Low sulfur fuel oil blends for stability enhancement and associated methods
11667858 · 2023-06-06
Assignee
Inventors
- Richard L. Eller (Findlay, OH, US)
- Peg Broughton (Findlay, OH, US)
- V. Elijah Mullins (Findlay, OH, US)
- John R. Weber (Findlay, OH, US)
- Jeffrey A. Sexton (Findlay, OH, US)
Cpc classification
C10L2200/0438
CHEMISTRY; METALLURGY
C10L2290/543
CHEMISTRY; METALLURGY
C10L10/00
CHEMISTRY; METALLURGY
C10G69/04
CHEMISTRY; METALLURGY
C10G2300/107
CHEMISTRY; METALLURGY
C10L2230/14
CHEMISTRY; METALLURGY
C10L2290/547
CHEMISTRY; METALLURGY
C10L2270/026
CHEMISTRY; METALLURGY
C10G2300/304
CHEMISTRY; METALLURGY
International classification
C10G69/04
CHEMISTRY; METALLURGY
Abstract
Fuel oil compositions, and methods for blending such fuel oil compositions, to enhance initial compatibility and longer term stability when such fuel oil compositions are blended to meet IMO 2020 low sulfur fuel oil requirements (ISO 8217). In one or more embodiments, asphaltenic resid base stocks are blended with high aromatic slurry oil to facilitate initial compatibility such that low sulfur cutter stocks, e.g., vacuum gas oil and/or cycle oil, may be further blended therein to cut sulfur content while maintaining longer term stability. These fuel oil compositions are economically advantageous when used as marine low sulfur fuel oils because greater concentrations of high viscosity resids are present in the final blend.
Claims
1. A method of making a low sulfur marine bunker fuel oil composition, the method comprising: producing a vacuum tower bottoms having a sulfur content of less than about 2 percent by weight; filtering a decant oil to at least partially remove fluid catalytic cracking catalyst fines to reduce an aluminum and a silicon content and produce a filtered decant oil therefrom; blending the filtered decant oil into the vacuum tower bottoms, the filtered decant oil having a sulfur content of less than about 1 percent by weight; and blending a vacuum gas oil having a sulfur content of less than about 0.1 percent by weight into the vacuum tower bottoms that is blended with the filtered decant oil to define the low sulfur marine bunker fuel oil composition, the low sulfur marine bunker fuel oil composition having about 12 percent to about 50 percent by volume of the vacuum tower bottoms, at least about 16 percent by volume of filtered decant oil and about 25 percent to about 74 percent by volume of vacuum gas oil, the low sulfur marine fuel oil composition also having a combined volume of the vacuum tower bottoms and the filtered decant oil that is at least about 50 percent, a final sulfur content of less than about 0.5 percent by weight, and an aromatic content of greater than about 50 percent by weight.
2. The method of claim 1, further comprising producing the decant oil in a fluid catalytic cracker that has a hydrotreated hydrocarbon feed thereto.
3. The method of claim 1, wherein the low sulfur marine bunker fuel oil composition has between about 16 percent to about 40 percent by volume of the filtered decant oil.
4. The method of claim 1, wherein the low sulfur marine bunker fuel oil composition has an aromatics content between about 50 percent to about 85 percent.
5. The method of claim 1, wherein the vacuum tower bottoms and the decant oil each have a total aged sediment of greater than about 0.1 percent by weight.
6. The method of claim 5, wherein the low sulfur marine bunker fuel oil composition has a total aged sediment of less than about 0.1 percent by weight.
7. A method of making a low sulfur fuel oil composition as a low sulfur marine bunker fuel oil, the method comprising: obtaining a residuum having a sulfur content of at least about 1.5 percent by weight, the residuum comprising between about 12 percent to about 50 percent by volume of the low sulfur fuel oil composition; introducing a catalytic cracked aromatic process oil into a blend tank along with the residuum to define an intermediate blend, the catalytic cracked aromatic process oil being from a fluid catalytic cracker and having a sulfur content of less than about 0.5 percent by weight, the catalytic cracked aromatic process oil also comprising at least about 16 percent by volume of the low sulfur fuel oil composition, the combined concentration of residuum and the catalytic cracked aromatic process oil in the low sulfur fuel oil composition comprising at least about 50 percent by volume; and introducing a low sulfur cutter stock into the intermediate blend in the blend tank to define the low sulfur fuel oil composition, the low sulfur cutter stock selected from the group consisting of a vacuum gas oil, a cycle oil, and a diesel fuel, the low sulfur cutter stock comprising a sulfur content of less than about 0.15 percent by weight and comprising between about 25 percent to about 74 percent by volume of the low sulfur fuel oil composition, the low sulfur fuel oil composition comprising a sulfur content of less than about 0.5 percent by weight, a total aromatics content of at least about 45% by volume, and the combined concentration of residuum and catalytic cracked aromatic process oil of at least about 35% by volume.
8. The method of claim 7, wherein the residuum comprises at least one of atmospheric tower bottoms or vacuum tower bottoms.
9. The method of claim 7, wherein the catalytic cracked aromatic process oil comprises a decant oil that has at least some of an aluminum or a silicon removed therefrom prior to introducing the decant oil into the blend tank.
10. The method of claim 7, wherein the combined concentration of residuum and catalytic cracked aromatic process oil in the low sulfur fuel oil composition comprises at least about 60 percent by volume.
11. The method of claim 7, wherein the combined concentration of residuum and catalytic cracked aromatic process oil in the low sulfur fuel oil composition comprises at least about 70 percent by volume.
12. The method of claim 7, wherein the low sulfur fuel oil composition comprises a sulfur content of less than about 0.45 percent by weight.
13. The method of claim 7, further comprising filtering the catalytic cracked aromatic process oil to remove, at least partially, fluid catalytic cracking catalyst fines therefrom prior to the blending of the catalytic cracked aromatic process oil with the residuum, and blending a heel hydrocarbon fraction with at least one of the residuum, the catalytic cracked aromatic process oil, or the intermediate blend.
14. A method of making a low sulfur marine bunker fuel oil, the method comprising: producing a vacuum tower residuum in a vacuum distillation column, the vacuum tower residuum having a sulfur content of less than about 2 percent by weight and a total aged sediment of greater than 0.1 percent by weight; filtering a catalytic cracked aromatic process oil to remove, at least partially, fluid catalytic cracking catalyst fines therefrom; introducing the catalytic cracked aromatic process oil into a blend tank along with the vacuum tower residuum to define an intermediate blend, the catalytic cracked aromatic process oil comprising at least one of a decant oil or a cycle oil that is produced from a hydrotreated gas oil feed to a fluid catalytic cracker, the catalytic cracked aromatic process oil having a sulfur content of less than about 0.5 percent by weight and a total aged sediment of greater than about 0.1 percent by weight, the intermediate blend having a total aged sediment of less than about 0.1 percent by weight, the catalytic cracked aromatic process oil contributing less than about 60 weight percent of cracked stock to the low sulfur marine bunker fuel oil; blending an added low sulfur cutter stock with the intermediate blend in the blend tank to define the low sulfur fuel oil composition, the low sulfur cutter stock comprising one or more of a vacuum gas oil or a diesel fuel, the low sulfur cutter stock having a sulfur content of less than about 0.5 percent by weight; and providing the low sulfur fuel oil composition as the low sulfur marine bunker fuel oil, the vacuum tower residuum comprising between about 12 percent to about 50 percent by weight of the low sulfur marine bunker fuel oil, the catalytic cracked aromatic process oil comprising at least about 16 percent by volume of the low sulfur marine bunker fuel oil, and the low sulfur cutter stock comprising between about 25 percent to about 74 percent by volume of the low sulfur marine bunker fuel oil, the low sulfur marine bunker fuel oil having a sulfur content of less than about 0.5 percent by weight, a total aromatics content of at least about 45 percent by weight, and a combined concentration of vacuum tower residuum and catalytic cracked aromatic process oil of at least about 35 percent by volume.
15. The method of claim 14, wherein the vacuum tower residuum has a sulfur content of less than about 1.5 percent by weight.
16. The method of claim 14, wherein providing the low sulfur fuel oil composition as the low sulfur marine bunker fuel oil occurs without hydrotreating the low sulfur fuel oil composition after blending the low sulfur cutter stock with the intermediate blend.
17. The method of claim 14, wherein the catalytic cracked aromatic process oil comprises a decant oil that has at least some aluminum or silicon removed therefrom prior to introducing the decant oil into the blend tank.
18. The method of claim 14, further comprising blending a heel hydrocarbon fraction with at least one of the residuum, the catalytic cracked aromatic process oil, or the intermediate blend.
19. A low sulfur marine bunker fuel oil composition comprising: a volume % of between about 25 to about 75 of an intermediate blend of an asphaltenic resid and an aromatic rich hydrocarbon fraction; and a volume % of between about 25 to about 75 of a low sulfur cutter stock.
20. The bunker fuel oil composition of claim 19, wherein the asphaltenic resid and the aromatic rich hydrocarbon fraction intermediate blend comprises an asphaltenes in a weight % greater than about 1, a resins in a weight % of between about 1 to about 25, and an aromatics in a weight % of between about 1 to about 75.
21. The bunker fuel oil composition of claim 19, wherein the aromatic rich hydrocarbon fraction comprises an aromatic content greater than about 50 weight %.
22. The bunker fuel oil composition of claim 19, wherein the low sulfur cutter stock comprises one or more of a vacuum gas oil, a cycle oil, a diesel fuel, a middle distillate, or a substantially paraffinic stock.
23. A low sulfur marine bunker fuel oil composition comprising: at least about 35% by volume of an asphaltenic residuum blended with an asphaltene stabilizer; and about 24% to about 75% by volume of a low sulfur cutter stock.
24. The bunker fuel oil composition of claim 23, wherein the asphaltene stabilizer comprises one or more of a resin-containing fraction or a highly aromatic fraction.
25. The bunker fuel oil composition of claim 24, wherein the highly aromatic fraction comprises one or more of a decant oil, a cycle oil, a slurry oil, a light cycle oil, or an aromatic stock.
26. The bunker fuel oil composition of claim 24, wherein the aromatic rich hydrocarbon fraction comprises an aromatic content greater than about 50 weight %.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1) These and other features, aspects, and advantages of the disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and, therefore, are not to be considered limiting of the scope of the disclosure.
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DETAILED DESCRIPTION
(9) So that the manner in which the features and advantages of the embodiments of the compositions and related methods disclosed herein, as well as others, which will become apparent, may be understood in more detail, a more particular description of embodiments of compositions and related methods briefly summarized above may be had by reference to the following detailed description of embodiments thereof, in which one or more are further illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only various embodiments of the compositions and related methods disclosed herein and are therefore not to be considered limiting of the scope of the compositions and related methods disclosed herein as it may include other effective embodiments as well.
(10) With the implementation of lower sulfur specifications for marine fuel oil under IMO 2020, refiners have turned to blending high sulfur refinery products, such as resid, with low sulfur distillates to meet the low sulfur and other fuel specifications. However, the blend must have initial compatibility in order to prevent asphaltenes suspended in the heavy blend fraction from precipitating out of solution upon blending. Moreover, the blend must also have longer term stability, such that the asphaltenes present in the heavy blend fraction remain in solution over time during sale, distribution, and other outputting, e.g., during storage and/or transport.
(11) Applicant has recognized and found that if the base stock asphaltenic resid does not itself have sufficient stability prior to adding more paraffinic low sulfur distillates, such as sweet gas oil and/or diesel fuel, then the blend has an increased risk of asphaltene precipitation. This discovery, for example, is more than just the general perception that asphaltene precipitation increases as the density variation between asphaltenic resid and cutter stocks increases. Here, Applicant has recognized that the base stock asphaltenic resid, e.g., either the atmospheric tower bottoms or vacuum tower bottoms, must itself have a degree of stability prior to adding more paraffinic low sulfur distillates, such as sweet gas oil and/or diesel fuel or other middle distillates.
(12) The colloidal instability index (CII) is one approach, and is often used, to ascertain the instability of a crude oil. CII is computed from a SARA analysis, which is a measure of the chemical composition of the aromatics, resins, saturates, and asphaltenes in a sampled hydrocarbon. CII is expressed as the ratio of the sum of asphaltenes and saturates to the sum of aromatics and resins. Although traditionally used with respect to crude oils, CII has been extrapolated and used to ascertain the stability of fractions of heavier oils, such as resids. Generally, if the CII is less than 0.7, then the hydrocarbon is stable, but if the CII is greater than 0.9, then the hydrocarbon is unstable and likely to precipitate asphaltenes. A CII between 0.7 and 0.9 represents a region of moderate stability or growing instability.
(13) Applicant also has discovered that CII data, when computed for some severely cracked resids, is misleading with respect to compatibility and stability. For example, Table I below lists characteristics of several example resid base stock, including their SARA analysis and CII data:
(14) TABLE-US-00001 TABLE I SHORT RESID Ex. 1 Ex. 2 Ex. 3 Ex. 4 SPG @ ~15° C. 1.03 0.99 1.03 0.97 Visocisty @ ~50° C. (cSt) 473.78 355.43 1200 888.93 Sulfur (wt %) 1.74 2.51 0.54 1.38 Pour Point (° C.) 53.6 Flash Point (° C.) 178 99 API Gravity @ ~60° F. 5.8 11.9 5.4 14.3 Heptane Insolubles 6.42 8.78 6.94 8.55 Saturates 10.38 15.7 12.81 12.42 Aromatics 70.16 50.06 49.25 46.93 Resins 10.32 20.88 26.95 19.86 Asphaltenes 9.12 13.34 10.99 20.77 Aromatics/Resins 6.80 2.40 1.83 2.36 CII 0.242 0.409 0.312 0.499 Solubility S.sub.BN 110 140 Insolubility I.sub.N 76 40
(15) The first resid, labeled as Ex.1, is a crude-derived vacuum tower bottoms resid that is further processed and may be characterized as being severely cracked. The high aromatic content at about 70 percent is indicative of a severely cracked resid. But, the CII for this fraction is 0.24, which is indicative of a very stable hydrocarbon one that should not precipitate asphaltenes upon blending with low sulfur distillates. Applicant has further found, however, that this Ex.1 resid fraction, is problematic and readily precipitates asphaltenes upon blending with low sulfur distillates and cutter stock, such as sweet gas oil and/or diesel fuel or other middle distillates, e.g., jet fuel, kerosene, etc.
(16)
(17) As illustrated in
(18) Applicant has thus still further recognized that adding a high aromatic and/or resin stock, such as a decant oil, to a given resid stock provides the unexpected result of improving the initial compatibility and the longer term stability of the resid stock upon blending with cutter stocks such that more paraffinic, low-sulfur cutter stocks may be blended with the resid stock. A decant oil, otherwise known as DCO or slurry oil, is a catalytic cracked aromatic process oil that is the heaviest cut from a fluid catalytic cracker.
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(20) TABLE-US-00002 TABLE II DISTILLATE Decant Oil LSVGO HTGO HPVGO SPG @ ~15° C. 1.08 0.90 0.91 0.90 Visocisty @ ~50° C. (cSt) 189.68 23.35 Sulfur (wt %) 0.30 0.05 0.53 0.05 Pour Point (° C.) −1 24 Flash Point (° C.) 109.5 159.0 API Gravity @ ~60° F. −0.3 25.3 22.6 22.3 Heptane Insolubles 0.29 0.17 <0.1 <0.1 Saturates 10.05 56.12 42.50 55.78 Aromatics 86.45 41.85 56.40 43.42 Resins 2.4 0.53 0.8 0.8 Asphaltenes 1.1 0 0.3 0 CII 0.125 1.324 0.748 1.261 Solubility S.sub.BN 176 44 41 32 Insolubility I.sub.N 69 0 0 0
(21) As shown in
(22) Applicant has, therefore, discovered a synergistic effect of adding an aromatic rich hydrocarbon fraction, such as decant oil or cycle oil, to stabilize an asphaltenic resid prior to adding distillates as diluents to subsequently drive down the sulfur content. This synergetic effect, as shown in
(23)
(24) Therefore,
(25)
(26) Resid fractions having high concentrations of decant oils (slurry) may cause the final LSFO blends to be out of specification due to high metal concentrations. Under IMO 2020 (see ISO 8217, RMG 380), LSFO has a maximum limit of 60 ppm of combined aluminum plus silicon content. FCC catalysts typically have a silicon and/or aluminum support matrix that incorporates rare earth metals for catalytic activity. Decant oils (slurry), which are produced by the FCC unit, can contain high amounts of FCC catalyst fines, largely composed of aluminum and/or silicon. However, the presence of these fines in the decant oil (slurry) can be eliminated by filtering decant oil (slurry) off of the FCC unit before blending. In one or more embodiments, at least partial amounts of aluminum and/or silicon may be removed from the decant oil (slurry) prior to further blending, e.g., by filtering, decanting, electric field separation, centrifuge, etc. With respect to the electric field separation, a Gulftronic electrostatic separator manufactured by General Atomics of San Diego, Calif. may be used to remove FCC catalyst fines from the decant/slurry oil.
(27)
(28) As can be seen in
(29) Indeed, the importance of this result is not in the stability itself, but rather the synergistic effect of the combination of the resid and decant oil to further permit blending of low-sulfur cutter stocks. Also shown in
(30) In one or more embodiments, resids, such as vacuum tower bottoms or atmospheric tower bottoms, may be blended with low sulfur cutter stocks to create LSFO meeting the 0.5% maximum sulfur content required by IMO 2020 (see ISO 8217, RMG 380). However, the dilution of asphaltenic resids—those resids having asphaltenes with cutter stocks high in saturate content may disrupt the supportive matrix, thought to be provided by resins, in the resid, which can lead to asphaltene precipitation and sediment formation. Highly aromatic stocks, such as slurry/decant oil, can be blended with the resid to stabilize the asphaltenes and improve both initial compatibility and long-term (aged) stability of the final LSFO blend. In some cases, synergistic effects are noted in which the aged sediment of the blend is lower than the starting residual and low sulfur blend components. Similarly, aromatic stocks can be used as a stabilizing binder for blending incompatible finished LSFOs as long as the final product specifications are not violated.
(31) Disclosed herein, therefore, are low sulfur marine bunker fuel oil blends, and methods of making such blends, to improve initial compatibility and aged stability of asphaltenic resids. The blending of resid fractions with dense, aromatic decant (DCO)/slurry oils, created from hydrotreated FCC feed, prior to final dilution, or the blending of resid fractions with cracked hydrocarbon fractions solely, or a combination thereof, facilitates in lowering the overall sulfur content of the blend to meet the LSFO specification, e.g., IMO 2020, while minimizing density changes and providing added aromaticity to support asphaltene stability. It will be understood that the ratios for final LSFO blend components may be adjusted to meet the sulfur and other fuel specifications.
(32) As is known to those skilled in the art, resid or residuum is any refinery fraction left behind after distillation. Resid may refer to atmospheric tower bottoms and/or vacuum tower bottoms.
(33) Atmospheric tower bottoms (ATB), also called long resid, is the heaviest undistilled fraction (uncracked) in the atmospheric pressure distillation of a crude oil, as is known to those skilled in the art. ATB has crude oil components with boiling points above about 650° F. (343° C.), which is below the cracking temperature of the crude oil.
(34) Vacuum tower bottoms (VTB), also called short resid, is the heaviest undistilled fraction (uncracked) in the vacuum distillation of a hydrocarbon feedstock, as is known to those skilled in the art. VTBs may have one or more of the following characteristics: a density at 15° C. of between about 0.8 and about 1.1 g/ml, a sulfur content of between about 1.0 and about 3.0 wt %, a pour point of between about −20 and about 75° C., a kinematic viscosity of between about 50 and about 12,000 cSt (50° C.), a flash point of between about 50 and about 200° C., and an API density of between about 3.0 and about 20. Moreover, VTBs generated from sweet run hydrocarbon feedstock (e.g., hydrotreated feedstock to the vacuum tower) may have sulfur content below about 1.0 wt %, below about 0.9 wt %, below about 0.8 wt %, below about 0.7 wt %, below about 0.6 wt %, below about 0.5 wt %, below about 0.4 wt %, below about 0.3 wt % or even below about 0.2 wt %.
(35) Decant oil (DCO), also known as slurry oil, is a high-boiling catalytic cracked aromatic process oil and is the heaviest cut off of a fluid catalytic cracker unit, as is known to those skilled in the art. Decant oil may have one or more of the following characteristics: a density at 15° C. of between about 0.9 and about 1.2 g/ml, a sulfur content of between about 0.20 and about 0.50 wt %, a pour point of between about −5 to about 5° C., a kinematic viscosity of between about 100 and about 200 cSt (50° C.), a flash point between about 50 and about 150° C., and an API of between about −1.0 and about 1.0.
(36) Vacuum gas oil (VGO) may be light and/or heavy gas oil cuts from the vacuum distillation column, as is known to those skilled in the art. VGO may have one or more of the following characteristics: a density at 15° C. of between about 0.85 and about 1.1 g/ml, a sulfur content of between about 0.02 and about 0.15 wt %, a pour point of between about to 15 about 35° C., a kinematic viscosity of between about 15 and about 35 cSt (50° C.), a flash point between about 100 and about 175° C., and an API of between about 15 and about 30.
(37) Cycle oil is the diesel-range, cracked product from the fluid catalytic cracker unit, as is known to those skilled in the art. Cycle oil may be light, medium or heavy and may have one or more of the following characteristics: a density at 15° C. of between about 0.75 and about 1.0 g/ml, a sulfur content of between about 0.01 and about 0.25 wt %, a kinematic viscosity of between about 2 and about 50 cSt (50° C.), a flash point between about 50 and about 70° C., and an API of between about 25 and about 50.
(38) In one or more of such blends, about 5 to about 80 percent by volume of an atmospheric tower bottoms, vacuum tower bottoms, or a combination of both is utilized as a base stock. The resid base stock imparts viscosity and compatibility to the blend, but tends to be high in sulfur content, and may be between about 1.0 to about 2.0 or more by weight percent, which is well above the IMO 2020 sulfur specification of 0.5 weight percent. In one or more embodiments, the sulfur content of the resid base stock (i.e., atmospheric tower bottoms, vacuum tower bottoms, or a combination of both) may be greater than 1.0 wt %, greater than 1.1 wt %, greater than 1.2 wt %, greater than 1.3 wt %, greater than 1.4 wt %, greater than 1.5 wt %, greater than 1.6 wt %, greater than 1.7 wt %, greater than 1.8 wt %, greater than 1.9 wt %, or even greater than 2.0 wt %. The sulfur content of the resid base stock may also be less than or equal to each of the several values described above. For example, the sulfur content of the resid base stock may be less than 2.0 wt %, less than 1.5 wt %, less than 0.5 wt %, less than 0.25% or even less. To improve finished LSFO stability, about 5 to about 50 percent by volume of a residual cracked stock, such as decant oil (DCO) or slurry oil, is blended into the resid base stock. The decant oil tends to have a lower sulfur content than the resid base stock, and such sulfur content may be less than about 1.0 percent by weight, less than about 0.9 percent by weight, less than about 0.8 percent by weight, less than about 0.7 percent by weight, less than about 0.6 percent by weight, less than about 0.5 percent by weight, less than about 0.4 percent by weight, less than about 0.3 percent by weight, less than about 0.2 percent by weight, or even less than about 0.1 percent by weight. As described above, the synergistic effect of the decant oil and resid blend with respect to initial compatibility and/or longer term stability permits additional blending of up to about 75 percent by volume with low sulfur cutter stocks, such as light cycle oil (LCO), medium cycle oil (MCO), heavy cycle oil (HCO), and vacuum gas oil (VGO) cracked hydrocarbons or combinations thereof. These cracked hydrocarbons tend to be the lowest of the three blend components with respect to sulfur, and such sulfur content may less than about 0.1 percent by weight, less than about 0.15 percent by weight, less than about 0.20 percent by weight, less than about 0.25 percent by weight, less than about 0.30 percent by weight, less than about 0.40 percent by weight, less than about 0.45 percent by weight, or even less than about 0.50 percent by weight.
(39) In one or more other such blends, about 12 to about 50 percent by volume of an atmospheric tower bottoms, vacuum tower bottoms, or a combination of both is utilized as a base stock. Again, to improve finished LSFO stability, about 16 to about 40 percent by volume of a residual cracked stock, such as decant oil or slurry oil, is blended into the resid base stock. The synergistic effect of the residual cracked stock (i.e., decant oil) and base stock resid blend permits additional blending of between about 25 to about 74 percent by volume of low sulfur cutter stocks, such as LCO, MCO, HCO, and VGO cracked hydrocarbons or combinations thereof, which may be paraffinic depending on the hydrocarbon fraction. In one or more embodiments of such blends, the blend characteristics may include one or more of the following: the kinematic viscosity is between about 50.1 and about 80.0 cSt, the API is between about 10.0 and about 18.9, the pour point is below 7° C. and the CCAI is greater than 810.
(40) In one or more other such blends, about 15 percent to about 25 percent by volume of an atmospheric tower bottoms, vacuum tower bottoms, or combination of both is utilized as a base stock. Again, to improve finished LSFO stability, about 30 percent to about 45 percent by volume of residual cracked stock, such as a decant oil or slurry oil, is blended into the resid base stock. Thus, the ratio of the residual cracked stock (i.e., FCC cracked hydrocarbon products) to base stock resid may be 1.5 to 1 or even greater. Thus, more than 1.5, more than 1.6, more than 1.7, more than 1.8, more than 1.9 or even more than 2 times as much residual cracked stock may be used as compared to base stock resid. The synergistic effect of the residual cracked stock and base stock resid blend permits additional blending of between about 30 percent and about 50 percent by volume of low sulfur cutter stocks, such as LCO, MCO, HCO, and VGO cracked hydrocarbons or combination thereof, which may be paraffinic depending on the hydrocarbon fraction.
(41) The utilization of vacuum tower bottoms (VTB) resid stock is enhanced if it is blended with decant oil (slurry oil) in sufficient volumetric proportions to create a synergistic blend. Thus, in one or more blend embodiments, initial compatibility and/or longer term stability are improved when VTB and decant oil (slurry) oil have a combined concentration of at least about 25 percent by volume of the final blend, with the remaining portion being composed of a cutter stock, such as light cycle oil, medium cycle oil, heavy cycle oil, vacuum gas oil, or combinations thereof. In one or more other embodiments, the combined concentration of VTB and decant oil is at least about 10 percent by volume, at least about 15 percent by volume, at least about 20 by volume, at least about 30 percent by volume, at least about 35 percent by volume, at least about 40 percent by volume, at least about 45 percent by volume, at least about 50 percent by volume, at least about 55 percent by volume, at least about 60 percent by volume, at least about 65 percent by volume, at least about 70 percent by volume, at least about 75 percent by volume, at least about 80 percent by volume, at least about 85 percent by volume, at least about 90 by volume, at least about 95 percent by volume, with the remaining portion in each case being composed of a cutter stock, such as light cycle oil, medium cycle oil, heavy cycle oil, vacuum gas oil, or combinations thereof, or other hydrocarbon fractions or additives, as known by those skilling the art. In at least one embodiment, the final blend comprises mainly vacuum tower bottoms and decant oil.
(42) The utilization of atmospheric tower bottoms (ATB) in combination with VTB, or the utilization of ATB resid stock alone, is enhanced if these resid stocks are blended with decant oil (slurry oil) in sufficient volumetric proportions to create a synergistic blend. Thus, in one or more blend embodiments, initial compatibility and/or longer term stability are improved when ATB, VTB, and decant oil (slurry oil), or ATB and decant oil, have a combined concentration of at least 50 percent by volume of the final blend, with the remaining portion being composed of a cutter stock, such as light cycle oil, medium cycle oil, heavy cycle oil, vacuum gas oil, or combinations thereof. In one or more other embodiments, the combined concentration of ATB, VTB, and decant oil, or ATB and decant oil, is at least about 10 percent by volume, at least about 15 percent by volume, at least about 20 percent by volume, at least about 25 percent by volume, at least about 30 percent by volume, at least about 35 percent by volume, at least about 40 percent by volume, at least about 45 percent by volume, at least about 55 percent by volume, at least about 60 percent by volume, at least about 65 percent by volume, at least about 70 percent by volume, at least about 75 percent by volume, at least about 80 percent by volume, at least about 85 percent by volume, at least about 90 by volume, at least about 95 percent by volume, with the remaining portion in each case being composed of a cutter stock, such as light cycle oil, medium cycle oil, heavy cycle oil, vacuum gas oil, or combinations thereof, or other hydrocarbon fractions or additives, as known by those skilled in the art. In at least one embodiment, the final blend comprises mainly atmospheric tower bottoms and decant oil.
(43) In one or more embodiments, the stability of the blend is further enhanced by the addition of two or more cutter stocks in combination. In such embodiments, the blend includes between about 15 percent to about 25 percent by volume of a base stock that is an atmospheric tower bottoms, vacuum tower bottoms, or a combination of both. To increase the stability of the resid base stock, between about 20 percent to about 40 percent by volume of a residual cracked stock, such as decant oil or slurry oil, is blended into the resid base stock. Thus, the ratio of the residual cracked stock (i.e., FCC cracked hydrocarbon products) to resid may be 1.5 to 1 or even greater. Thus, more than 1.5, more than 1.6, more than 1.7, more than 1.8, more than 1.9 or even more than 2 times as much residual cracked stock may be used as compared to resid. As previously mentioned, the synergistic effect of the decant/slurry oil and resid blend permits additional blending of between about 40 to about 65 percent by volume of more paraffinic, but lower sulfur cutter stocks, such as VGO, low sulfur VGO or combinations thereof. The blending of lower sulfur cutter stocks ensures that the final LSFO blend that includes the resid base stock and the decant/slurry oil will meet the required lower sulfur specification. However, in one or more embodiments, it has been found that adding LCO that is high in aromatic content in addition to VGO may enhance stability of the overall four component blend. Such added LCO may be in an amount of between about 0 percent by volume to about 15 percent by volume, which is equal to or less than the amount of VGO/LSVGO added to the blend. In one or more embodiments of such blends, the blend characteristics may include one or more of the following: the kinematic viscosity is between about 5 and about 20 cSt, the API is between about 10 and about 16, the flash point is below about 140° C. and the CCAI is greater than about 830.
(44) TABLE III below gives the characteristics of several blend components, e.g., various VTB resids, decant/slurry oil, DGO, and LCO used in the several prophetic examples of final four-component blends (i.e., Blend A to Blend E) according to the disclosure herein. TABLE IV below gives the final blend compositions and the resulting characteristics for these several prophetic examples. In each of Blend A to Blend E, the four components blended as shown create a stable mixture in which the aged sediment is calculated below 0.1%.
(45) TABLE-US-00003 TABLE III Blend Component Resid A Resid B Resid C DCO/Slurry DGO LCO SPG @ ~15° C. 0.99 0.98 1.03 1.08 0.90 0.93 Viscocisty @ ~50° C. (cSt) 355.43 2234.82 8358.95 189.68 23.35 2.12 Sulfur (wt %) 2.51 0.42 0.54 0.30 0.05 0.05 Pour Point (° C.) −1 24 Flash Point (° C.) 82.5 83.5 109.5 159 57.5 API Gravity @ ~60° F. 11.9 12.9 5.4 −0.3 25.3 20.7 Heptane Insolubles 8.78 0.29 0.17 Saturates 15.7 13.29 12.81 10.05 56.12 16.67 Aromatics 50.06 54.1 49.25 85.45 41.85 83.32 Resins 20.88 22.1 26.95 2.4 0.53 0 Asphaltenes 13.34 10.5 10.99 1.1 0 0 CII 0.41 0.31 0.31 0.13 1.32 0.20 Solubility S.sub.BN 176 44 Insolubility I.sub.N 69 0
(46) TABLE-US-00004 TABLE IV Blend A Blend B Blend C Blend D Blend E Resid A 0 0 0 0 10.37 Resid B 55.23 0 0 0 0 Resid C 0 14.59 19.79 20.45 0 DCO/slurry 24.74 21.92 35.18 34.59 27.59 DGO 17.08 61.40 40.36 40.17 60.00 LCO 2.96 2.09 4.67 4.78 2.04 API Gravity @ ~60° F. 11.47 15.77 12.96 11.21 15.82 Density @ ~15° C. (g/ml) 0.96 0.95 0.96 0.98 0.95 Viscosity @ ~50° C. (cSt) 17.54 10.86 6.92 7.56 9.59 Sulfur (wt %) 0.32 0.19 0.40 0.25 0.39 Water by Distillation (vol %) 0.04 0.04 0.04 0.04 0.04 Flash Point (° C.) 102.06 122.84 124.97 104.50 135.34 Pour Point (° C.) 0 0 0 0 0 Potential Total Sediment (wt %) <0.01 <0.01 <0.01 <0.01 0.06 Ash Content (wt %) 0 0 0 0 0 Vanadium (wppm) 9.14 0.19 14.71 0.19 18.00 Sodium (wppm) 6.36 0.84 2.52 0.79 2.61 Aluminum + Silicon (wppm) 5.55 5.50 13.42 7.89 6.76 Copper (wppm) 0.30 0.25 0.30 0.24 0.31 Calcium (wppm) 3.38 0.17 0.72 0.16 0.99 Zinc (wppm) 0.57 0.24 0.33 0.16 0.56 Phosphorus (wppm) 1.43 0.84 1.09 0.79 1.16 Nickel (wppm) 8.95 0.26 6.91 0.24 7.48 Iron (wppm) 10.59 0.22 1.64 0.23 3.58 Micro Carbon Residue (wt %) 10.76 1.19 5.00 1.81 3.01 Total Acid Number (mg KOH/ 0.12 0.04 0.10 0.04 0.10 CCAI 830.64 834.94 847.49 853.99 841.57 Saturates 0.20 0.37 0.28 0.27 0.37 Aromatics 0.64 0.56 0.63 0.62 0.59 Resins 0.20 0.05 0.09 0.08 0.07 Asphaltenes 0.11 0.04 0.04 0.06 0.04 CII 0.38 0.66 0.44 0.47 0.62 Solubility Index S.sub.BN Insolubility Index I.sub.N 69 69 69 69 69
(47)
(48) The use of three or more component blends also provides some flexibility regarding other desired or required blend properties. For example, and to limit the scope in any way, the decant/slurry oil may be blended with a greater amount of a heavy resid such that the resulting decant/resid blend is too heavy and would not meet the density specification of the final blend without additional components. A VGO or other sweet hydrocarbon fraction may be blended with the decant/resid to bring the sulfur of the resulting blend into specification. Moreover, a lighter distillate, such as kerosene, diesel, etc., may then be added to three-component blend of resid/decant/VGO to bring the density of the resulting and final four-component blend into specification. Thus, as described herein, the use of four components permits the utilization of a greater amount of resid while still providing a final blend that meets sulfur and density specifications.
(49)
Example 1
(50) In a first non-limiting, prophetic example of the above-described blending to achieve LSFO that meets specification under ISO 2020, a vacuum tower resid (RESID), a decant oil (DECANT) and a vacuum gas oil (VGO) were blended such that the final blend had 22.6% by volume of RESID, 14.3% by volume of DECANT, and 63.1% by volume of VGO. TABLE V gives the characteristics of the RESID, DECANT, VGO and the final blend. The combination of VTB and Decant was 36.9% by volume. The data provided in TABLE V for each of the RESID, DECANT, and VGO is based upon a certified analysis of each respective blend component that was performed by a third party analyzer. The data for the final blend (BLEND) given in TABLE V is based on a certified analysis of a hand blend that was also performed by the third party analyzer. Based on the characteristics thereof given in the far right column of TABLE V, the BLEND meets the marine bunker fuel oil specifications under IMO 2020, including the total sulfur content, which is below 0.5% at about 0.41% by weight. The BLEND also has a total aged sediment of less than 0.10 weight percent, which is indicative of longer term stability. As given in TABLE V, the BLEND also has an aromatics content of about 46% as well as a combined aluminum and silicon concentration of about 30 ppm. The solubility index is typically used to assess crude oil blending compatibility/stability, however, the solubility index has also proven useful when assessing the compatibility/stability of blending refined product. As with crude oil, refined product blends are typically compatible/stable when the solubility coefficient SBN of the blend is greater than the highest insolubility coefficient IN of any blend coefficient. Here, the BLEND has a solubility coefficient SBN of 85.3, which is higher than the highest insolubility index of any blend component (i.e., 69 for the DECANT). Thus, the solubility index confirms that compatibility and stability of the instant LSFO blend.
(51) TABLE-US-00005 TABLE V BLEND COMPONENT Test Method Characteristic RESID DECANT VGO BLEND ASTM D4052 API Gravity @ 60° F. 12.5 −0.3 22.4 17.4 ASTM D445 Test Temperature ° C. 50.0 50.0 50.0 50 Kinematic Viscosity, cST 108.9 109.8 26.87 27.6 ASTM D97 Pour Point, ° C. −18 0 30 −9 ASTM D4530 Carbon Residue, wt % 7.28 4.75 2.57 Micro Carbon Residue, wt % 7.28 4.75 <0.1 2.57 ASTM D5762 Nitrogen, ppm 2758 1428 1139 IP 501 Vanadium, ppm 42 <1 9.6 Sodium, ppm 13 <1 1.3 Aluminum, ppm 12 6 14.2 Silicon, ppm 14 14 15.8 Aluminum + Silicon 26 20 30 Iron 26 1 6.8 Nickel 17 <1 3.9 Copper 0.2 <0.1 <1 ASTM D4294 Sulfur Content, wt % 1.93 0.382 0.104 0.178 ASTM D6560 Asphaltenes, wt % 2.3 0.5 0.8 ASTM D6379 Total Aromatics, wt % 38.9 63.7 46.1 ASTM D1160 AET at IBP, ° F. 367 431 454.9 173 AET at 5% Recovered, ° F. 474 585 573 261 AET at 10% Recovered, ° F. 514 657 617 304 AET at 20% Recovered, ° F. 569 705 677 345 AET at 30% Recovered, ° F. 627 732 719 373 AET at 40% Recovered, ° F. 705 752 754 394 AET at 50% Recovered, ° F. 768 786 413 AET at 60% Recovered, ° F. 787 817 433 AET at 70% Recovered, ° F. 817 847 457 AET at 80% Recovered, ° F. 850 884 490 AET at 90% Recovered, ° F. 915 934 502 AET at 95% Recovered, ° F. 971 AET at 98% Recovered, ° F. 1014 AET at EP, ° F. 705 957 1066.3 Special Observation cracking, cracking, max T @ 389 F. 599 F. 90% Recovery, vol % 41 93 100 Residue, vol % 59 7 Cold Trap Recovery, vol % 0 0 Loss, vol % 0 0 ASTM D5705 Test Temperature ° C. 60 60 Hydrogen Sulfide in 12 12.43 Vapor, ppm
(52) In one or more methods of blending the marine bunker fuel oil compositions disclosed herein, lower economic value resid base stock is used to as great an extent as possible because of its economic advantage when used in LSFO. LSFO is generally sold on the basis of weight; therefore, LSFO having denser hydrocarbon components provide greater economic return on a volume basis. However, the resid base stocks tend to be high in sulfur content and in viscosity, both of which have lower limits under IMO 2020 (see ISO 8217, RMG 380). In one or more embodiments, the method optimizes the amount of resid stock, but uses a quantity of decant oil, e.g., from about 16% to about 40% by volume, to stabilize the resid base stock such that a low sulfur cutter stock, such as cycle oil or vacuum gas oil, may be used to reduce viscosity and sulfur to meet specification in the final blend. In effect, the cracked stocks, such as decant oil (slurry oil), are used as compatibility and/or stability enhancers for the residual hydrocarbon base. This creates robust blending opportunities to achieve final fuel blends having higher density but also having initial compatibility and longer term stability (e.g., reducing asphaltene precipitation). Here, the use of low sulfur decant oil from hydrotreated FCC feeds also works to reduce sulfur content of the blend thereby reducing the amount of economically more expensive low sulfur distillate or low sulfur hydrocarbon that will be required to meet the final blend specification.
(53) In one or more methods of blending the LSFO, a resid feed stock, such as vacuum tower bottoms, is produced. This short resid has a sulfur content of at least about 1.5 percent by weight. Optionally, the bottoms from the fluidized catalytic cracker (FCC) unit, i.e., decant oil (slurry oil), is filtered or decanted to remove FCC catalyst fines concentration, (e.g., aluminum, silicon, etc.) thereby reducing the concentration of aluminum and/or silicon in the filtered or decanted oil. Such additional filtering and/or decanting facilitates the achievement of the maximum combined aluminum and silicon concentration in the final blend. The decant oil is produced in a fluid catalytic cracker using a hydrotreated feed that is fed to the fluid catalytic cracker. The resulting low sulfur decant oil, having a sulfur content of less than about 1.2 percent by weight, less than about 1.0 percent by weight, less than about 0.8 percent by weight, less than about 0.6 percent by weight, less than 0.4 percent by weight or even less than 0.2 percent by weight, is either blended with the resid feed stock or added into a tank holding the resid feed stock. The blended resid feed stock is held in a tank until further blending with the cutter stocks to create the final blend. The decant oil mitigates the paraffin nature of cutter stocks to enhance the compatibility of the cutter stocks in the final blend. A cutter stock, such as a LCO, MCO, HCO, and/or VGO, having a sulfur content of less than about 0.5 percent by weight, less than about 0.4 percent by weight, less than about 0.3 percent by weight, less than about 0.2 percent by weight, or even less than about 0.1 percent by weight, is then either blended with the resid base stock and decant oil or added into a tank holding the resid base stock and decant oil. The cutter stock reduces the final blend sulfur content to less than 0.5 percent by weight and facilitates meeting the other final fuel specifications, e.g., viscosity, etc., as will be understood by those skilled in the art.
(54) TABLE VI below gives the characteristics of several blend components, e.g., various resids, decant oil, LCO, HCO and VGO, used in the several prophetic examples of final blends (i.e., Blend 1 to Blend 14) according to the disclosure herein. TABLE VII below gives the final blend compositions for the several prophetic examples of such final blends according to the disclosure herein. TABLES VIII and IX provide the characteristics for the several prophetic examples of such final blends having the corresponding final blend compositions given in TABLE VII and that use various blend components, whose characteristics are given in TABLE VI. Within TABLES VIII and IX, the values in bold italics represent characteristics of the respective final blend that do not meet the specifications required under IMO 2020 (see ISO 8217, RMG 380). However, with slight adjustments to the blend component concentrations, these blends could be brought to within specification under IMO 2020.
(55) TABLE-US-00006 TABLE VI Test Blend Components Method Characteristic Resid 1 Resid 2 Resid 3 Resid 4 Resid 5 Decant Oil VGO LCO HCO API Gravity @ ~60° F. 5.8 11.9 12.9 14.3 13.9 −0.3 25.3 39.0 39.0 Density @ ~15° C. (g/ml) 0.999 0.987 0.949 0.939 0.960 1.049 0.900 0.830 0.830 Viscocisty @ ~50° C. (cSt) 473.78 355.43 2234.82 888.93 10116.20 189.68 23.35 5.00 35.06 Sulfur (wt %) 1.74 2.51 0.42 1.38 1.59 0.30 0.05 0.05 0.17 Flash Point (° C.) 178.0 99.0 132.0 109.5 159.0 57.5 60.5 Pour Point (° C.) 53.6 35.0 24.0 Potential Total Sediment (wt %) Ash Content (wt %) 10 Vanadium (wppm) 42.8 167.0 16.5 71.8 93.1 0.3 0.2 0.2 0.2 Sodium (wppm) 9.4 16.1 10.8 7.6 1.1 1.0 1.0 1.0 1.0 Aluminum + Silicon (wppm) 27 40 20 1 Copper (wppm) 0.3 0.4 0.3 0.5 0.3 0.3 0.3 0.3 0.3 Calcium (wppm) 4.69 7.64 6.02 2.77 5.74 0.20 0.20 0.20 0.20 Zinc (wppm) 1.24 3.11 0.91 1.02 2.31 0.40 0.40 0.40 Phosphorus (wppm) 1.16 2.53 1.79 1.35 2.45 1.00 1.00 1.00 1.00 Nickel (wppm) 31.7 67.6 16.1 33.3 37.5 0.3 0.3 0.3 0.3 Iron (wppm) 55 31.4 19.1 7.04 20.7 0.40 0.20 0.20 0.21 Micro Carbon Residue (wt %) 17.16 14.25 17.32 15.57 12.3 4.73 0.04 0.27 0.76 Total Acid Number (mg KOH/kg) 0.10 0.76 0.19 0.18 0.32 0.03 0.02 0.01 0.03 Saturates 10.38 15.7 15.05 13.29 28.52 10.05 56.12 11.21 22.09 Aromatics 70.16 50.06 55.13 54.10 47.43 86.45 41.85 88.78 72.08 Resins 10.32 20.88 18.57 22.1 13.09 2.40 0.53 0 1.77 Aspaltenes 9.12 13.3 11.2 10.5 10.9 1.1 0 0 4.1 CII 0.242 0.409 0.357 0.312 0.652 0.125 1.324 0.126 0.354 Heptane Insolubles 6.42 8.78 8.55 2.43 0.29 0.17
(56) TABLE-US-00007 TABLE VII Blend Compositions Bind #1 Bind #2 Bind #3 Bind #4 Bind #5 Bind #6 Bind #7 Component Resid 1 12.02 23.28 Resid 2 12.84 Resid 3 25.50 Resid 4 24.81 23.36 Resid 5 24.59 Decant Oil 30.66 40.32 53.94 36.94 50.23 47.02 13.59 Vacuum Gas Oil 44.53 46.84 37.56 63.12 Light Cycle Oil 34.05 26.42 Heavy Cycle Oil 28.38 Blend Compositions Bind #8 Bind #9 Bind #10 Bind #11 Bind #12 Bind #13 Bind #14 Component Resid 1 24.71 Resid 2 23.81 Resid 3 26.29 25.50 22.42 Resid 4 25.89 25.51 Resid 5 Decant Oil 42.35 57.12 36.94 16.24 41.76 32.00 13.70 Vacuum Gas Oil 32.95 16.59 37.56 61.33 32.35 42.49 62.49 Light Cycle Oil Heavy Cycle Oil
Example 2
(57) In non-limiting, prophetic Example 2, Blend #1 is composed of Resid 4, a sweet run vacuum tower bottom blend, to which Decant Oil and Vacuum Gas Oil have been added. The final blend has about 24.8 percent by volume Resid 4, 30.7 percent by volume Decant Oil, and 55.5 percent by volume Vacuum Gas Oil. The characteristics of the Resid 4, Decant Oil, and Light Cycle Oil are given in TABLE VI. The final blend, Blend #1, has the characteristics given in TABLE VIII and is projected to meet the marine bunker fuel oil specifications under IMO 2020, including the total sulfur content, which is below 0.5% at about 0.46% by weight. Blend #1 is also calculated to meet the total aged sediment requirement of less than 0.10 weight percent, which is indicative of longer term stability. As given in TABLE VIII, Blend #1 has an aromatics content of about 61%. Blend #1 also has a combined volume of vacuum tower bottoms and decant oil that is higher than 50%—at about 55.5%.
Example 3
(58) In non-limiting, prophetic Example 3, Blend #3 is composed of Resid 1, a severely cracked vacuum tower bottoms, to which Decant Oil and then Light Cycle Oil have been added. The final blend has about 12 percent by volume of Resid 1, about 54 percent by volume of Decant Oil and about 34 percent by volume of Light Cycle Oil. The characteristics of the Resid 1, Decant Oil, and Light Cycle Oil are given in TABLE VI. The final blend, Blend #3, has the characteristics given in TABLE VIII and is projected to meet the marine bunker fuel oil specifications under IMO 2020, including the total sulfur content, which is below 0.5% at about 0.41% by weight. Blend #3 is also calculated to meet the total aged sediment requirement of less than 0.10 weight percent, which is indicative of longer term stability. As given in TABLE VIII, Blend #3 has an aromatics content of about 88%. In one or more embodiments, the total aromatics content of the final blend is at most 90%, at most 85% at most 80%, at most 75%, at most 70%, at most 65%, at most 60%, or even at most 55%, in order to mitigate and/or control particulate emissions upon combustion of the LSFO. Blend #3 also has a combined volume of vacuum tower bottoms and decant oil that is higher than 50%—at about 66%.
Example 4
(59) In non-limiting, prophetic Example 4, Blend #10 is composed of Resid 3, a mildly cracked sweet run vacuum tower bottom blend, to which Decant Oil and then Vacuum Gas Oil have been added. The final blend has about 25.5 percent by volume of Resid 3, about 36.9 percent by volume of Decant Oil and about 37.6 percent by volume of Vacuum Gas Oil. The characteristics of the Resid 3, Decant Oil, and Vacuum Gas Oil are given in TABLE VI. The final blend, Blend #10, has the characteristics given in TABLE IX and is projected to meet the marine bunker fuel oil specifications under IMO 2020, including the total sulfur content, which is below 0.5% at about 0.24% by weight. Here, there is sulfur giveaway and possible room to increase the volume of the Resid 3, if the other IMO requirements of the final blend can be met. Blend #10 is also calculated to meet the total aged sediment requirement of less than 0.10 weight percent, which is indicative of longer term stability. As given in TABLE IX, Blend #3 has an aromatics content of about 64%. Blend #10 also has a combined volume of vacuum tower bottoms and decant oil that is higher than 50% at about 62.4%.
(60) Although only Blend #1, Blend #3 and Blend #10 are discussed above in the Examples 2 through 4, respectively, each of Blends #1 through #14 of TABLE VII is a non-limiting example of the blend compositions and associated methods disclosed herein.
(61) TABLE-US-00008 TABLE VIII Example Blends Characteristic Blend 1 Blend 2 Blend 3 Blend 4 Blend 5 Blend 6 Blend 7 API Gravity @ ~60° F. 13.87 12.25 11.71 11.81 11.78 25.84 16.47 Density @ ~15° C. (g/ml) 0.96 0.97 0.97 0.97 0.96 0.90 0.94 Viscocisty @ ~50° C. (cSt) 39.91 31.32 99.69 60.10 129.26 33.29 25.05 Sulfur (wt %) 0.46 0.48 0.41 0.24 0.49 0.49 0.51 Water by Distillation (vol %) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Flash Point (° C.) 128.94 118.63 100.03 100.17 93.31 150.09 156.69 Pour Point (° C.) Potential Total Sediment (wt %) <0.01 0.02 0.02 <0.01 <0.01 0.04 0.54 Ash Content (wt %) 0.00 0.00 1.25 0.00 0.00 0.00 2.51 Vanadium (wppm) 17.94 21.71 5.59 4.36 16.68 24.92 10.90 Sodium (wppm) 2.63 2.94 2.05 3.48 2.51 1.03 3.11 Aluminum + Silicon (wppm) 13.88 9.26 11.77 8.41 17.17 11.11 3.66 Copper (wppm) 0.36 0.32 0.30 0.30 0.35 0.30 0.30 Calcium (wppm) 0.84 1.16 0.76 1.67 0.79 1.67 1.33 Zinc (wppm) 0.42 0.57 0.27 0.37 0.32 0.91 0.55 Phosphorus (wppm) 1.09 1.20 1.02 1.20 1.03 1.39 1.04 Nickel (wppm) 8.47 8.97 4.25 4.31 7.88 10.22 8.18 Iron (wppm) 1.96 4.30 7.18 5.06 1.88 5.66 13.98 Micro Carbon Residue (wt %) 5.47 3.94 5.01 6.31 6.23 3.49 5.05 Total Acid Number (mg KOH/kg) 0.06 0.12 0.03 0.07 0.06 0.10 0.04 CCAI 845.62 865.49 844.33 851.23 838.00 788.07 842.18 Saturates 0.30 0.31 0.10 0.27 0.11 0.40 0.38 Aromatics 0.60 0.62 0.85 0.63 0.80 0.51 0.56 Resins 0.06 0.04 0.03 0.06 0.06 0.04 0.03 Asphaltenes 0.03 0.02 0.02 0.03 0.03 0.04 0.02 CII 0.50 0.50 0.14 0.45 0.16 0.79 0.69 Solubility Index S.sub.BN Insolubility Index I.sub.N 69 69 69 69 69 69 69
(62) TABLE-US-00009 TABLE IX Example Blends Characteristic Blend 8 Blend 9 Blend 10 Blend 11 Blend 12 Blend 13 Blend 14 API Gravity @ ~60° F. 8.79 6.76 11.81 17.67 10.91 13.45 17.94 Density @ ~15° C. (g/ml) 0.99 1.00 0.97 0.94 0.97 0.96 0.94 Viscocisty @ ~50° C. (cSt) 46.73 97.42 60.10 31.04 58.11 41.99 23.91 Sulfur (wt %) 0.59 0.29 0.24 0.18 0.50 0.47 0.70 Water by Distillation (vol %) 0.00 0.00 0.00 0.00 0.00 0.00 0.05 Flash Point (° C.) 142.73 88.93 100.17 115.31 122.79 127.86 134.01 Pour Point (° C.) Potential Total Sediment (wt %) 0.10 0.02 0.02 0.02 <0.01 <0.01 0.06 Ash Content (wt %) 2.52 0.00 0.00 0.00 0.00 0.00 0.00 Vanadium (wppm) 10.99 4.36 4.36 3.99 18.35 18.39 41.61 Sodium (wppm) 3.12 3.47 3.48 3.27 2.67 2.67 4.75 Aluminum + Silicon (wppm) 9.35 12.18 8.41 4.28 16.19 14.31 3.72 Copper (wppm) 0.30 0.30 0.30 0.30 0.36 0.36 0.33 Calcium (wppm) 1.33 1.67 1.67 1.55 0.85 0.85 20.46 Zinc (wppm) 0.43 0.29 0.37 0.44 0.58 0.42 1.01 Phosphorus (wppm) 1.04 1.20 1.20 1.18 1.09 1.09 1.38 Nickel (wppm) 8.23 4.29 4.31 3.96 8.65 8.67 17.00 Iron (wppm) 14.12 5.08 5.06 4.62 2.02 2.00 7.97 Micro Carbon Residue (wt %) 6.48 7.21 6.31 4.91 6.09 5.64 4.30 Total Acid Number (mg KOH/kg) 0.04 0.07 0.07 0.06 0.06 0.06 0.02 CCAI 875.07 874.34 851.23 830.07 845.62 845.62 840.77 Saturates 0.24 0.18 0.27 0.38 0.25 0.29 0.39 Aromatics 0.69 0.72 0.63 0.53 0.65 0.61 0.51 Resins 0.38 0.06 0.06 0.05 0.07 0.07 0.06 Asphaltenes 0.03 0.03 0.03 0.03 0.09 0.03 0.03 CII 0.37 0.28 0.45 0.71 0.39 0.48 0.75 Solubility Index S.sub.BN Insolubility Index I.sub.N 69 69 69 69 69 69 69
(63) As shown in the above Examples 1-4, the three component blends of a VTB (or ATB) blended with a decant oil (slurry oil) and a low sulfur cutter stock, such as VGO and/or cycle oil, in the appropriate blend ratios will meet the LSFO fuel specification IMO 2020 requirements (see ISO-8217, RMG-380). As described previously, these blend components are blended for their synergistic effect to stabilize the resid hydrocarbon fraction while permitting subsequent dilution with cutter stock to meet low sulfur and viscosity requirements, among others, of the finished blended product.
Example 5
(64) In Example 5, an atmospheric tower bottoms, a decant/slurry oil, and a low sulfur vacuum gas oil were blended to achieve an LSFO marketed to meet the specification under ISO 2020 (see ISO 8217, RMG 380). TABLE X below gives the characteristics of each of the blend components used to create this blend.
(65) TABLE-US-00010 TABLE X BLEND COMPONENT Characteristic ATB DCO LSVGO API Gravity @ 60° F. 12.2 −0.5 24.5 SPG 1.0 1.1 0.9 Viscosity, cST 2244 186 20.9 Viscosity, Sfs 1058.5 87.7 10.93 Viscosity (calc) 1.941 1.5 0.901 Flash Point, ° C. 110 76.7 82.2 Pour Point, ° C. 9 0 33 Micro Carbon Residue, wt % 16.5 4.3 0.1 Vanadium, ppm 72 2 1 Sodium, ppm 8 1 1 Aluminum + Silicon 15 220 4 Sulfur Content, wt % 1.74 0.34 0.04
(66) To create the blend of Example 5, about 23.0 percent by volume of ATB, about 28.0 percent by volume of decant/slurry oil, and about 46.8 percent by volume of low sulfur vacuum gas oil were blended to achieve an LSFO achieving the IMO 2020 specification per ISO 8217. The characteristics of the final blend, which are based on a certified analysis, are given in TABLE XI below. It should be noted that the sulfur content of the final blend is about 0.299 percent by weight, which is less than the maximum allowable of 0.5 percent by weight. The potential total sediment (i.e., total sediment aged) of 0.01 weight percent is also well below the maximum allowable of 0.1 weight percent and its low value is indicative of a compatible and stable fuel oil blend. Here, the ATB and decant/slurry oil constitute about 51.0 percent by volume of the blend. The final blend has a solubility coefficient SBN of 148.9, which is much higher than 69, the highest insolubility index IN of any blend component. Thus, the solubility index confirms that compatibility and stability of the instant LSFO blend.
(67) TABLE-US-00011 TABLE XI TEST METHOD CHARACTERISTIC BLEND ASTM D4052 API Gravity @ 60° F. 14.8 ASTM D445 Viscosity, cST @ 50° C. 35.41 ASTM D93B Flash Point, ° C. 101.1 ASTM D97 Pour Point, ° C. −9 ASTM D4530 Micro Carbon Residue, wt % 1.67 IP 501 Vanadium, ppm 11.5 IP 501 Sodium, ppm 2.2 IP 501 Aluminum, ppm 20.5 IP 501 Silicon, ppm 23.8 IP 501 Aluminum + Silicon 44.3 IP 501 Phosphorus 0.8 IP 501 Iron 2.9 IP 501 Zinc 0.4 IP 501 Calcium 0.9 ASTM D664A TAN Acidity, mgKOH/g <0.10 ASTM D482 Ash, wt % <0.010 ASTM D4294 Sulfur Content, wt % 0.299 ASTM D4870 Accelerated Total Sediment, wt % <0.01 ASTM D4870 Potential Total Sediment, wt % 0.01 Calc CCAI 859 ASTM D4740 Compatibility, D4740 2 ASTM D95 Water, vol % 0.05 ASTM D7061 Separability Number, % 0.1 ASTM D7061 Oil:Toluene Ratio, wt % 1:09
Example 6
(68) In Example 6, a vacuum tower bottoms, a decant/slurry oil, a low sulfur vacuum gas oil and a heel portion were blended to achieve an LSFO marketed to meet the specification under ISO 2020 (see ISO 8217, RMG 380). TABLE XII below gives the characteristics of each of the blend components used to create this blend.
(69) TABLE-US-00012 TABLE XII BLEND COMPONENT Characteristic VTB DCO LSVGO HEEL API Gravity @ 60° F. 15.6 0.5 25.2 14 SPG 0.962 1.072 0.903 0.973 Viscosity, cST 510 168 20.9 60 Viscosity, Sfs 240.6 79.2 10.93 28.3 Viscosity (calc) 1.702 1.478 0.901 1.215 Flash Point, ° C. 67.8 65.5 110 96.7 Pour Point, ° C. 9 0 30 −9 Micro Carbon Residue, wt % 16.5 4.3 0.1 3.9 Vanadium, ppm 72 2 1 13 Sodium, ppm 8 1 1 3 Aluminum + Silicon 15 182 4 14 Sulfur Content, wt % 1.35 0.3 0.04 0.415
(70) To create the blend of Example 6, about 23.6 percent by volume of VTB, about 19.7 percent by volume of decant/slurry oil, about 55.1 percent by volume of low sulfur vacuum gas oil and about 1.6% by volume of a heel portion were blended to achieve an LSFO achieving the IMO 2020 specification per ISO 8217. The characteristics of the final blend, which are based on a certified analysis, are given in TABLE XIII below. It should be noted that the sulfur content of the final blend is about 0.401 percent by weight, which is less than the maximum allowable of 0.5 percent by weight. The accelerated total sediment of 0.01 weight percent is also well below the maximum allowable of 0.1 weight percent and its low value is indicative of a compatible and stable fuel oil blend. Here, the VTB and decant/slurry oil constitute about 43.3 percent by volume of the blend.
(71) TABLE-US-00013 TABLE XIII TEST METHOD CHARACTERISTIC BLEND ASTM D4052 API Gravity @ 60° F. 16.9 ASTM D445 Viscosity, cST @ 50° C. 62.51 ASTM D93B Flash Point, ° C. 110 ASTM D97 Pour Point, ° C. −9 ASTM D4530 Micro Carbon Residue, wt % 2.54 IP 501 Vanadium, ppm 19 IP 501 Sodium, ppm 4 IP 501 Aluminum, ppm 9 IP 501 Silicon, ppm 2.4 IP 501 Aluminum + Silicon 11.4 IP 501 Phosphorus 0.1 IP 501 Iron 4 IP 501 Zinc 0.6 IP 501 Calcium 1 ASTM D664A TAN Acidity, mgKOH/g 0.17 ASTM D482 Ash, wt % 0.011 ASTM D4294 Sulfur Content, wt % 0.401 ASTM D4870 Accelerated Total Sediment, wt % 0.01 Calc CCAI 836 ASTM D4740 Compatibility, D4740 1 ASTM D95 Water, vol % 0.05
Example 7
(72) In Example 7, a vacuum tower bottoms, a decant/slurry oil, a low sulfur vacuum gas oil and a heel portion were blended to achieve an LSFO marketed to meet the specification under ISO 2020 (see ISO 8217, RMG 380). TABLE XIV below gives the characteristics of each of the blend components used to create this blend.
(73) TABLE-US-00014 TABLE XIV BLEND COMPONENT Characteristic VTB DCO LSVGO HEEL API Gravity @ 60° F. 15 0.5 25.2 19.9 SPG 0.966 1.072 0.903 0.935 Viscosity, cST 510 168 24 51.1 Viscosity, Sfs 24.6 79.2 12.55 24.1 Viscosity (calc) 1.702 1.478 0.952 1.168 Flash Point, ° C. 67.8 65.5 110 84.7 Pour Point, ° C. 9 0 30 12 Micro Carbon Residue, wt % 16.5 4.3 0.1 3.7 Vanadium, ppm 72 2 1 21.2 Sodium, ppm 8 1 1 3 Aluminum + Silicon 15 4 4 28 Sulfur Content, wt % 1.3 0.347 0.04 0.427
(74) To create the blend of Example 7, about 16.7 percent by volume of VTB, about 34.4 percent by volume of decant/slurry oil, about 25.6 percent by volume of low sulfur vacuum gas oil and about 23.3% by volume of a heel portion were blended to achieve an LSFO achieving the IMO 2020 specification per ISO 8217. The characteristics of the final blend, which are based on a certified analysis, are given in TABLE XV below. It should be noted that the sulfur content of the final blend is about 0.49 percent by weight, which is just less than the maximum allowable of 0.5 percent by weight. The potential total sediment (i.e., total sediment aged) of <0.01 weight percent is also well below the maximum allowable of 0.1 weight percent and its low value is indicative of a compatible and stable fuel oil blend. Here, the VTB and decant/slurry oil constitute about 51.1 percent by volume of the blend.
(75) TABLE-US-00015 TABLE XV TEST METHOD CHARACTERISTIC BLEND ASTM D4052 API Gravity @ 60° F. 11.9 ASTM D445 Viscosity, cST @ 50° C. 77.86 ASTM D93B Flash Point, ° C. 85 ASTM D97 Pour Point, ° C. −12 ASTM D4530 Micro Carbon Residue, wt % 3.76 IP 501 Vanadium, ppm 18 IP 501 Sodium, ppm 14 IP 501 Aluminum, ppm 13 IP 501 Silicon, ppm 10 IP 501 Aluminum + Silicon 23 IP 501 Phosphorus 0.3 IP 501 Zinc 0.2 IP 501 Calcium 0.8 ASTM D664A TAN Acidity, mgKOH/g 0.15 ASTM D482 Ash, wt % 0.011 ASTM D4294 Sulfur Content, wt % 0.49 ASTM D4870 Accelerated Total Sediment, wt % 0.01 ASTM D4870 Potential Total Sediment, wt % <0.01 Calc CCAI 866 ASTM D4740 Compatibility, D4740 1 ASTM D95 Water, vol % 0.1 ASTM D7061 Separability Number, % 0.5 ASTM D7061 Oil:Toluene Ratio, wt % 0:09
(76) The ISO 8217, Category ISO-F RMG 380 specifications for residual marine fuels are given below in TABLE XVI. As used in this disclosure, achieving or meeting the IMO 2020 specifications per ISO 8217 for a particular fuel oil blend is with respect to the values for the blend characteristics as listed in Table XVI below and as confirmed by the respective test methods and/or references provided in ISO 8217. As understood by those skilled in the art, the other specifications provided in ISO 8217, e.g., RMA, RMB, RMD, RME, and RMK, may sought to be achieved by adjusting the blend compositions.
(77) TABLE-US-00016 TABLE XVI Category ISO-F RMG Characteristics Unit Limit 380 Test Method(s) and References Kinematic Viscosity @ 50° C. cSt Max 380.0 ISO 3104 Density @ 15° C. kg/m.sup.3 Max 991.0 ISO 3675 or ISO 12185 CCAI Max 870 Calculation Sulfur mass % Max 0.5 ISO 8754 or ISO 14596 or ASTM D4294 Flash Point ° C. Min 60.0 ISO 2719 Hydrogen Sulfide mg/kg Max 2.00 IP 570 Acid Number mgKOH/g Max 2.5 ASTM D664 Total Sediment - Aged mass % Max 0.10 ISO 10307-2 Carbon Residue - Micro Method mass % Max 18.00 ISO 10370 Pour Point Winter ° C. Max 30 ISO 3016 (upper) Summer ° C. Max 30 Water vol % Max 0.50 ISO 3733 Ash mass % Max 0.100 ISO 6245 Vanadium mg/kg Max 350 IP 501, IP 470 or ISO 14597 Sodium mg/kg Max 100 IP 501, IP 470 Al + Si mg/kg Max 60 IP 501, IP 470 or ISO 10478 Used Lubricating Oil (ULO): mg/kg Max Ca > 30 and IP 501 or IP470, IP 500 Ca and Z or Ca and P Z > 15 or CA > 30 and P > 15
(78) In the drawings and specification, several embodiments of low sulfur marine bunker fuel oil compositions, and methods of blending such compositions, to increase initial compatibility and enhance longer term stability have been disclosed, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. Embodiments of compositions and related methods have been described in considerable detail with specific reference to the illustrated embodiments. However, it will be apparent that various modifications and changes to disclosed features can be made within the spirit and scope of the embodiments of compositions and related methods as may be described in the foregoing specification, and features interchanged between disclosed embodiments. Such modifications and changes are to be considered equivalents and part of this disclosure.