cashew nut shell liquid fraction to the challenged fraction being 3.0 or higher, optionally 4.5 or higher; and 20 vol% to 94 vol% of a conventional fraction having a TSP of 0.10 wt% or less, wherein the fuel oil or fuel oil blend component comprises a TSP of 0.10 wt% or less.

10. The fuel oil or fuel oil blend component of claim 9, wherein the conventional fraction comprises an insolubility number of 20 or less and a toluene equivalence of 20 or less.

11. The fuel oil or fuel oil blend component of any of claims 9 to 10, wherein the conventional fraction comprises 60 wt% or more of a mineral fraction, relative to a weight of the conventional fraction, or wherein the conventional fraction comprises a T90 distillation point of 450°C or higher, or a combination thereof.

12. The fuel oil or fuel oil blend component of any of claims 9 to 11 , wherein the conventional fraction has a BMCI of 50 or less.

13. The fuel oil or fuel oil blend component of any of claims 9 to 11 , wherein the conventional fraction has a BMCI of 50 to 70, and wherein the fuel oil or fuel oil blend component comprises 1.5 vol% or more of the challenged fraction.

14. The fuel oil or fuel oil blend component of any of claims 9 to 11 , wherein the conventional fraction has a BMCI of 70 or higher, and wherein the fuel oil or fuel oil blend component comprises 2.0 vol% or more of the challenged fraction.

15. The fuel oil or fuel oil blend component of any of claims 9 to 14, wherein the blended fraction comprises 3.0 vol% or more of the challenged fraction, or wherein the blended fraction comprises 5.0 vol% or more of the challenged fraction.

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