FUEL OIL COMPOSITION

Description

FIELD

The field is related to a fuel oil composition and a process of making the same. Particularly, the field relates to a marine fuel oil composition produced from bio-oil.

BACKGROUND

Hydrocarbon conversion processes typically require reactor systems, and associated conduits and piping, adapted for hydrocracking, reforming, fluidized catalytic cracking, and other similar processes.

Bio-oils are obtained by thermochemical processes including liquefaction or pyrolysis. Notably biomass pyrolysis includes several classes of processes such as flash, fast, slow or catalytic pyrolysis. Pyrolysis is a thermal decomposition process in the absence of oxygen with thermal cracking of the feedstocks to gas, liquid and solid products. A catalyst can be added to enhance the conversion in catalytic pyrolysis. Various technologies have been deployed for large scale biomass pyrolysis. They include bubbling fluidized beds, circulating fluidizing beds, ablative pyrolysis, vacuum pyrolysis, and rotating cone pyrolysis reactors. Catalytic pyrolysis generally leads to bio-oil having a lower oxygen content than bio-oil obtained by thermal decomposition. The selectivity between gas, liquid and solid is well related to the reaction temperature and vapor residence time. Lower temperature, for example, around 400° C. and longer residence time, for example, a few minutes to a few hours, obtained by slow pyrolysis, favors the production of solid product, also called char or char coal, with typically 35 wt % gas, 30 wt % liquid, and 35 wt % char. Very high temperature of above 800° C. used in the gasification processes favors gas production, typically more than 85 wt %. Intermediate reaction temperature, typically about 450° C. to about 550° C., and short vapor residence time, typically about 10 to about 20 s, for the pyrolysis, favor the liquid yield: typically 30 wt % gas, 50 wt % liquid, and 20 wt % char. Intermediate reaction temperature, typically about 450° C. to about 550° C., and very short vapor residence time, typically about 1 to about 2 s, for the flash pyrolysis or fast pyrolysis, favor even more the liquid yield: typically 10 to about 20 wt % gas, about 60 to about 75 wt % liquid, about 10 to about 20 wt % char. The highest liquid yields may be obtained by the flash pyrolysis processes, with up to 75 wt %.

Bio-oils can be processed to provide low-cost renewable liquid fuels; indeed, they can be used as fuel for boilers, as well as for stationary gas turbines and diesel engines. Furthermore, fast pyrolysis has been demonstrated at fairly large scales, of the order of several hundred tons per day. Nevertheless, there has not been any significant commercial uptake of this technology. The reasons may relate mostly to the poor physical and chemical properties of bio-oils in general and fast pyrolysis bio-oils in particular. For example, some of the undesirable properties of pyrolysis bio-oils may include: (1) corrosivity on account of their high water and acidic contents; (2) relatively low specific calorific value on account of the high oxygen content, which typically is around 40% or more by mass; (3) chemical instability on account of the abundance of reactive functional groups like carboxyl groups and phenolic groups that can lead to polymerization on storage and consequent phase separation; (4) relatively high viscosity and susceptibility to phase separation under high shear conditions, for instance in a nozzle; (5) incompatibility with, on account of insolubility in, conventional hydrocarbon based fuels; (6) blockage in nozzles and pipes caused by adventitious char particles, which will always be present in unfiltered bio-oil to a greater or lesser degree. All these aspects combine to render bio-oil handling, shipping storage and usage difficult and expensive.

The economic viability of bio-oil production for fuel or energy applications therefore depends on finding appropriate methods to upgrade it to a higher quality liquid fuel at a sufficiently low cost.

Over the last two decades, the approach of direct hydroprocessing of bio-oil to convert it to stable oxygenates or hydrocarbons has been studied intensively. A major obstacle to the catalytic hydroprocessing of bio-oil has been its propensity to polymerize under heating above about 100° C., leading ultimately to the formation of extraneous solids or coke at temperatures above about 140° C., with consequences like reactor plugging and catalyst deactivation.

Diesel engines have been widely used the marine industry. In particular, four-stroke diesel engines have been operational in surface ships and submarines since the 1910s. Since that time a series of innovations and improvements have been made to marine diesel engines and to the fuels that can be used in those engines. However, a persistent problem since the introduction of marine diesel engines is the high volume of objectionable emissions produced by these engines and in particular the emission of sulphur oxides. Recently there has been widespread international regulatory efforts designed to reduce the harmful emissions from marine engines, especially close to land and cities, where air pollution is a concern. The additional impact of CO2 emissions on climate is also a concern which has led to a desire for lower carbon intensity marine fuels.

To meet emissions goals, the EU is implementing Fuel EU Maritime Regulation which will limit the carbon intensity of maritime transport. One way for shipping operators to meet these requirements will be to utilize bio-renewable marine fuel. Currently, renewable liquid fuel options for existing engines on shipping vessels are limited. Use of CO2 derived methanol is an emerging option but it requires different engines to utilize it. Fuels derived from ethanol or triglyceride feedstocks are expensive to produce and have other lucrative markets in sustainable aviation fuel (SAF). Lignocellulosic biomass derived fuels are a promising option. However, pyrolysis of lignocellulosic biomass to produce a liquid fuel to date results in a corrosive pyrolysis oil that is highly susceptible to polymerization and plugging during processing and is therefore not well suited to be used directly as a marine fuel.

Therefore, there is a need for solution to produce a marine fuel oil that addresses environmental requirements for marine fuel while meeting the marine fuel specification.

SUMMARY

The present disclosure provides a marine fuel oil composition. The marine fuel oil composition comprises an acid number of less than about 2.5 mg KOH/g, a flash point temperature greater than about 140° F., and an oxygen concentration of at least about 2 wt %. The marine fuel oil composition may be used as a fuel stream or as a blend stock with other fuel(s). Further, a process for producing marine fuel oil is disclosed. The marine fuel oil of the present disclosure meets the marine fuel specifications without removing all of the oxygen from it. This allows for less hydrogen consumption and a higher yield. Furthermore, the presence of oxygenates in the marine fuel oil is found to increase flashpoint of fuels with lower boiling points, meaning that more marine fuel can be obtained from a given feed source. The marine fuel oil composition may provide a blend stock for blending with one or both of a bio-derived marine fuel oil and a petroleum-derived marine fuel oil.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a schematic diagram of a process for producing marine fuel oil in accordance with an embodiment of the present disclosure.

FIG. 2 illustrates a graph plotted between the acid number and the oxygen content of the marine fuel oil in accordance with yet another exemplary embodiment of the present disclosure.

FIG. 3 illustrates a graph plotted between the flash point and the T5 boiling temperature of the marine fuel oil in accordance with an exemplary embodiment of the present disclosure.

FIG. 4 illustrates a graph plotted between the percentage of oxygen in the marine fuel oil vs T5 temperature in accordance with another exemplary embodiment of the present disclosure.

DEFINITIONS

As used herein the terms “reactor”, “process equipment,” “process units,” or “reactor components” shall include any and all process equipment and process units that are utilized in biomass, bio-oil, or hydrocarbon conversion processes including any upstream and/or downstream equipment from the particular unit and/or ancillaries, such as furnace tubes, associated piping, heat exchangers, heater tubes, and the like.

As used herein, the term “predominant” or “predominate” or “predominance” means greater than 50%, suitably greater than 75% and preferably greater than 90%.

As used herein, the term “carbon number” refers to the number of carbon atoms per molecule.

As used herein, “petroleum stream” or “petroleum feedstock” may refer to crude oil, crude oil refinery distillates, crude oil refinery residue, cracked products or hydrocarbons from a crude oil refinery, liquefied coal, bitumen, typically extracted from the ground or sea floor.

As used herein, the term “True Boiling Point” (TBP) means a test method for determining the boiling point of a material which corresponds to ASTM D-2892 for the production of a liquefied gas, distillate fractions, and residuum of standardized quality on which analytical data can be obtained, and the determination of yields of the above fractions by both mass and volume from which a graph of temperature versus mass % distilled is produced using fifteen theoretical plates in a column with a 5:1 reflux ratio.

As used herein, the term “T5”, “T10” or “T90” means the temperature at which 5 mass percent or 10 mass percent or 90 mass percent, as the case may be, respectively, of the sample boils using ASTM D-86 or TBP. In examples herein, the T5, T10, T90 and other distillation properties of a laboratory or pilot plant sample may at times be accurately estimated by simulated distillation, methods such as ASTM D2887, ASTM D2713, ASTM D632 or ASTM D7169, which utilize calibrated gas chromatographic analyses to simulate the boiling distribution of a sample.

As used herein, the term “vacuum gas oil” (VGO) includes hydrocarbons having an initial boiling point above approximately 343° C. (650° F.), with a T10 boiling point temperature using ASTM D1160 of approximately 370° C. (698° F.) and a T90 boiling point temperature using ASTM D1160 of approximately 500° C. (932° F.).

As used herein, the terms “mol % H” and “mol % C” refer to the percentage of moles of hydrogen or carbon atoms, respectively, of the total moles of hydrogen or carbon atoms in oil. For example, if the bio-oil composition contains 5 moles of hydrogen atoms and 10 moles of carbon atoms and it is said that the bio-oil contains 10 mol % H of aldehydes and 20 mol % C of carboxylic acids and esters it means that 0.5 moles of hydrogen atoms in the bio-oil correspond to H atoms of molecules within an aldehyde functional group and 2 moles of carbon atoms in the bio-oil correspond to C atoms of molecules within either a carboxylic acid or ester functional group.

As used herein, the term “bioderived” or “biogenic” material means a material that comes from or made of, but not limited to, plants, animals, microorganisms, algae, or biopolymers.

As used herein, the term “recycle ratio” or “recycle rate” means the ratio of the recycle flow rate to the fresh feed flow rate.

DETAILED DESCRIPTION

Current ISO 8217 specifications for resid-based marine fuels include acid number of less than 2.5 mg KOH/g, and minimum flashpoint of 60° C. (140° F.). The present disclosure provides a marine fuel oil composition which may be derived from biocrude or bio-oil. The marine fuel oil composition of the present disclosure is a stabilized composition that meets the ISO 8217 specifications, either independently or when used as a blend-stock component with a petroleum-derived marine fuel such as atmospheric gas oil, vacuum gas oil, vacuum residuum or diesel or when used as a blend-stock component with a renewable-derived marine fuel. Applicant found that the marine fuel oil composition can be produced without removing all of the oxygen. This allows for less hydrogen consumption and therefore lower carbon intensity and results in a higher yield of marine fuel. The presence of oxygenates in the marine fuel composition is found to increase its flashpoint at a lower boiling point, meaning that more marine fuel oil can be obtained from a given bio-crude. The marine fuel oil composition can be used as a fuel stream or as a blend stock with other fuel(s).

Biocrude or bio-oil polymerization during deoxygenation or hydrotreating reactions is a major challenge when attempting to convert bio-oil to fuels. The present disclosure provides a process to upgrade a biomass-based feed such as bio-oil in the presence of a catalyst and a stable oil to produce an upgraded bio-oil. The upgraded bio-oil can be used directly as fuel oil such as marine fuel. Alternatively, the upgraded bio-oil can be used as a feed stock for an FCC unit, a hydroprocessing unit, or a reforming unit to produce an intermediate blend or fuel. The upgrading process may include various analyses such as for a content of the reactor to generate spectroscopy data to identify molecular functional groups that are responsible for bio-oil polymerization. Identification and tracking of functional group evolution as a function of catalyst or process conditions helps in targeting the groups responsible for rapid polymerization and charring providing the potential to selectively eliminate them thereby enhancing the performance of the upgrading process. As described later in detail, the process comprises converting some of the oxygenate groups present in the feed, for example, to control charring potential.

Bio-oil perhaps derived from lignocellulosic biomass is a complex mixture of compounds, including oxygenates, that are obtained from the breakdown of biopolymers in biomass. Bio-oils can be derived from plants such as grasses and trees, wood chips, chaff, grains, grasses, corn, corn husks, weeds, aquatic plants, hay and other sources of lignocellulosic material, such as derived from municipal waste, food processing wastes, forestry wastes and cuttings, energy crops, or agricultural and industrial wastes (such as sugar cane bagasse, oil palm wastes, sawdust or straws). Bio-oils can also be derived from pulp and paper by-products (recycled or not). Bio-oils are generally obtained from these biomass feeds by thermochemical liquefaction, notably pyrolysis, such as flash, fast, slow or catalytic pyrolysis. Hydrothermal liquefaction may also be utilized to generate bio-oil feeds. Several different processes which produce bio-oil can be utilized to produce biocrude feed.

Bio-oil is a highly oxygenated, polar hydrocarbon product that typically contains at least about 10 mass % oxygen, typically about 10 to 60 mass % oxygen, more typically about 30 to about 50 mass % oxygen on a water-free basis. In general, bio-oil comprises oxygenates that may include alcohols, aldehydes, ketones, acetates, ethers, esters, organic acids and aromatic oxygenates such as phenols and phenol ethers. Oxygen is also present as free water which constitutes at least about 10 mass %, typically about 15 to about 35 mass % of the bio-oil. These properties render bio-oil immiscible with fuel grade hydrocarbons, even with aromatic hydrocarbons, which typically contain little or no oxygen.

In an aspect of the present disclosure, the biomass-based feed stream may comprise a bio-oil stream obtained by pyrolysis of a biomass feedstock.

The biomass-based feed stream in the present disclosure may further contain other oxygenates derived from biomass such as vegetable oils or animal fat derived oils. Vegetable oil or animal fat-derived oil comprises fatty matter and therefore correspond to a natural or elaborate substance of animal or vegetable origin, mainly containing triglycerides. This essentially involves oils from renewable resources such as fats and oils from vegetable and animal resources (such as lard, tallow, fowl fat, bone fat, fish oil and fat of dairy origin), as well as the compounds and the mixtures derived therefrom, such as fatty acids or fatty acid alkyl esters. The products resulting from recycling of animal fat and of vegetable oils from the food processing industry can also be used, pure or in admixture with other constituent classes described above. The feeds may comprise vegetable oils from oilseed such as rape, erucic rape, soybean, jatropha, sunflower, palm, copra, palm-nut, arachidic, olive, corn, cocoa butter, nut, linseed oil or oil from any other vegetable. These vegetable oils very predominantly consist of fatty acids in form of triglycerides (generally above 97% by mass) having long alkyl chains ranging from 8 to 24 carbon number, such as butyric fatty acid, caproic, caprylic, capric, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, linolenic, arachidic, gadoleic, eicosapentaenoic (EPA), behenic, erucic, docosahexaenoic (DHA) and lignoceric acids. The fatty acid salt, fatty acid alkyl ester and free fatty acid derivatives such as fatty alcohols that can be produced by hydrolysis, by fractionation or by transesterification, for example, of triglycerides or of mixtures of these oils and of their derivatives also come into the definition of the “oil of vegetable or animal origin” feed in the present disclosure. All products or mixtures of products resulting from the thermochemical conversion of algae or products from the hydrothermal conversion of lignocellulosic biomass or algae (in the presence of a catalyst or not) or pyrolytic lignin are also feeds that can be used.

Moreover, the feed containing bio-oil can be coprocessed with petroleum and/or coal derived hydrocarbon feedstocks. The petroleum derived hydrocarbon feed stock can be straight run vacuum distillates, vacuum distillates from a conversion process such as those from coking, from fixed bed hydroconversion or from ebullated bed or slurry hydrocracking heavy fraction hydrotreatment processes, or from solvent deasphalted oils. The feeds can also be formed by mixing those various fractions in any proportions in particular deasphalted oil and vacuum distillate. They can also contain products from the fluid catalytic cracking units, such as light cycle oil (LCO) of various origins, heavy cycle oil (HCO) of various origins and any distillate fraction from fluid catalytic cracking generally having a distillation range of about 150° C. to about 370° C. They may also contain aromatic extracts and paraffins obtained from the manufacture of lubricating oils. The coal derived hydrocarbon feedstock can be products from the liquefaction of coal. Aromatics fractions from coal pyrolysis or coal gasification can also be used as bio-mass based feed.

FIG. 1 shows an exemplary embodiment of the process 100 for producing a marine fuel oil from a bio-oil. A bio-oil stream is taken in line 122 from a source, for example, a bio-oil storage drum 120. The bio-oil stream in line 122 may be passed to a mixer 140. Perhaps, the bio-oil stream in line 122 may be pumped via a pump 123 and a pumped bio-oil stream in line 124 be passed to the mixer 140. In an aspect, a control valve 125 is provided for maintaining a required flow rate of the bio-oil stream to the mixer 140.

In accordance with the present disclosure, a non-bio derived feed stream may also be passed to the mixer and mixed with the bio-oil stream. In an embodiment of the present disclosure, a petroleum stream is the non-bio derived feed stream. The petroleum stream is taken in line 132 from a source, for example, a petroleum storage drum 130. The petroleum stream in line 132 may be passed to the mixer 140. Perhaps the petroleum stream in line 132 may be pumped via a pump 133 and a pumped petroleum stream in line 134 is passed to the mixer 140. In an aspect, a control valve 135 is provided for maintaining a required flow rate of the petroleum stream to the mixer 140. In an embodiment, a sulfur source comprising a sulfiding agent in line 131 may be added to the petroleum stream in line 132 or the bio-oil stream in line 122 and passed to the mixer 140. The control valves 125 and 135 can be used to control or adjust the proportions of the bio-oil and the petroleum stream fed to the mixer 140.

In the mixer 140, the bio-oil stream in line 124 and the petroleum stream in line 134 are mixed and kept well mixed at a ratio perhaps with an excess of the petroleum stream at the startup of the process. In an embodiment, the bio-oil stream in line 124 and the petroleum stream in line 134 are mixed in the mixer 140 at a mass ratio of the bio-oil stream and the petroleum stream of about less than 1 at the start-up to provide a mixed stream. After mixing, a mixed stream in line 142 is taken from the mixer 140. In an aspect, the mixed stream 142 comprises the bio-oil stream and the petroleum stream in a ratio of about 0:100 to about 80:20 by mass at start-up. In an exemplary embodiment, the petroleum stream in line 134 is vacuum gas oil (VGO). The mixed stream in line 142 may be reacted with hydrogen in the presence of a catalyst in a reactor to produce an upgraded bio-oil stream.

In an embodiment, the mixed stream in line 142 is passed to a liquid phase hydrotreating (LPH) reactor 150. As described later in detail, a recycle stream in line 163 may also be passed to the reactor 150. A hydrogen stream in line 144 may also passed to the reactor 150. In an embodiment, the hydrogen stream in line 144 may be blended or mixed with the mixed stream in line 142 and passed to the reactor 150. A catalyst stream in line 145 may also be passed to the reactor 150. In an embodiment, the catalyst stream in line 145 may be blended or mixed with the mixed stream in line 142. to provide a combined stream in line 146 which is passed to the reactor 150. In an alternate embodiment, the catalyst stream in line 145 may be combined with the bio-oil in tank 120 and taken line 122. In another alternate embodiment, the catalyst stream in line 145 may be combined with the petroleum feed in tank 130 and taken in line 132. In yet another alternate embodiment, the catalyst stream in line 145 may be added to the recycle stream in line 163 or in line 139 to provide a combined recycle stream which is passed to the reactor 150. In the reactor 150, the petroleum stream, the bio-oil stream, the recycle stream, and the hydrogen stream may be reacted over a catalyst in a continuous liquid phase to provide an upgraded bio-oil stream comprising marine fuel oil in line 154. At least about 50 wt % of the upgraded bio-oil stream is bio-derived. Preferably, about 100 wt % of the upgraded bio-oil stream is bio-derived.

Liquid phase hydrotreating (LPH) is used for upgrading the heavy hydrocarbon feedstocks to produce distillate and residuum products. The hydrotreating catalyst typically comprises a solid particulate compound of a catalytically active metal, metal sulfide, or a metal in elemental form, either alone or supported on a refractory material such as an inorganic metal oxide (e.g., alumina, silica, titania, zirconia, and mixtures thereof). Other suitable refractory materials include carbon, coal, and clays. Zeolites and non-zeolitic molecular sieves are also useful as solid supports. One advantage of using a solid particulate either alone or supported is its ability to act as a “coke getter” or adsorbent of asphaltene precursors that have a tendency to foul process equipment upon precipitation.

Catalytically active metals for use in LPH include those from Group IVB, Group VB, Group VIB, Group VIIB, or Group VIII of the Periodic Table, which are incorporated in the heavy hydrocarbon feedstock in amounts effective for catalyzing desired hydrotreating reactions to provide, for example, lower boiling hydrocarbons that may be fractionated from the LPH effluent as naphtha and/or distillate products in the substantial absence of the solid particulate. Representative metals include iron, nickel, molybdenum, vanadium, tungsten, cobalt, ruthenium, and mixtures thereof. The catalytically active metal may be present as a solid particulate in elemental form or as an organic compound or an inorganic compound such as a sulfide (e.g., iron sulfide) or other ionic compound. Metal or metal compound nanoaggregates may also be used to form the solid particulates.

In some embodiments, the metal compounds can be formed in situ, as solid particulates, from a catalyst precursor such as a metal sulfite (e.g., iron sulfite monohydrate) that decomposes or reacts in the LPH reaction zone environment, or in a pretreatment step, to form a desired, well-dispersed and catalytically active solid particulate (e.g., as iron sulfide or molybdenum sulfide). Catalyst precursors also include oil-soluble organometallic compounds containing the catalytically active metal of interest that thermally decompose to form the solid particulate (e.g., iron sulfide or molybdenum sulfide) having catalytic activity. Such compounds are generally highly dispersible in the heavy hydrocarbon feedstock and normally convert under pretreatment or LPH reaction conditions to the solid particulate that is contained in the slurry effluent. Catalyst precursors also include oil-soluble organometallic compounds, inorganic molybdenum compounds, or chelated metal compounds containing the catalytically active metal. Molybdenum chelates including molybdenum octoate, molybdenum dithiocarbamate, and molybdenum naphthenate and molybdenum compounds such as ammonium heptamolybdate and phosphomolybdic acid thermally decompose to form the solid particulate through reaction with sulfidation components in the feed or other sulfidation additives such as dimethyl disulfide, di-tert-butyl (poly)sulfide, dibenzyl disulfide, (di)allyl (di)sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur or thiourea to form, for example, molybdenum disulfide having catalytic activity. An exemplary in situ solid particulate preparation, involving pretreating, the heavy hydrocarbon feedstock and precursors of the ultimately desired metal compound, is described, for example, in U.S. Pat. No. 5,474,977.

In another aspect, a catalyst precursor with the sulfidation component or the sulfidation additive may be provided in a line 131 and added to the petroleum stream in line 132. In another aspect, a catalyst or a catalyst precursor may be added to the feed stream in line 122 or the petroleum stream in line 132.

Alternatively, such metal sulfides or other active metal compounds can be formed ex-situ or in a separate process step through typical methods for producing metal sulfides. One such method includes hydrothermal synthesis where a molybdenum compound and sulfidation component are added to water with an additional reducing agent such as citric acid, oxalic acid, or hydrochloric acid or gaseous hydrogen. In some cases, the sulfidation component may also act as a reducing agent such as thiourea, ammonium sulfite, dimethyl sulfite, or dithiothreitol. The hydrothermal synthesis solution may be loaded into an autoclave reactor and sealed. If gaseous hydrogen is the reducing agent, the autoclave reactor can be pressurized from about 1378 kPag (200 psig) to about 10342 kPag (1500 psig) with hydrogen gas or the hydrogen gas can flow and bubble through the autoclave reactor. The autoclave reactor is then heated to a synthesis temperature of about 200° C. to about 300° C. under the foregoing hydrogen or inert gas pressure and held at the synthesis temperature for about 0.5 to about 16 hours. The autoclave reactor is allowed to cool to room temperature before depressurization and unloading. The solid catalyst can be collected such as by centrifugation, filtration, or drying. An example of hydrothermal metal sulfide synthesis is described in J. Espano, Phase Control in the Synthesis of Iron Sulfides, 145 J. Am. Chem. Soc. 18948-18955 (2023).

Another such method of forming metal sulfides ex situ could be a sulfiding procedure in a fixed bed reactor. Such methods involve loading a fixed bed reactor with a powdered or pelletized molybdenum compound and flowing a sulfiding gas, such as hydrogen sulfide, or a sulfiding liquid, such as oil doped with a sulfiding agent over the catalyst bed. The fixed bed reactor is heated to a sulfiding temperature of about 200° C. to about 350° C., for example, under the flow of sulfiding gas and/or hydrogen gas. The reactor is either pressurized before or after heating to sulfiding temperature to a pressure of about 1378 kPag (200 psig) to about 13790 kPag (2000 psig). The reactor may be heated slowly at, for example, 1° C./min, and held at selected temperature setpoints along the way to reach the final sulfiding temperature. The reactor may be held at temperature setpoints for hours to days. Once the sulfiding is complete, the reactor is cooled to room temperature and the catalyst is unloaded from the reactor in its metal sulfide form. The sulfided catalyst may be further reduced in particle size via grinding, milling, or other methods, so that it is a fine powder and highly dispersible.

Yet another method of forming metal sulfides ex situ could be a sulfiding procedure relying on chemical vapor deposition techniques. Such a method involves molybdenum compounds such as molybdenum trioxide, molybdenum dioxide, molybdenum foil, or dipotassium tetrathiomolybdate and sulfur compounds such as elemental sulfur, alkali sulfates, alkaline earth sulfates, or other metal sulfates or similar metal sulfites. A substrate is also used such as SiO₂/Si wafers, graphenes/graphites, or powdered or pelletized substrates commonly used as catalyst supports such as SiO₂, Al₂O₃, or TiO₂. Using a typical tube furnace synthesis reactor, the reactants and supports are placed in the reactor tube in a specific order with the sulfur source first (furthest upstream) followed by the molybdenum source downstream followed by the substrate further downstream. All compounds mentioned above are placed in a thermal zone in the tube furnace, typically in ceramic or other thermally and chemically resistant holders, which may be controlled as independent zones or as one zone. The substrate may be placed outside a thermal zone, if desired. This positioning is such that a gas flow through the tube first contacts the sulfur source, followed by the molybdenum source, followed by the substrate. A gas flow could include inert gas, hydrogen, steam, and/or oxygen/air. In typical operation, a gas flow is started, and the tube furnace reactor zones are heated to a temperature that is suitable to vaporize one or more of the compounds mentioned above at ambient pressure, typically equal to or less than 1000° C. The compounds vaporize and flow downstream where they react with each other and deposit on the substrate. The synthesis may run until complete consumption of all reactants or the substrate may be moved in and out of the apparatus so that the deposition time is limited to several minutes. After synthesis completion, the resulting metal sulfide is collected by removal of the substrate holder. The metal sulfide catalyst can be used as-is or, in the case of depositions of flat substrates like silicon wafers, the catalyst powder may be optionally scraped off for use without the silicon wafer. An example of chemical vapor deposition metal sulfide synthesis is described in W. Fu, Toward Edge Engineering of Two-Dimensional Layered Transition-Metal Dichalcogenides by Chemical Vapor Deposition,” 17 (17) ACS Nano 16348-16368 (2023).

Other suitable precursors include metal oxides that may be converted to catalytically active (or more catalytically active) compounds such as metal sulfides. In a particular embodiment, a metal oxide containing mineral may be used as a precursor of a solid particulate comprising the catalytically active metal (e.g., iron sulfide) on an inorganic refractory metal oxide support (e.g., alumina). Bauxite represents a particular precursor in which conversion of iron oxide crystals contained in this mineral provides an iron sulfide catalyst as a solid particulate, where the iron sulfide after conversion is supported on the alumina that is predominantly present in the bauxite precursor.

The active metals employed in the hydroprocessing catalysts of the present disclosure as hydrogenation components are the base metals of Group VIII, i.e., iron, cobalt, and nickel. In addition to these metals, other metals may also be employed in conjunction therewith, or on their own, including the metals of Group VIB, e.g., molybdenum and tungsten. The amount of hydrogenating metal in the catalyst can vary within wide ranges. Any amount between about 0.05 wt % and about 80 wt % may be used. In an aspect, molybdenum may be provided as a ground hydrotreating catalyst of particle size typically less than 60 mesh, preferably less than 100 mesh, more preferably less than 200 mesh, and even more preferably less than 400 mesh. The hydrotreating catalyst may be sulfided in situ or ex situ using any method mentioned throughout. In an aspect, molybdenum may be provided as an organic molybdenum such as molybdenum octoate or molybdenum dithiocarbamate which because it is oil or hydrocarbon soluble may be added directly to the hydrocarbon feed separately from or with the carbon particles. The molybdenum may react with sulfur provided in the hydrocarbon feed or an additive to produce molybdenum sulfide in the reactor which is the active form of the molybdenum catalyst.

Nickel may be provided as a catalyst in the way molybdenum is added.

In another aspect, the catalyst is a nickel and molybdenum sulfide catalyst where nickel is incorporated into the molybdenum sulfide molecular structure to enhance catalytic activity but may also form separate nickel sulfide phases with their own separate catalytic activity. In syntheses mentioned throughout that involve an aqueous solution, nickel can be added by simply introducing a nickel compound to the aqueous solution before heating to final synthesis temperature. In syntheses that involve a solid and gas or a solid and liquid method, nickel compounds may be physically mixed with the molybdenum compounds. For in situ formation of the nickel and molybdenum sulfide in the LPH, an oil-soluble nickel compound may be added directly to the feed or added from a separate line into the LPH. Nickel compounds that could be used include nickel octoate, nickel nitrate hexahydrate, nickel sulfate, nickel sulfite, nickel acetate tetrahydrate, nickel citrate hydrate, nickel hydroxide, or nickel hydroxide carbonate. The molar ratio of molybdenum to nickel can range from about 1:1 to about 5:1, preferably about 2:1 to about 4:1, or preferably about 2.5:1 to about 3.5:1.

The sulfur can be provided by a solid or liquid sulfiding agent that is added via line 131 into the petroleum stream in line 132 or added into a recycle stream to the reactor or premixed into the feed. Gaseous sulfiding agents like hydrogen sulfide can be added to the hydrogen line 144. Some preferred sulfiding agents are hydrogen sulfide, dimethyl disulfide, di-tert-butyl (poly) sulfide, dibenzyl disulfide, (di) allyl (di) sulfide, ammonium sulfite, dimethyl sulfite, dithiothreitol, elemental sulfur or thiourea.

An aqueous molybdenum may be derived from reacting MoO₃ with an aqueous acid or basic solution such as phosphoric acid or ammonium hydroxide, respectively. Molybdenum in aqueous or oil-soluble liquid form in a volume selected to achieve target concentration may be dropped onto carbon particles which may serve as a carrier.

Without help from other catalysts, the concentration of the molybdenum in the liquid feeds to the LPH reactor 150 may be more than 0 wppm and no more than about 2 weight % in the liquid feed, suitably no more than about 0.5 weight % in the liquid feed, and typically no more than about 2000 wppm in the liquid feed. In some cases, the concentration of molybdenum may be no less than 1000 wppm in the liquid feed, and preferably not less than 500 wppm of the feed.

In preferred embodiments where the catalyst contains both nickel and molybdenum, the concentration of the molybdenum in the liquid feed to the LPH reactor is the same as specified above. The concentration of the nickel in the liquid feed to the LPH reactor may be more than 0 wppm and no more than about 2 wt % in the liquid feed, suitably no more than about 0.5 weight % in the liquid feed, and typically no more than about 2000 wppm in the liquid feed. In some cases, the concentration of nickel may be no less than 500 wppm in the liquid feed, and preferably not less than 1000 wppm of the feed. By feed, the aggregate of all feed streams to the reactor is meant.

In preferred embodiments a stream containing catalyst may be recycled to the reactor. Thus, the concentration of molybdenum in the reactor can be controlled at a steady state greater than the concentration of molybdenum in the liquid feed. The concentration of molybdenum in the reactor liquid is typically between 0.1 wt % and 10 wt %, preferably between 0.5 wt % and 7 wt % and more preferably between 2 wt % and 7 wt %, and even more preferably between 0.2 wt % and 3 wt %.

Conditions in the LPH reactor 150 generally include a temperature from about 315° C. (600° F.) to about 538° C. (1000° F.), or about 321° C. (610° F.) to about 482° C. (900° F.), or about 340° C. (644° F.) to about 470° C. (878° F.), a pressure from about 3.5 MPa (500 psig) to about 30 MPa (4351 psig), suitably 5.5 MPa (800 psig) to about 19.3 MPa (2800 psig), preferably 6.8 MPa (1000 psig) to about 13.8 MPa (2000 psig), or more preferably no more than about 10.3 MPa (1500 psig), and a reactor liquid residence time from about 0.1 to about 8 hrs, preferably 2 to about 6 hrs, or 1 to about 5 hrs, or about greater than 3 hrs.

In another exemplary embodiment of the present disclosure, the LPH reactor 150 may be a continuous stirred tank reactor (CSTR). Operating conditions in the CSTR 150 may be as given above but may preferably include a temperature from about 300° C. (572° F.) to about 500° C. (932° F.), a pressure from about 6.8 MPa (1000 psig) to about 13.8 MPa (2000 psig), and a residence time of about 30 mins. to about 8 hours. From the LPH reactor 150, the upgraded bio-oil stream is taken in line 154.

In an aspect, the LPH reactor 150 may be selected from a bubble column reactor, a slurry reactor, and an ebullated bed reactor to facilitate contact and mixing of gases with liquid or slurry materials. Other types of reactors may be used to facilitate the contact and the mixing.

In another aspect, the LPH reactor 150 may be a once-through reactor for processing the streams to produce the upgraded bio-oil stream.

Under the hydrotreating conditions, the catalyst in the LPH reactor 150 may hydrodeoxygenate the mixed stream in line 142. In an aspect, the catalyst in the LPH reactor 150 may hydrodeoxygenate carbonyl compounds more selectively than other oxygenates such as phenolics and alcohols.

The composition of the material inside the LPH reactor 150 such as the reaction mixture may also be characterized by a band area ratio of oxygenates measured by ATR-IR spectroscopy. In an exemplary embodiment, the composition of the reaction mixture inside the reactor 150 should comprise a ratio of oxygenates of one or more of a (C—O)/C ratio from about 0 to about 0.7 or preferably from about 0 to about 0.5, or more preferably from about 0 to about 0.4; a (C═O)/C ratio from about 0 to about 0.5 or preferably from about 0 to about 0.4 or more preferably from about 0 to about 0.3; an OH/C ratio from about 0 to 2.5, or preferably from about 0 to about 1.5, or more preferably from about 0 to about 1; and an O/C ratio from about 0 to 1.7; or preferably from about 0 to about 1 or more preferably from about 0 to about 0.6.

The upgraded bio-oil stream in line 154 is passed to a hot separator 160. In the hot separator 160, heavy oil is separated from light oil. A hot bottoms stream is taken in line 156 from the bottoms of the hot separator 160. The hot bottoms stream which contains catalyst is separated and taken in line 156 from the hot separator 160. The hot bottoms stream in line 156 comprises a majority of the catalyst, for example all the catalyst exiting from the reactor 150, may be taken in the hot bottoms stream in line 156. In an aspect, the hot bottoms stream in line 156 may be characterized as a heavy oil stream comprising catalyst. Light oil is taken in a hot overhead stream in line 155 from the hot separator 160. Water is also separated in the hot separator 160 which is taken with the light oil in the hot overhead stream in line 155. The hot separator 160 may be run at a temperature of about 250° C. to about 400° C. and at a pressure of about the pressure of the reactor 150.

The hot bottoms stream in line 156 may be passed to a recycle tank 177. A recycle oil stream comprising the catalyst is taken in line 158 from the bottom of the recycle tank 177. A heavy oil stream comprising the marine fuel oil in line 179 may be taken from the recycle tank 177. A predominance of the catalyst may be in the recycle oil stream in line 158. The recycle oil stream in line 158 may be recycled to the reactor 150 perhaps through a pump 157.

The heavy oil stream in line 179 may be taken in such a way to avoid taking the bulk of the catalyst in this stream. In an aspect, the heavy oil stream in line 179 may be separated to remove a marine fuel oil stream lean of catalyst. Separation may include filtration, centrifuge, vacuum flashing, or wiped film evaporation to remove catalyst from a marine fuel oil stream lean of catalyst.

In an embodiment, the heavy oil stream in line 179 may be passed to a catalyst separation vessel 136 for separating catalyst that may be present. In exemplary embodiment, the catalyst separation vessel 136 may be selected from a filtration vessel, a centrifuge, a vacuum distillation column, a wiped film evaporator, a gravity settler, or a combination thereof. In the catalyst separation vessel 136, the catalyst is separated to produce a heavy oil product stream which may include the marine fuel oil. The marine fuel oil stream is taken in line 137 from the catalyst separation vessel 136. A concentrated catalyst stream comprising catalyst in heavy oil is taken in line 138 from the vessel 136. The recycle oil stream in line 158 may be combined with the concentrated catalyst stream in line 138 to provide a combined recycle oil stream in line 139 which is recycled to the reactor 150. In other embodiments, the heavy oil stream in line 179 is separated to remove a marine fuel oil stream which may comprise a similar amount of catalyst as the recycle stream 139 and the catalyst is separated from the marine oil stream in one or more downstream processing steps.

A wiped film evaporator (WFE) uses a hinged blade with minimal clearance from the internal surface to agitate the flowing catalyst containing stream to effect separation of catalyst from heavy oil. In the catalyst separation vessel 136 comprising a WFE, the heavy oil stream in line 179 enters tangentially above a heated internal tube and is distributed evenly over an inner circumference of the tube by the rotating blade perhaps at vacuum. Catalyst particles spiral down the wall while bow waves developed by rotor blades generate highly turbulent flow and optimum heat flux. The heavy oil evaporates rapidly and vapors can flow either co-currently or counter-currently against the catalyst particles. In a simple WFE design, heavy oil may be condensed in a condenser located outside but as close to the evaporator as possible.

Other evaporative techniques may be used to separate the catalyst from the marine fuel oil in the catalyst separation vessel 136.

The hydrotreating conditions of the LPH reactor 150 for the liquid phase hydrotreating of the bio-oil stream are selectively chosen and the hydrotreating conditions of the LPH reactor 150 can be adjusted to allow for less oxygen conversion along with less hydrogen consumption. Applicants found that oxygen content over the overall product can be about 5 to about 10 wt % and about 3 to about 6% in the marine fuel fraction while still meeting ISO 8217 specifications including the acid number specifications. In some embodiments the ISO 8217 specifications may be met by a marine fuel entirely comprising stabilized bio-oil treated in the LPH reactor 150 and in other embodiments the marine fuel composition can be blended with a petroleum-derived marine fuel oil in order to meet the ISO 8217 specifications. Also, the oxygenates that remain in the marine fuel comprise a minimum amount of phenols. This occurs for reasons that are unique to the present process. First, more of the carboxylic acids remaining in the product after LPH are lower boiling compounds that would not be included in a heavier marine fuel cut. Second, the hydrotreating of the bio-oil in the LPH reactor 150 deoxygenates carbonyl compounds more selectively than other oxygenates such as phenolics and alcohols to produce a marine fuel which meets the existing marine fuel specifications, independently or after blending with a petroleum-derived marine fuel oil blendstock. The significant amount of oxygen remaining in the product means that less hydrogen is consumed in the LPH process and may not need a second costly fixed bed hydrotreating process. Furthermore, low hydrogen consumption is associated with lower cost (since less hydrogen needs to be produced externally) and with lower carbon intensity since most economically viable hydrogen production pathways such as methane steam reforming have high carbon intensity.

In an aspect, a portion of the marine fuel oil stream in line 137 may be taken in line 166 and passed to a stripping column 190 to strip the light materials. A stripping media such as steam may be passed to the stripping column 190 in a stripping media line 191. Lighter material may be taken in an overhead line 192 from the stripping column 190. The lighter material in the overhead line 192 may be diverted to other uses such as naphtha and jet fuel production. A stripped marine fuel oil stream may be taken from the bottoms of the stripping column 190 in line 194. The stripping column 190 may be operated at a bottoms temperature of about 75° C. to about 250° C. In an embodiment, the remaining marine fuel oil stream is taken in line 184. A control valve 11 may be provided on line 184 to regulate the flow of the marine fuel oil stream to the unit 180. Alternatively, stream 192 may be combined with streams 286 and/or 281 or portions of these streams to produce a marine fuel oil blend stock.

The hot overhead stream comprising the light oil in line 155 may be cooled and charged to a cold separator 165. In the cold separator 165, gaseous components may be separated from the light oil. The gaseous components are separated and taken in line 164 from the cold separator 165. The cold overhead stream in line 164 may be purified to obtain a hydrogen stream which may be recycled to the reactor 150, or recycled to the reactor 150 without purification. A bottoms light oil stream comprising the upgraded bio-oil stream and aqueous components is taken in line 169 from the cold separator 165. The bottoms light oil stream in line 169 comprises water that should be separated from the upgraded bio-oil stream. The cold separator 165 may be operated at a temperature of about 0 to about 75° C. and at a pressure of about the pressure of the reactor 150.

In an embodiment, the bottoms light oil stream in line 169 is passed to an aqueous separator 147 for separating water from the upgraded bio-oil. Water is separated and taken in an aqueous bottoms line 148 from the aqueous separator 147. A light upgraded bio-oil stream is taken in line 159 from the aqueous separator 147 lean in water concentration. The aqueous separator 147 may be operated at a temperature of about 0 to about 75° C. and at a pressure of about 0 MPa (gauge) (0 psig) to about 1 Mpa (gauge) (150 psig).

In an embodiment, the light upgraded bio-oil stream in line 159 may be fractionated in a fractionation column 170 to separate the light upgraded bio-oil stream in line 168 into one or more hydrocarbon streams. The light upgraded bio-oil stream in line 159 may be passed to the fractionation column 170 to provide an overhead stream in line 171. The overhead stream in line 171 may be passed to a receiver 173 to further separate the overhead stream. From the receiver 173, LPG and light gases are separated in an overhead stream in line 172. The liquid stream in line 174 from the receiver 173 is separated into a reflux stream in line 175 and a naphtha stream in line 176. The reflux stream in line 175 is recycled back to the fractionation column 170. A kerosene stream may be taken in line 181 from a side of the fractionation column 170. From the bottoms of the fractionation column 170, a diesel stream may be taken in line 178. A reboiling stream may be taken from the diesel stream in line 178, heated in the reboiler 183 and a reboiled stream in line 185 may be passed to the fractionation column 170. A diesel product stream may be taken in line 186 from the bottom of the fractionation column 170.

In an embodiment, the diesel product stream 186 can be combined with other streams such as stream 181, 137 or 194 to produce the marine fuel oil blend stock.

The fractionation column 170 may be operated at vacuum pressure. In an embodiment, fractionation column 170 may be operated at an overhead pressure of about 34 kPa (gauge) (5 psig) to about 173 kPa (gauge) (25 psig), and a bottoms temperature of about 500° C. (932° F.) to about 750° C. (1382° F.) or about 500° C. (932° F.) to about 600° C. (1112° F.).

In an embodiment, a marine fuel oil blend stock may be produced by blending the stripped marine fuel oil stream in line 194 with an entirety or a portion of one or more of the marine fuel oil stream in line 184, the kerosene stream in line 181, and the diesel product stream in line 186. In an exemplary embodiment, a kerosene blend stream may be taken in line 281, and a diesel blend stream may be taken in line 286 for blending with stripped marine fuel oil stream in line 194 and produce the marine fuel oil blend stock.

The stripped marine fuel oil stream in line 194, the marine fuel oil stream in line 184, the kerosene blend stream in line 281, and/or the diesel blend stream in line 286 may be charged to a blending unit 180. The kerosene blend stream in line 281 may comprise a portion or an entirety of the kerosene stream in line 181. The diesel blend stream in line 286 may comprise a portion or an entirety of the diesel product stream in line 186. This embodiment may allow maximization of marine fuel oil yield while producing less diesel and/or jet fuels according to demand. A control valve may be provided on each of these lines to regulate their flow into the blending unit 180. A valve 21 is provided on the diesel blend line 286, a valve 31 is provided on the kerosene blend line 281, a valve 11 is provided on the marine fuel oil line 184, and valve 51 is provided on the stripped marine fuel oil line 194 to regulate their flow into the blending unit 180. One or both of a petroleum-derived marine fuel oil blend stock in line 294 and a bio-derived marine fuel oil blend stock in line 292 may be added into the blending unit 180.

The bio-derived marine fuel oil blend stock in line 292 may comprise an oxygen content of greater than about 2 wt % and at least one phenolic compound of more than about 0.0015 moles/g. The petroleum-derived marine fuel oil blend stock in line 294 may have a total acid number of less than about 2.5 mg KOH/g. Valves 61 and 71 may be provided on the bio-derived marine fuel oil blend stock in line 292 and the petroleum-derived marine fuel oil blend stock in line 294 respectively for regulating their flow rate into the blending unit 180. In the blending unit 180, the stripped marine fuel oil stream in line 194 may be blended or mixed with one or more of the marine fuel oil stream in line 184, the kerosene blend stream in line 281, the diesel blend stream in line 286, and one or both of the petroleum-derived marine fuel oil blend stock in line 294 and the bio-derived marine fuel oil blend stock to produce a marine fuel oil blend stock. The marine fuel oil blend stock is discharged in a blend stock line 182 from the blending unit 180. The streams that are blended together in the blending unit 180 to make the marine fuel oil blend stock in line 182 are selected based on their oxygen content, acid number, flashpoint, T5 and other distillation properties in order to meet an ISO-8217 marine fuel oil specification either independently or as a component in a blend with one or both of the bio-derived marine fuel oil blend stock in line 292 and the petroleum-derived marine fuel oil blend stock in line 294.

In accordance with the present disclosure, the marine fuel oil blend stock in line 182 may be analyzed online or offline using one or more of the infrared (IR) spectroscopy and NMR spectroscopy, The NMR spectroscopy determines the physical and chemical properties of atoms or molecules. Proton (¹H) NMR is one of the most widely used NMR methods. Different nuclei can also be detected by NMR spectroscopy, ¹H (proton), ¹³C (carbon 13), ¹⁵N (nitrogen 15), ¹⁹F (fluorine 19), among many more. ¹H and ¹³C are the most widely used and their procedures are as below:

¹H Liquid State Procedure

NMR spectra of the samples were collected by employing a Bruker Avance Spectrometer operating at a frequency of 500.1317 for 1H experiments. The samples were prepared by dissolving 2-3 drops of bio-oil in 0.6 mL of chloroform-d with a trace quantity of tetramethylsilane being added as an internal reference. Quantitative results were obtained using a 90° pulse with 10 ms length and 10 seconds of delay between acquisitions. The number of scans was 128. Processing included baseline correction and the use of 1 Hz exponential line broadening before Fourier transformation. The spectra were further integrated by regions corresponding to the following lumped functional groups: 0.5-1.5 ppm alkanes, 1.5-3 ppm aliphatics alpha to heteroatom or unsaturation, 3-4.4 ppm alcohols, methylene-dibenzene, 4.4-6 ppm olefins, methoxys, carbohydrates, 6-7.18 ppm (hetero) aromatics, furans, 7.18-8.5 ppm (hetero) aromatics, 8.5-10.1 ppm aldehydes.

¹³C Liquid State Procedure

NMR spectra of the samples were collected by employing a Bruker Avance Spectrometer operating at a frequency of 125.7715 for 13C experiments. The samples were prepared using a 50:50 (v/v) mixture of chloroform-d and bio-oil analyte. Additionally, a trace quantity of tetramethylsilane was added as an internal reference and chromium acetylacetonate was used as a relaxation agent. Quantitative results were obtained using an inverse-gated pulse sequence, and all 13C spectra were acquired by using 11.3 μs pulses and 10 seconds of delay between acquisitions. The number of scans was 2048. Processing included baseline correction and the use of 3 Hz exponential line broadening before Fourier transformation. The spectra were further integrated by regions corresponding to the following lumped functional groups: 0-27 ppm short aliphatics, 27-54 ppm long and branch aliphatics, 54-94 ppm alcohols, ethers, phenyl methoxy groups, carbohydrates (R—OH), 94-167 ppm aromatics, olefins, heteroaromatics, furans, 167-186 ppm esters, carboxylic acids, 186-225 ppm ketones, aldehydes. The sum of the 167-186 ppm and 186-225 ppm regions is also referred to as total C═O or total carbonyls.

The oxygen content of the marine fuel oil blend stock in line 182 may be characterized by a band area ratio of oxygenates measured by Attenuated Total Reflectance (ATR) infrared (IR) spectroscopy. ATR-IR is a sampling technique in which the sample is placed in intimate contact with a crystal having a high index of refraction. The IR light is brought in from the bottom and reflected from the surface of the crystal. Samples were placed as-is onto a diamond crystal for ATR IR spectrum collection (64 scans, 2 cm−1 resolution). The IR spectra may be collected on a Nicolet is 50 FTIR spectrometer or an equivalent research-grade instrument, truncated and baseline corrected in GRAMS AI software, and deconvolved and plotted in OriginPro 2016.

For integration and deconvolution of the spectra, two approaches may be taken. Simple integration of spectral regions may be performed for different functional groups. The integration areas for various functional groups are measured. In accordance with the present disclosure, the following are roughly the integration areas for each functional group: about 3100-3695 cm⁻¹ for hydroxyl (—OH) groups, about 2800-2995 cm⁻¹ for hydrocarbon groups, and about 1000-1315 cm⁻¹ regions for methoxy groups. For the C═O and C═C regions which span from about 1500 cm⁻¹ to about 1800 cm⁻¹, the spectra may be deconvolved by first baseline correcting the region, then fitting multiple peaks using the Origin Pro software. Spectra may not be normalized before deconvolution since there is no internal standard, thus, only area ratios may be used for sample comparison. The aromatic C═C band area is typically from the deconvolved bands in the region ranging from about 1500 cm⁻¹ to about 1600 cm⁻¹, the alkene C═C band area in the region ranging from about 1600 cm⁻¹ to about 1700 cm⁻¹, and the C═O band area in the region ranging from about 1700 cm⁻¹ to about 1800 cm⁻¹. Depending on the complexity of the region, some spectra could be deconvoluted into 6 bands or as many as 9 bands.

Total carbon “C” value may also be calculated. The total carbon “C” value is equal to the sum of the integrated regions of CHx stretching and C═C stretching so that C equals (CHx+C═C) integrated band areas. Similarly, the total oxygen “O” value is equal to the sum of the integrated regions of C═O and C—O stretching so that O equals (C═O+C—O) integrated band areas. All other band areas identify the specific molecular vibrations that they represent.

Based on the band area values of these functional groups, a band area ratio value is also calculated for various functional groups. Band area ratio is a unitless parameter which remains the same for all measuring instruments. For instance, a band area ratio of C═O/C—O can be calculated and indicates the relative amount of C═O vs C—O bonds in the sample. Similarly, from the “total carbon ‘C’” value, “total oxygen ‘O’” value and the band areas, a metric of C═O oxygenates to total oxygen mole ratio can be calculated as the ratio of C═O oxygenates band to the ratio of “total oxygen ‘O’” to “total carbon ‘C’”. A metric of C—O oxygenates to total oxygen mole ratio can be calculated as the ratio of C—O oxygenates band to the ratio of “total oxygen ‘O’” to “total carbon ‘C’”.

The marine fuel oil blend stock in line 182 may also be characterized by its viscosity at different temperatures, namely at 50° C. as per the ISO 8217 specifications. The samples were analyzed using an Anton Paar MCR 302 rheometer equipped with a 50 mm Cone-Plate geometry and a Peltier temperature control system to ensure precise thermal regulation during measurements. The cone is machined at an angle of one degree and truncated to establish a fixed gap spacing of approximately 97 μm, consistent with standard Cone-Plate configurations. Samples are analyzed without dilution to preserve their native properties. Instrument control and data acquisition are performed using RheoCompass software, enabling accurate and reproducible rheological measurements under the specified conditions. Viscosity measurements were conducted at multiple shear rates from about 0.5 to about 100 s⁻¹, and the data that is reported here was collected at a shear rate of about 0.793 s⁻¹ for all samples. Most of the samples appeared to behave like Newtonian fluids, as the viscosity was nearly constant regardless of the shear rate. In a typical embodiment, the marine fuel oil blend stock in line 182 may comprise a viscosity of more than about 2 cSt. In a preferred embodiment, the marine fuel oil blend stock in line 182 may comprise a viscosity of more than about 10 cSt. In an exemplary embodiment, the marine fuel oil blend stock in line 182 may comprise a viscosity of more than about 20 cSt.

Further, the marine fuel oil blend stock in line 182 may be analyzed to measure oxygen concentration through a carbon, hydrogen, nitrogen, oxygen (CHNO) elemental analysis as a proxy for oxygenate concentration. In a typical embodiment, the marine fuel oil blend stock in line 182 may comprise a total oxygen concentration of less than about 8 wt %. In a preferred embodiment, the marine fuel oil blend stock in line 182 may comprise a total oxygen concentration of less than about 6 wt %. In an exemplary embodiment, the marine fuel oil blend stock in line 182 may comprise a total oxygen concentration of less than about 5 wt %.

The oxygenates that may remain present in the marine fuel oil blend stock in line 182 may include one or more of the aldehyde, ester, carboxylic acid, ketone, hydroxyl, ether, sugar, phenol and alcohol groups. In an embodiment, the marine fuel oil blend stock in line 182 may comprise a carbon mole % of one or more carbonyl containing groups selected from aldehyde, ester, carboxylic acid, and ketone in amount of less than about 1.2 mole % of the total carbon present in the marine fuel oil as measured by ¹³C NMR spectroscopy. In an preferred embodiment, the marine fuel oil blend stock in line 182 may comprise a carbon mole % of one or more carbonyl containing groups selected from aldehyde, ester, carboxylic acid, and ketone in amount of less than about 0.9 mole % of the total carbon present in the marine fuel oil blend stock as measured by ¹³C NMR spectroscopy. In an exemplary embodiment, the marine fuel oil blend stock in line 182 may comprise a carbon mole % of one or more carbonyl containing groups selected from aldehyde, ester, carboxylic acid, and ketone in amount of less than about 0.15 mole % of the total carbon present in the marine fuel oil blend stock as measured by ¹³C NMR spectroscopy. In this definition, mole % of carbon is measured as the integrated ¹³C NMR intensity of the sum of the regions (δ=196 ppm to δ=225 ppm corresponding to ketones and aldehydes and δ=167 ppm to δ=186 ppm corresponding to esters and carboxylic acids). The sum describes the total amount of carbon atoms contained in the carbonyl (i.e. C═O) functional group and does not include the rest of the carbon in the molecule. In another embodiment, the marine fuel oil blend stock in line 182 may comprise a carbon mole % of one or more-OH or ether containing groups selected from hydroxyl, ether, sugar, aromatic-OH, aromatic ethers, and alcohol in amount of greater than about 0.2 mole % of the total carbon present in the marine fuel oil as measured by ¹³C NMR spectroscopy. In this definition, mole % of carbon is measured as the integrated ¹³C NMR intensity of the region (8=54 ppm to 8=94 ppm) and describes the total amount of carbon atoms contained in the functional group and does not include the rest of the carbon in the molecule.

In an aspect, the marine fuel oil blend stock in line 182 may comprise a C═O/C—O oxygenates mole ratio of less than about 0.9 as measured by ATR-IR spectroscopy. In an embodiment, the marine fuel oil blend stock in line 182 may comprise a C═O/C—O oxygenates mole ratio of less than about 0.5 as measured by ATR-IR spectroscopy. In a preferred embodiment, the marine fuel oil blend stock in line 182 may comprise a C═O/C—O oxygenates mole ratio of less than about 0.25 as measured by ATR-IR spectroscopy.

In another aspect, the marine fuel oil blend stock in line 182 may comprise a C═O oxygenates to total oxygen mole ratio of less than about 0.40 as measured by ATR-IR spectroscopy. In an embodiment, the marine fuel oil blend stock in line 182 may comprise a C═O oxygenates to total oxygen mole ratio of less than about 0.35 as measured by ATR-IR spectroscopy. In a preferred embodiment, the marine fuel oil blend stock in line 182 may comprise a C═O oxygenates to total oxygen mole ratio of less than about 0.2 as measured by ATR-IR spectroscopy.

Further, the marine fuel oil blend stock in line 182 may comprise a minimum concentration of phenols out of the total oxygenates present in the marine fuel oil blend stock. The concentration of phenols in the marine fuel oil blend stock in line 182 may be measured by phenolic acid titration. The specifics of phenolic acid titration are described in the example herein. In an embodiment, the marine fuel oil blend stock in line 182 may comprise at least about 0.0010 moles of phenolic compounds per gram of the marine fuel blend stock as measured by phenolic acid titration. In an exemplary embodiment, the phenolic compounds may include cresol and n-propyl phenol.

In an exemplary embodiment, the marine fuel oil blend stock in line 182 may comprise a flash point temperature greater than about 60° C. (140° F.) according to ISO 8217. The marine fuel oil blend stock in line 182 may typically comprise a minimum T5 temperature of at least about 132° C. (270° F.). However, the T5 temperature must typically be higher to provide a required flash point temperature greater than about 60° C. (140° F.) as required by ISO 8217. We have found that the oxygenates in the marine fuel oil blend stock tend to elevate the flash point temperature thus allowing a lower T5 temperature for the oxygen-containing marine fuel oil blend stock, translating to a greater yield of marine fuel. Evaluating this relationship, we have determined an embodiment of the marine fuel oil blend stock composition may comprise a T5 temperature of at least (−21.663×(wt % oxygen in said marine fuel oil composition)+432)° F. when said marine fuel oil composition comprises an oxygen concentration of greater than about 4.44 wt %, and the T5 temperature is at least about 337° F. when said marine fuel oil composition comprises an oxygen concentration of no more than about 4.44 wt %.

In an aspect, the marine fuel oil blend stock may comprise an oxygen concentration of at least about 2 wt % or at least about 3 wt % or at least about 4 wt %.

Acid number is a suitable method for measuring carboxylic acid content. Briefly, acid number is obtained via typical potentiometric titration using a solution of tetra-n-butylammonium hydroxide and isopropanol as the titrant. A standard method of benzoic acid and N,N-dimethylformamide is run every 3 hours to ensure results. The sample is weighed and added to a beaker. The N,N-dimethylformamide solution is added to the beaker (internal standard) and the mixture is stirred under nitrogen for 5 mins before titration.

In an embodiment, the marine fuel oil blend stock in line 182 may comprise an acid number of less than about 2.5 mg KOH/g. A plot of acid number as a function of oxygen wt % in marine fuel is shown in FIG. 2. Acid number meets the specification of 2.5 mg KOH/g when the oxygen concentration in the marine fuel was less than 5%.

In another embodiment, the marine fuel oil blend stock in line 182 may comprise an acid number greater than about 2.5 mg KOH/g, but the blend stock then must be blended with a low-acid petroleum based blend stock in order to meet the ISO-8217 specification as a marine fuel. In this embodiment, the marine fuel oil blend stock in line 182 is blended with a petroleum based blend stock with an acid number of less than 2.5 mg KOH/g. The acid number of the blended bio-based marine fuel oil blend stock with the petroleum based blend stock is less than 2.5 mg KOH/g.

In an embodiment, the marine fuel oil blend stock in line 182 may have a density of no more than about 1.01 grams per cm³ at 15° C.

Examples

A 2 L stirred tank reactor pilot plant was operated under several different testing regimes to continuously upgrade bio-oil. Bio-oil used in these tests was thermal pyrolysis oil from one of two suppliers (A or B) produced from softwood (SW) or hardwood (HW). In total, seven tests were performed. In a feed tank, the bio-oil and a molybdenum compound like Mo octoate were blended together and fed to the reactor. A stream of sulfiding material was added either to the feed tank or co-fed to the reactor. A hydrogen gas stream was added into the bio-oil feed stream upstream of the reactor. After reaction, the product stream went through hot separators, cold separators, and an oil-water separator to finally provide a light oil product stream, a heavy oil product stream, and an aqueous stream. In all runs, the heavy oil product stream was recycled back into the reactor to provide a source of recycled, activated catalyst and deoxygenated oil. For the study, a total of seven experiments were performed and seven marine compositions with different oxygen contents were produced. The operating conditions and the parameters of the seven experiments are in Table 1 below:

TABLE 1
						Wt % of Mo
				Bio-Oil		in heavy oil	% bio-oil
				Supplier		(stream	of total
	Temperature	Pressure	Residence	and	Catalyst	137)/in	bio-oil +
Exp.	(° F.)	(psig)	Time (hr)	Source	Compound	reactor (150)	VGO feed

A	721	1300	6.3	A-SW	Suspended	0.69/1.21	86%
					Mo, Mo
					octoate
B	717	1301	4.3	A-SW	Mo octoate	1.65/3.32	100%
C	736	1300	4.3	A-SW	Mo octoate	1.35/2.82	100%
D	720	1299	4.3	A-SW	Mo octoate	1.36/2.70	100%
E	727	1296	7.8	B-SW	Aqueous	0.49/1.51	100%
					Ni/Mo/P
F	744	1299	7.8	B-SW	Aqueous	0.33/1.31	100%
					Ni/Mo/P
G	756	1300	5.2	B-HW	Aqueous	not measured	100%
					Ni/Mo/P

For each experiment A to G, the light oil product from the condensate of the light upgraded bio-oil stream in line 159, and the heavy oil product stream in line 137 were collected. The total liquid oil product generally consisted of approximately 64% light oil and 36% heavy oil. For the experiments, three light oil products and one heavy oil product were taken and characterized. Three additional products were taken as a combined sample containing both light oil and heavy oil in the ratio that the products were formed in.

The seven samples were analyzed for acid number (carboxylic acid number), phenolic content (phenolic acid number), and oxygen content. Acid number of the seven marine fuel oil streams were measured based on the method as per C. Dence, Determination of Carboxyl Groups, S. Lin Methods in Lignin Chemistry, Springer Series in Wood Science. Springer, Berlin, Heidelberg 458-464. https://doi.org/10.1007/978-3-642-74065-7. The details of the acid number test are as below:

Materials:

0.05N tetra-n-butylammonium hydroxide solution (TnBAH): Prepared by diluting 50.0 mL of 1.0N TnBAH (Aldrich, SAP #1014519, 100 mL) solution to 1.00 L in isopropanol. Components were mixed thoroughly before transferring the solution to a Dosimat bottle. The 1.0N TnBAH solution was blanketed with nitrogen and stored in the refrigerator.

Benzoic Acid: p-Hydroxybenzoic Acid, was stored in a dessicator when not in use.

Hydrochloric Acid additive solution: 2 mL of concentrated HCl was added to 100 mL of deionized water and mixed thoroughly. 4 mL of this solution was added to ˜140 mL of dimethylformamide (DMF) for titration of samples.

Standardization of the Titrant:

0.15-0.20 g of dried benzoic acid was added into a titration beaker and the weight was recorded to the nearest 0.1 mg, 120 mL of DMF was added and titrate with the TnBAH solution. The standardization was done in duplicate. Normality was calculated to 3 significant figures as per the below formula:

N = g ⁢ Benzoic ⁢ acid ( mL ⁢ titrant ) ⁢ ( 0 . 1 ⁢ 2 ⁢ 2 ⁢ 1 ⁢ 2 )

Standardization was repeated every 3 hours when using this procedure.

Titration of Samples:

Prior to the first sample analysis, 0.05-0.08 g of p-hydroxybenzoic acid was weighed into a titration beaker. 140 mL of DMF and 4 mL of the HCl additive solution was added. The resultant solution was titrated through the 3^rd inflection. This was the blank used to calculate the HCl correction, and can be used as a QC for the Phenolic Hydroxyl titrations.

0.3-0.4 g of lignin and 0.05-0.08 g of p-hydroxybenzoic acid were weighed into a titration beaker. 140 mL of DMF and 4 mL of the HCl additive solution were added. Beaker was blanketed with nitrogen and stirred for 5 minutes before titration. Titration was performed with 0.05N TnBAH to the 3^rd inflection.

Calculations:

The theoretical titer of the internal standard used was calculated in the blank or sample titration:

a ⁢ ( mL ) = g ⁢ pHBA 0 . l ⁢ 3812 ⁢ ( N )

and HCl interference was calculated from the blank c (mL)=[(measured volume to reach 2nd inflection of blank)−(measured 1st inflection)]−(a (mL, calculated above)), then,

m ⁢ Eq ⁢ carboxyl / g ⁢ sample = [ ( y ) - ( x ) - ( c ) - ( a ) ] ⁢ N w m ⁢ Eq ⁢ phenolic ⁢ hydroxyls / g ⁢ sample = [ ( z ) - ( y ) - ( a ) ] ⁢ N w

where,

• • x=mL at first inflection point;
  • y=mL at second inflection point;
  • z=mL at third inflection point.

The foregoing method was used to measure acid number typically without use of the p-hydroxybenzoic acid internal standard for expedience. However, use of the internal standard is typically recommended. For acid number, carboxyl acid number and phenolic acid number values were measured using the aforesaid procedure for both the heavy oil product stream and the light oil product stream.

From the phenolic acid number, which is reported as mg KOH/g, a molar concentration of phenolics is calculated by dividing mg KOH/g by 1000 times the molar mass of KOH.

An elemental analysis for oxygen concentration was also performed for the three light oil products and one heavy oil product. The elemental analysis was performed via ASTM method D5291 and ASTM UOP649.

The measured properties of the seven oil products are as below in Table 2.

TABLE 2
		%		Carboxylic	Phenolic
		O,		acid number,	acid number,	Phenolics,
Exp.	Stream	wt %	API	mg KOH/g	mg KOH/g	moles/g

A	Light oil	4.2	33.0	0	96.2	0.0017
	product
B	Light oil	9.0	28.87	7.69	102.9	0.0018
	product
C	Light oil	13.0	22.7	26	101.8	0.0018
	product
D	Heavy oil	5.9	4.3	4.2	113.8	0.0020
	product
E	Light +	8.1	21.3	27.7	101.4	0.0018
	Heavy oil
	product
F	Light +	7.5	21.3	25.4	95.8	0.0017
	Heavy oil
	product
G	Light +	9.5	20.9	20.2	97.3	0.0017
	Heavy oil
	product

The three light oil products and the one heavy oil product of experiments A to D were fractionated into five fractions each. The three samples that were combinations of light and heavy oil products (experiments E though G) were fractionated into four fractions. The fractions and weight recoveries are shown in Table 3 below:

TABLE 3
					T5 distillation
					(° F.) (based on
		Initial	Final		simulated	Flashpoint	Viscosity at
Experiment	Cut	BP (° F.)	BP (° F.)	Wt %	distillation)	(° F.)	50° C. (cSt)

A	A1	25.9	185	18.9	85.8	<−7.6	Not measured
	A2	185	300.2	15.5	174.6	23	Not measured
	A3	300.2	401	16.9	302.0	100.4	Not measured
	A4	401	550.4	25.0	395.1	188.6	Not measured
	A5	550.4	814.1	23.7	561.9	314.6	Not measured
B	B1	32.2	185	21.9	82.0	<7.6	Not measured
	B2	185	300.2	17.2	168.6	50	Not measured
	B3	300.2	401	14.6	304.7	122	3.48
	B4	401	550.4	23.1	374.4	197.6	5.32
	B5	550.4	788.4	22.3	548.4	309.2	16.0
C	C1	61.9	185	21.7	83.8	<−5.8	Not measured
	C2	185	300.2	13.3	160.3	68	Not measured
	C3	300.2	401	14.6	284.5	122	2.46
	C4	401	550.4	26.9	376.3	212	5.10
	C5	550.4	977.5	22.3	545.4	312.8	13.4
D	D1	233.2	550.4	5.2	378.1	222.8	Not measured
	D2	550.4	699.8	21.2	517.8	287.6	5.08
	D3	699.8	800.6	23.4	676.9	402.8	13.3
	D4	500.6	899.6	16.7	718.9	455	1505
	D5	899.6	1380	33.5	735.4	442.4	Not measured
E	E1	68	300	25.7	100.4	3.2	Not measured
	E2	300	400	19.3	284.5	111	Not measured
	E3	400	550	27.5	376.9	205	5.84
	E4	550	1042	27.5	539.8	>302	50.7
F	F1	32	300	29.7	96.0	−2.2	Not measured
	F2	300	400	17.2	287.8	117	Not measured
	F3	400	550	30.4	376.7	208	4.89
	F4	550	1044	22.8	547.0	>302	42.8
G	G1	34	300	26.5	88.2	−5.8	Not measured
	G2	300	400	16.3	284.3	115	Not measured
	G3	400	550	32.1	371.3	210	Not measured
	G4	550	1015	25.0	530.1	>302	Not measured

The five cuts for each of the experiments A to D and the four cuts for experiment E to G were analyzed by simulated distillation for T5, flashpoint, organic oxygen concentration, acid number, phenolic acid number, ¹³C NMR, ¹H NMR and ATR-FTIR. The flash point as a function of T5 boiling temperature was plotted for the five cuts for each of the experiments A to D as shown in FIG. 3. Further results of the analyses are summarized as shown in Tables 4-7 below:

TABLE 4
	Relative		Oxygen	Carboxylic Acid	Phenolic Acid
	Density		Content	Number	Number (mg
Cut	(g/mL)	API	(wt %)	(mg KOH/g)	KOH/g)

A1	0.826	39.8	3.01	0.5	0.65
A2	0.787	48.2	2.58	3.0	8.78
A3	0.889	27.6	5.23	2.3	162.9
A4	0.953	17.1	6.48	0	218.0
A5	0.953	17.0	1.61	0	4.70
B1	0.7505	56.9	7.48	0	2.53
B2	0.8168	41.6	9.2	0	12.2
B3	0.9006	25.5	7.82	19.9	135
B4	0.9674	14.6	8.95	8.8	247.5
B5	0.9831	12.3	3.75	2.9	101.2
C1	0.7944	46.6	15	0	1.95
C2	0.8556	33.9	16.4	0	35.6
C3	0.9145	23.2	12.4	67.1	79.6
C4	0.9441	18.4	10.5	12.5	215.8
C5	1.0141	8.0	5.2	0	122.9
D1	0.974	13.8	9.1	11.9	215.4
D2	0.993	11.0	5.2	0	133.8
D3	1.0276	6.2	4.1	0	121.2
D4	1.0492	3.4	4.1	0	123.8
D5	1.0681	1.0	3.8	0	114.9
E1	0.812	42.8	8.6	30.7	5.3
E2	0.898	26.1	9.0	80.5	58.3
E3	0.965	15.2	7.9	19.5	199.8
E4	1.011	8.5	4.7	5.7	109.8
F1	0.759	54.8	8.3	35.0	<1
F2	0.895	26.6	8.9	86.9	50.5
F3	0.964	15.3	7.6	17.7	187
F4	1.024	6.7	3.6	7.4	98.3
G1	0.794	46.7	8.4	0	26.3
G2	0.899	26.0	10.3	51.1	55.9
G3	0.973	14.0	8.7	6.1	204.7
G4	1.060	2.0	4.2	4.3	98.0

TABLE 5
13C NMR of Fractionated Products

13C NMR

				R—OH, Aro-OH,
				R—O—R,
			Aro-H, C═C,	R—OCH3, Sugars
		R—COO—R,	Furans	Alcohols, ethers,	R—CH2—R,
	R > C═O,	R—COOH	Aromatics,	phenolic-	R > CH—R	R—CH3,
	R—CHO	Esters,	Olefins,	methoxys,	Long and	R—CH2—R
	Ketones,	carboxylic	heteroaromatic,	carbohydrates	branched	Short
	aldehydes	acids	furans	sugars	aliphatics	aliphatics
	δ 196 ppm-	δ 167 ppm-	δ 94 ppm-	δ 54 ppm-	δ 27 ppm-	δ 0 ppm-
Cuts	δ 225 ppm	δ 186 ppm	δ 167 ppm	δ 94 ppm	δ 54 ppm	δ 27 ppm

A1	0.56	0.12	10.57	2.04	21.17	65.54
A2	0.35	0.15	18.37	0.93	26.81	53.39
A3	0.00	0.12	40.09	0.17	22.37	37.25
A4	0.00	0.00	48.94	0.34	18.40	32.32
A5	0.00	0.00	37.97	0.46	25.42	36.15
B1	2.47	0.04	9.16	3.70	20.57	64.06
B2	1.73	0.32	6.40	7.15	27.20	57.20
B3	0.72	0.66	29.92	1.49	26.66	40.54
B4	0.31	0.32	47.99	0.41	17.45	33.52
B5	0.00	0.00	37.55	0.38	26.22	35.85
C1	6.02	0.35	12.7	6.37	17.49	57.07
C2	4.47	1.56	4.91	9.44	26.44	53.17
C3	3.04	2.41	19.94	2.75	28.35	43.51
C4	1.09	0.94	42.56	0.52	18.14	36.74
C5	0	0	36.24	0.13	23.97	39.66
D1	0.87	0.57	43.92	0.48	18.62	35.54
D2	0	0	38.4	0.62	26.47	34.51
D3	0	0	45.98	0.59	23.71	29.73
D4	0	0	50.17	0	20.57	29.26
D5	0	0	63.46	0	15.62	20.92
E1	5.12	2.27	15.41	5.77	29.42	42.01
E2	3.00	4.34	19.44	10.20	29.29	33.73
E3	1.51	1.97	41.08	4.62	22.03	28.80
E4	0	0.50	40.80	5.72	26.98	25.99
F1	4.27	1.85	14.59	6.18	29.84	43.27
F2	2.20	3.34	18.46	9.33	30.51	36.16
F3	1.22	1.34	42.04	5.11	22.16	28.14
F4	0	0.15	47.48	5.75	24.07	22.55
G1	5.83	1.61	11.25	3.49	26.96	50.86
G2	3.97	1.79	20.52	2.75	28.98	41.99
G3	1.52	0	45.92	1.27	18.72	32.56
G4	0	0	59.53	0.33	20.02	20.12

TABLE 6
1H NMR of Fractionated Products

1HNMR

						Aro-CH3,
				C═C,		C═C—CH2
			Aro-H,	R—OCH3,	R—OH,	aliphatics
			Furans	Sugars	R—O—CH2—R	alpha to	R—CH3,
		Aro-H	(hetero)	olefins,	alcohols,	heteroatom	R—CH2—R,
	R—CHO	(hetero)	aromatics,	methoxy,	methylene-	or	R > CH—R
Cuts	aldehydes	aromatics	furans	carbohydrates	dibenzene	unsaturation	alkanes

A1	0	0.25	2.64	2.51	1.01	31.81	61.78
A2	0	0.18	12.38	0.14	0.57	33.25	53.48
A3	0	1.60	15.92	0.04	0.79	37.54	44.11
A4	0	3.52	7.28	0	2.01	30.57	56.63
A5	0.02	0.13	0.27	3.25	2.39	35.06	58.89
B1	20.57	64.06	0.02	0.13	0.27	3.25	2.39
B2	27.20	57.20	0.01	0.02	0.59	1.53	5.03
B3	26.66	40.54	0.00	0.25	8.23	0.09	2.13
B4	17.45	33.52	0.00	0.77	15.76	0.03	1.11
B5	26.22	35.85	0.00	3.69	6.43	0.08	2.89
C1	0.18	0.26	0.54	4.83	4.61	47.29	42.3
C2	0.03	0.02	0.38	1.15	6.88	44.2	47.32
C3	0.01	0.1	6.14	0.08	2.85	41.2	49.62
C4	0	0.49	12.62	0	1.74	43.62	41.53
C5	0	3.49	6.33	0.02	3.2	42.28	44.67
D1	0	0.97	13.21	0.3	2.05	42.46	41.01
D2	0	2.62	6.79	0.18	2.76	41.06	46.59
D3	0	5.7	6.81	0.06	4.58	40.31	42.53
D4	0	7	7.12	0.09	4.53	40.85	40.45
D5	0	8.78	5.74	0	6.55	40.56	38.37
E1	0.01	0.42	0.74	3.18	4.90	42.89	47.86
E2	0	0.41	4.38	5.07	1.20	39.26	49.68
E3	0	1.17	10.96	4.58	1.56	40.93	40.81
E4	0.01	4.47	5.56	0.80	5.46	40.26	43.44
F1	0	0.33	1.00	3.87	4.49	43.40	46.90
F2	0	0.59	7.37	1.08	1.19	40.11	49.67
F3	0	1.82	10.46	4.35	1.76	41.75	39.85
F4	0.13	7.50	5.41	1.27	6.01	40.47	39.20
G1	0	0.26	0.77	2.17	3.42	41.88	51.51
G2	0	0.41	6.66	1.94	1.01	39.92	50.05
G3	0	2.18	11.87	3.82	2.53	43.69	35.91
G4	0.20	12.65	5.01	0.30	6.75	40.52	34.57

TABLE 7
ATR-FTIR of Each Fractionated Product

			C═O/	C—O/	Aromatic	CH3 + CH2 +	OH/
		Total O/	Total	Total	C═C/Total	CH/Total	Total
Cut	O wt %	Total C	Carbon	Carbon	Carbon	C═C	Carbon

A1	3.01	0.04	0.02	0.03	0	163	0.13
A2	2.58	0.05	0.02	0.03	0.01	43.3	0.04
A3	5.23	0.24	0.02	0.21	0.1	8.25	0.49
A4	6.48	0.26	0.02	0.24	0.14	5.41	0.7
A5	1.61	0.05	0.01	0.04	0.04	19.8	0.07
B1	7.48	0.17	0.08	0.09	0.01	35.8	0.3
B2	9.2	0.21	0.11	0.1	0	47.9	0.62
B3	7.82	0.31	0.1	0.21	0.09	8.24	0.45
B4	8.95	0.37	0.06	0.31	0.16	4.76	0.92
B5	3.75	0.1	0.02	0.08	0.06	14.1	0.26
C1	15	0.48	0.27	0.21	0.01	12.3	0.93
C2	16.4	0.45	0.29	0.16	0.01	16.5	1.23
C3	12.4	0.56	0.32	0.24	0.05	7.77	0.48
C4	10.5	0.44	0.15	0.29	0.11	4.36	0.87
C5	5.2	0.22	0.06	0.16	0.07	10.8	0.36
D1	9.05	0.36	0.1	0.26	0.12	5.47	0.78
D2	5.19	0.16	0.04	0.12	0.07	11.5	0.36
D3	4.07	0.15	0.02	0.12	0.08	11.1	0.32
D4	4.13	0.15	0.02	0.13	0.08	10.2	0.35
D5	3.78	0.16	0.03	0.13	0.09	9.01	0.36
E1	0.42	0.08	0.21	0.29	0.13	0.02	29.9
E2	0.46	0.11	0.2	0.3	0.16	0.03	10.5
E3	0.41	0.02	0.13	0.15	0.26	0.11	6.76
E4	0.15	0.01	0.03	0.04	0.12	0.06	15
F1	0.41	0.09	0.2	0.29	0.12	0.02	32.3
F2	0.48	0.11	0.22	0.33	0.16	0.03	13.2
F3	0.39	0.02	0.13	0.15	0.24	0.1	7.04
F4	0.16	0.01	0.04	0.04	0.12	0.07	12.1
G1	0.42	0.08	0.23	0.31	0.11	0.01	84.4
G2	0.5	0.11	0.23	0.35	0.15	0.04	19
G3	0.38	0.01	0.13	0.14	0.24	0.13	4.1
G4	0.25	0.01	0.08	0.09	0.16	0.12	7.32

A marine fuel blend stock composition was simulated using a selection of the five cuts of the experiments A to D above. To composite a simulated marine fuel composition, results from the heavy oil product of Experiment D were combined with a portion of one of the light oil product streams of Experiments A, B and C based on the weight percent recovered in the fractionation. Marine fuel compositions with initial boiling point of 300° F. or 400° F. were composited (the analyses of cuts 3, 4, 5 from the corresponding light oil+sample D were composited to generate the 300° F.+marine fuel oil blend stock and the analyses of cuts 4, 5 from the corresponding light oil+sample D were composited to generate the 400° F.+marine fuel oil blend stock). The same data was compiled for Experiment G, which was the total product (both light oil and heavy oil) to generate blends at each IBP. Properties of the simulated composited marine fuel oil blend stocks are provided in Table 8 below:

TABLE 8
Composited Marine Fuels

										ROH
		Wt %		Carboxylic	Phenolic					and
	Relative	O in		Acid	Acid	Mol	C═O/	C═O/	C═O	ROR
	density	light	Wt %	Number (mg	Number (mg	phenolics/	C—O	total O	by 13C	by 13C
Cuts	(g/mL)	oil	O	KOH/g)	KOH/g)	g	(FTIR)	(FTIR)	NMR	NMR

300° F. IBP Marine Fuel Properties

D + (A3 +	0.982	4.3	4.44	0.60	126.9	0.0023	0.19	0.15	0.051	0.32
A4 + A5)
D + (B3 +	0.995	9	5.7	5.10	147.1	0.0026	0.26	0.20	0.33	0.48
B4 + B5)
D + (C3 +	0.996	13	6.9	11.25	140.4	0.0025	0.46	0.28	1.15	0.61
C4 + C5)
G2 + G3 +	0.986	N/A	7.5	15.48	135.3	0.0024	0.80	4.2	1.94	1.28
G4

400° F. IBP Marine Fuel Properties

D + (A4 +	0.997	4.3	4.32	0.33	121.1	0.0022	0.20	0.16	0.040	0.34
A5)
D + (B4 +	1.008	9	5.3	2.98	148.8	0.0027	0.23	0.18	0.18	0.34
B5)
D + (C4 +	1.007	13	6.2	3.52	148.8	0.0027	0.34	0.24	0.56	0.32
C5)
G3 + G4	1.011	N/A	6.7	5.31	158.0	0.0028	0.92	10.8	0.85	0.86

A plot of T5 necessary for 140° F. Flash Point as a function of wt % oxygen in the composited Marine Fuel is shown in FIG. 4. For the marine fuel oil of the disclosed composition, increased oxygen concentration enables the T5 to be lower while still providing at least 140° F. flash point as opposed to fully hydrotreated material. The presence of oxygenates increases the flashpoint, so a lower T5 cut point can be used. However, the oxygenate concentration cannot be too high, otherwise the acid number specification may not be met. As shown in the plot of FIG. 4, the dotted triangle is area of significant advantage.

T5 (° F.) was greater than (−21.6*(wt % oxygen in marine fuel)+431.96)° F. when the percentage of oxygen in the marine fuel oil was at least 4.44%. When the percentage of oxygen is less than 4.44% in the marine fuel oil, the T5 should be at least 337° F. to meet the flash point.

SPECIFIC EMBODIMENTS

While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.

A first embodiment of the present disclosure is a marine fuel oil composition, the marine fuel oil composition comprising an acid number of less than about 2.5 mg KOH/g, a flash point temperature greater than about 140° F., and an oxygen concentration of at least about 2 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises a T5 temperature of at least (−21.6×(wt % oxygen in the marine fuel oil composition)+432)° F. when the marine fuel oil composition comprises an oxygen concentration of greater than about 4.44 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the T5 temperature is at least about 337° F. when the marine fuel oil composition comprises an oxygen concentration of no more than about 4.44 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises a total oxygen concentration of less than about 8 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises a C═O/C—O oxygenates mole ratio of less than about 0.9. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises a C═O oxygenates to total oxygen mole ratio of less than about 0.4. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises at least about 0.0010 moles of phenolic compounds per gram. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein a carbon mole % of one or more of group selected from aldehyde, ester, carboxylic acid, and ketone in said marine fuel oil composition is less than about 1.2 mole % of the total carbon. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein a carbon mole % of one or more of group selected from hydroxyl, ether, sugar, and alcohol in said marine fuel oil composition is greater than about 0.2 mole % of the total carbon An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the marine fuel oil composition comprises a minimum T5 temperature of at least about 270° F.

A second embodiment of the present disclosure is a marine fuel oil composition, the marine fuel oil composition comprising an acid number of less than about 2.5 mg KOH/g, a flash point temperature greater than about 140° F., and a T5 temperature of at least (−21.6×(wt % oxygen in the marine fuel oil composition)+432)° F. when the marine fuel oil composition comprises an oxygen concentration of greater than about 4.44 wt % and the T5 temperature is at least about 337° F. when the marine fuel oil composition comprises an oxygen concentration of no more than about 4.44 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the marine fuel oil composition comprises a C═O/C—O oxygenates mole ratio of less than about 0.9. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the marine fuel oil composition comprises a C═O oxygenates to total oxygen mole ratio of less than about 0.4. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the marine fuel oil composition comprises a hydrotreated bio-oil. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the marine fuel oil composition comprises an oxygen concentration of at least about 2 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the marine fuel oil composition comprises a minimum T5 temperature of at least about 270° F.

A third embodiment of the present disclosure is a process for producing marine fuel oil, comprising reacting a bio-oil stream with hydrogen in the presence of a catalyst in a reactor to produce an upgraded bio-oil stream; and separating a marine fuel oil stream from the upgraded bio-oil stream, the marine fuel oil comprising an acid number of less than about 2.5 mg KOH/g and a flash point temperature greater than about 140° F. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the marine fuel oil comprises an oxygen concentration of no less than about 2 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the marine fuel oil comprises a T5 temperature of at least (−21.6×(wt % oxygen in the marine fuel oil)+432)° F. when the marine fuel oil comprises an oxygen concentration of greater than about 4.44 wt %. An embodiment of the present disclosure is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the marine fuel oil comprises a T5 temperature of at least about 337° F. when the marine fuel oil composition comprises an oxygen concentration of no more than about 4.44 wt %.

A fourth embodiment of the present disclosure is a marine fuel oil composition having a density of no more than about 1.01 grams per cm³ at 15° C., a flashpoint of at least about 60° C. and a carbon mole % of a hydroxyl, an ether, a sugar, or an alcohol in the marine fuel oil composition is greater than about 0.2 mole % of a total carbon, the marine fuel oil composition is produced by blending a bio-derived marine fuel oil blend stock comprising an oxygen content of at least about 2 wt % and at least one phenolic compound of more than about 0.0010 moles/g with a petroleum-derived marine fuel oil blend stock having a total acid number less than about 2.5 mg KOH/g.

Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present disclosure to its fullest extent and easily ascertain the essential characteristics of this disclosure, without departing from the spirit and scope thereof, to make various changes and modifications of the disclosure and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.